WO2006054101A2 - Mass spectrometer - Google Patents
Mass spectrometer Download PDFInfo
- Publication number
- WO2006054101A2 WO2006054101A2 PCT/GB2005/004457 GB2005004457W WO2006054101A2 WO 2006054101 A2 WO2006054101 A2 WO 2006054101A2 GB 2005004457 W GB2005004457 W GB 2005004457W WO 2006054101 A2 WO2006054101 A2 WO 2006054101A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- ion
- ion guide
- filter device
- ions
- 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.)
- Ceased
Links
Classifications
-
- 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
- H01J49/4205—Device types
- H01J49/421—Mass filters, i.e. deviating unwanted ions without trapping
- H01J49/4215—Quadrupole mass filters
-
- 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
- H01J49/426—Methods for controlling ions
- H01J49/427—Ejection and selection methods
- H01J49/428—Applying a notched broadband signal
Definitions
- the centre and/or width of the one or more mass to charge ratio transmission windows may vary in a substantially progressive, non-progressive, linear, non-linear, quadratic, smooth, stepped, regular, random or quasi-random manner.
- the ion guide or mass filter device preferably has an ion entrance region and an ion exit region and wherein in a mode of operation y% of the ions received by the preferred ion guide or mass filter device at the ion entrance region are preferably attenuated and/or radially ejected from the preferred ion guide or mass filter device before reaching the ion exit region, wherein y is selected from the group consisting of: (i) ⁇ 1; (ii) 1-5; (iii) 5-10; (iv) 10-15; (v) 15-20; (vi) 20-25; (vii) 25-30; (viii) 30-35; (ix) 35-40; (x) 40-45; (xi) 45-50; (xii) 50-55; (xiii) 55-60; (xiv) 60-65; (xv) 65-70; (xvi) 70-75; (xvii) 75-80; (xviii) 80-85; (xix) 85-90; (xx) 90
- the multipole rod set preferably comprises a quadrupole rod set, a hexapole rod set, an octapole rod set or a rod set comprising more than eight rods.
- the ion tunnel or ion funnel preferably comprises a plurality of electrodes or at least 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 electrodes having apertures through which ions are transmitted in use and wherein at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of the electrodes have apertures which are of substantially the same size or area or which have apertures which become progressively larger and/or smaller in size or in area.
- planar, plate or mesh electrodes are preferably arranged generally in the plane in which ions travel in use.
- AC or RF voltage means are preferably provided for supplying the plurality of planar, plate or mesh electrodes with an AC or RF voltage and wherein adjacent planar, plate or mesh electrodes are preferably supplied with opposite phases of the AC or RF voltage.
- the stack or array of planar, plate or mesh electrodes preferably comprises a plurality or at least 2, 3, 4, 5, 6, I 1 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 planar, plate or mesh electrodes arranged generally in the plane in which ions travel in use. At least some or at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of the planar, plate or mesh electrodes are preferably supplied with an AC or RF voltage and wherein adjacent planar, plate or mesh electrodes are supplied with opposite phases of the AC or RF voltage.
- the ion mobility spectrometer or separator preferably comprises a plurality of axial segments or at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 axial segments.
- the mass spectrometer preferably further comprises an ion trap or ion trapping region arranged upstream and/or downstream of the preferred ion guide or mass filter device.
- Ions are preferably arranged in a mode of operation to be mass selectively and/or resonantly ejected from the ion trap or ion trapping region.
- ions may in a mode of operation be arranged to be non-mass selectively and/or resonantly ejected from the ion trap or ion trapping region.
- Fig. 4A illustrates an embodiment wherein a broadband frequency signal having a relatively wide range of frequencies is applied to a quadrupole rod set ion guide and Fig. 4B illustrates an alternative embodiment wherein a broadband frequency signal having a narrower range of frequencies is applied to a quadrupole rod set mass filter operating as a low resolution mass filter;
- All four rods 2a,2b are maintained at substantially the same DC voltage or potential.
- a two phase RF voltage supply 3 is connected to the rods 2a, 2b such that adjacent rods have opposite phases of an RF voltage applied to them whilst diametrically opposed rods 2a;2b have the same phase RF voltage applied to them.
- the RF voltage applied to the rods 2a, 2b creates a radial pseudo-potential well which acts to confine ions radially within the ion guide 1. Ions are not confined axially within the ion guide 1.
- a second preferred ion guide or mass filter device 6b may be provided upstream of an ion accumulation or ion storage device 20 (such as an ion trap) and preferably downstream of an ion source 11.
- the second preferred ion guide or mass filter device 6b is preferably arranged so as to reduce the total ion current entering the ion accumulation or ion storage device 20 by only selectively transmitting species of parent or precursor ions which are known or considered to be of analytical interest. This can also help to reduce space charge effects and capacity effects.
- An ion source 11 is preferably arranged to emit a beam of ions 18 which is preferably received by the second preferred ion guide or mass filter device 6b.
- the mass to charge ratio profile or transmission window of the fragment, daughter, adduct or product ions and/or unfragmented parent or precursor ions which are preferably arranged to be onwardly transmitted by the first preferred ion guide or mass filter device 6a may or may not be arranged so as to be generally or substantially synchronised with the temporal arrival of specific parent or precursor ions or other ions which preferably emerge from the ion temporal separation region or device 22 and arrive at the entrance to the collision, fragmentation or reaction device 14.
- the mass to charge ratio profile or transmission window or windows of the fragment, daughter, adduct or product ions and/or unfragmented parent or precursor ions which are transmitted by the first preferred ion guide or mass filter device 6a may therefore preferably vary or be scanned with time.
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007542101A JP2008521189A (ja) | 2004-11-18 | 2005-11-18 | 質量分析計 |
| CA002586519A CA2586519A1 (en) | 2004-11-18 | 2005-11-18 | Mass spectrometer |
| EP05804395A EP1812950A2 (en) | 2004-11-18 | 2005-11-18 | Mass spectrometer |
| US11/719,665 US8952320B2 (en) | 2004-11-18 | 2005-11-18 | Mass spectrometer |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0425426.4 | 2004-11-18 | ||
| GBGB0425426.4A GB0425426D0 (en) | 2004-11-18 | 2004-11-18 | Mass spectrometer |
| US63195604P | 2004-11-30 | 2004-11-30 | |
| US60/631,956 | 2004-11-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2006054101A2 true WO2006054101A2 (en) | 2006-05-26 |
| WO2006054101A3 WO2006054101A3 (en) | 2007-01-18 |
Family
ID=33548493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2005/004457 Ceased WO2006054101A2 (en) | 2004-11-18 | 2005-11-18 | Mass spectrometer |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US8952320B2 (enExample) |
| EP (1) | EP1812950A2 (enExample) |
| JP (1) | JP2008521189A (enExample) |
| CA (1) | CA2586519A1 (enExample) |
| GB (2) | GB0425426D0 (enExample) |
| WO (1) | WO2006054101A2 (enExample) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100108879A1 (en) * | 2006-11-15 | 2010-05-06 | Micromass Uk Limited | Mass Spectrometer |
| US7964843B2 (en) | 2008-07-18 | 2011-06-21 | The George Washington University | Three-dimensional molecular imaging by infrared laser ablation electrospray ionization mass spectrometry |
| US8067730B2 (en) | 2007-07-20 | 2011-11-29 | The George Washington University | Laser ablation electrospray ionization (LAESI) for atmospheric pressure, In vivo, and imaging mass spectrometry |
| EP2126961B1 (en) * | 2007-02-24 | 2014-06-18 | Sociedad Europea De Analisis Diferencial De Movilidad S.L. | Method to accurately discriminate gas phase ions with several filtering devices in tandem |
| US8829426B2 (en) | 2011-07-14 | 2014-09-09 | The George Washington University | Plume collimation for laser ablation electrospray ionization mass spectrometry |
| US8901487B2 (en) | 2007-07-20 | 2014-12-02 | George Washington University | Subcellular analysis by laser ablation electrospray ionization mass spectrometry |
| US9881781B2 (en) | 2014-02-04 | 2018-01-30 | Micromass Uk Limited | Optimized multiple reaction monitoring or single ion recording method |
Families Citing this family (42)
| 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 |
| GB0514964D0 (en) | 2005-07-21 | 2005-08-24 | Ms Horizons Ltd | Mass spectrometer devices & methods of performing mass spectrometry |
| US7960694B2 (en) * | 2004-01-09 | 2011-06-14 | Micromass Uk Limited | Mass spectrometer |
| ATE512458T1 (de) | 2004-12-07 | 2011-06-15 | Micromass Ltd | Massenspektrometer |
| GB2432712B (en) * | 2005-11-23 | 2007-12-27 | Micromass Ltd | Mass spectrometer |
| GB0701476D0 (en) * | 2007-01-25 | 2007-03-07 | Micromass Ltd | Mass spectrometer |
| DE102007009272B3 (de) * | 2007-02-26 | 2008-05-15 | Bruker Daltonik Gmbh | Auswertung von Spektren in Schwingungs-Massenspektrometern |
| DE102007017055B4 (de) * | 2007-04-11 | 2011-06-22 | Bruker Daltonik GmbH, 28359 | Messung der Mobilität massenselektierter Ionen |
| US7718957B2 (en) * | 2008-06-03 | 2010-05-18 | Battelle Memorial Institute | Dynamic multiplexed analysis method using ion mobility spectrometer |
| US20100237236A1 (en) * | 2009-03-20 | 2010-09-23 | Applera Corporation | Method Of Processing Multiple Precursor Ions In A Tandem Mass Spectrometer |
| GB201118579D0 (en) * | 2011-10-27 | 2011-12-07 | Micromass Ltd | Control of ion populations |
| EP2807669A2 (en) | 2012-01-24 | 2014-12-03 | Thermo Finnigan LLC | Multinotch isolation for ms3 mass analysis |
| GB201205009D0 (en) * | 2012-03-22 | 2012-05-09 | Micromass Ltd | Multi-dimensional survey scans for improved data dependent acquisitions (DDA) |
| WO2013176901A1 (en) | 2012-05-23 | 2013-11-28 | President And Fellows Of Harvard College | Mass spectrometry for multiplexed quantitation using multiple frequency notches |
| CN103515183B (zh) * | 2012-06-20 | 2017-06-23 | 株式会社岛津制作所 | 离子导引装置和离子导引方法 |
| JP6491097B2 (ja) | 2012-10-22 | 2019-03-27 | プレジデント アンド フェローズ オブ ハーバード カレッジ | 質量分析法を使用する正確で干渉のない多重定量プロテオミクス |
| JP2016507151A (ja) * | 2013-02-18 | 2016-03-07 | マイクロマス ユーケー リミテッド | 自動排出イオントラップを用いた質量分析器における、気相反応の改善された効率および精密制御 |
| JP2016514343A (ja) * | 2013-02-18 | 2016-05-19 | マイクロマス ユーケー リミテッド | 自動放出イオントラップを用いた質量分析計における気相反応物の改善された反応監視を可能にする装置 |
| US20160020083A1 (en) * | 2013-03-14 | 2016-01-21 | President And Fellows Of Harvard College | Adjusting precursor ion populations in mass spectrometry using dynamic isolation waveforms |
| GB201315145D0 (en) | 2013-08-23 | 2013-10-09 | Smiths Detection Watford Ltd | Ion Modification |
| WO2015036848A1 (en) * | 2013-09-13 | 2015-03-19 | Dh Technologies Development Pte. Ltd. | Rf-only detection scheme and simultaneous detection of multiple ions |
| EP3157042B1 (en) * | 2013-10-16 | 2021-01-13 | DH Technologies Development Pte. Ltd. | Systems and methods for identifying precursor ions from product ions using arbitrary transmission windowing |
| US10163617B2 (en) | 2013-11-07 | 2018-12-25 | Dh Technologies Development Pte. Ltd. | Multiplexing of ions for improved sensitivity |
| WO2015071648A2 (en) | 2013-11-12 | 2015-05-21 | Micromass Uk Limited | Ion trap mass spectrometers |
| GB201319942D0 (en) * | 2013-11-12 | 2013-12-25 | Micromass Ltd | Ion Trap Mass Spectrometers |
| WO2015162415A1 (en) * | 2014-04-23 | 2015-10-29 | Micromass Uk Limited | Identification and removal of chemical noise for improved ms and ms/ms analysis |
| CN106663590B (zh) * | 2014-06-10 | 2019-03-26 | 英国质谱公司 | 离子引导器 |
| US9875885B2 (en) * | 2015-05-11 | 2018-01-23 | Thermo Finnigan Llc | Systems and methods for ion isolation |
| WO2017055978A1 (en) * | 2015-10-01 | 2017-04-06 | Dh Technologies Development Pte. Ltd. | Mass-selective axial ejection linear ion trap |
| US9741552B2 (en) * | 2015-12-22 | 2017-08-22 | Bruker Daltonics, Inc. | Triple quadrupole mass spectrometry coupled to trapped ion mobility separation |
| US11085927B2 (en) | 2016-06-03 | 2021-08-10 | President And Fellows Of Harvard College | Techniques for high throughput targeted proteomic analysis and related systems and methods |
| WO2018020363A1 (en) * | 2016-07-25 | 2018-02-01 | Dh Technologies Development Pte. Ltd. | Systems and methods for identifying precursor and product ion pairs in scanning swath data |
| US11810771B2 (en) | 2017-02-01 | 2023-11-07 | Dh Technologies Development Pte. Ltd. | Fourier transform mass spectrometer based on use of a fringing field to convert radial oscillations of excited ions to axial oscillations |
| GB2563565B (en) | 2017-04-13 | 2022-05-11 | Micromass Ltd | Mass spectrometry with increased duty cycle |
| EP3753043B1 (en) | 2018-02-16 | 2022-03-30 | Micromass UK Limited | Quadrupole devices |
| US12040173B2 (en) | 2019-03-11 | 2024-07-16 | Micromass Uk Limited | Quadrupole devices |
| WO2020240506A1 (en) | 2019-05-31 | 2020-12-03 | Dh Technologies Development Pte. Ltd. | Method for real time encoding of scanning swath data and probabilistic framework for precursor inference |
| CN111309060A (zh) * | 2020-03-27 | 2020-06-19 | 北京环拓科技有限公司 | 一种大气负氧离子观测仪的控制方法 |
| EP3916755A1 (en) | 2020-05-26 | 2021-12-01 | Thermo Finnigan LLC | Methods and apparatus for high speed mass spectrometry |
| GB202011470D0 (en) | 2020-07-24 | 2020-09-09 | Micromass Ltd | ION mobility separation |
| GB202306186D0 (en) * | 2023-04-27 | 2023-06-14 | Micromass Ltd | Mass spectrometer having parallel precursor ion isolation |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3334225A (en) * | 1964-04-24 | 1967-08-01 | California Inst Res Found | Quadrupole mass filter with means to generate a noise spectrum exclusive of the resonant frequency of the desired ions to deflect stable ions |
| US5134286A (en) * | 1991-02-28 | 1992-07-28 | Teledyne Cme | Mass spectrometry method using notch filter |
| US5187365A (en) * | 1991-02-28 | 1993-02-16 | Teledyne Mec | Mass spectrometry method using time-varying filtered noise |
| US5449905A (en) * | 1992-05-14 | 1995-09-12 | Teledyne Et | Method for generating filtered noise signal and broadband signal having reduced dynamic range for use in mass spectrometry |
| US5672870A (en) * | 1995-12-18 | 1997-09-30 | Hewlett Packard Company | Mass selective notch filter with quadrupole excision fields |
| US5598001A (en) * | 1996-01-30 | 1997-01-28 | Hewlett-Packard Company | Mass selective multinotch filter with orthogonal excision fields |
| US6177668B1 (en) | 1996-06-06 | 2001-01-23 | Mds Inc. | Axial ejection in a multipole mass spectrometer |
| US5793038A (en) * | 1996-12-10 | 1998-08-11 | Varian Associates, Inc. | Method of operating an ion trap mass spectrometer |
| WO1998052209A1 (en) * | 1997-05-12 | 1998-11-19 | Mds Inc. | Rf-only mass spectrometer with auxiliary excitation |
| US6093929A (en) | 1997-05-16 | 2000-07-25 | Mds Inc. | High pressure MS/MS system |
| GB9717926D0 (en) | 1997-08-22 | 1997-10-29 | Micromass Ltd | Methods and apparatus for tandem mass spectrometry |
| DE69825789T2 (de) | 1997-12-04 | 2005-09-01 | University Of Manitoba, Winnipeg | Vorrichtung und verfahren zur stoss-induzierten dissoziation von ionen in einem quadrupol-ionenleiter |
| GB2381653A (en) * | 2001-11-05 | 2003-05-07 | Shimadzu Res Lab Europe Ltd | A quadrupole ion trap device and methods of operating a quadrupole ion trap device |
| WO2003056604A1 (en) * | 2001-12-21 | 2003-07-10 | Mds Inc., Doing Business As Mds Sciex | Use of notched broadband waveforms in a linear ion trap |
| US6630662B1 (en) | 2002-04-24 | 2003-10-07 | Mds Inc. | Setup for mobility separation of ions implementing an ion guide with an axial field and counterflow of gas |
| US7351957B2 (en) | 2002-04-29 | 2008-04-01 | Mds Inc. | Broad ion fragmentation coverage in mass spectrometry by varying the collision energy |
| JP3791455B2 (ja) | 2002-05-20 | 2006-06-28 | 株式会社島津製作所 | イオントラップ型質量分析装置 |
| US6900431B2 (en) * | 2003-03-21 | 2005-05-31 | Predicant Biosciences, Inc. | Multiplexed orthogonal time-of-flight mass spectrometer |
| US7388197B2 (en) * | 2004-07-27 | 2008-06-17 | Ionwerks, Inc. | Multiplex data acquisition modes for ion mobility-mass spectrometry |
| US7456396B2 (en) * | 2004-08-19 | 2008-11-25 | Thermo Finnigan Llc | Isolating ions in quadrupole ion traps for mass spectrometry |
-
2004
- 2004-11-18 GB GBGB0425426.4A patent/GB0425426D0/en not_active Ceased
-
2005
- 2005-11-18 WO PCT/GB2005/004457 patent/WO2006054101A2/en not_active Ceased
- 2005-11-18 CA CA002586519A patent/CA2586519A1/en not_active Abandoned
- 2005-11-18 EP EP05804395A patent/EP1812950A2/en not_active Withdrawn
- 2005-11-18 JP JP2007542101A patent/JP2008521189A/ja active Pending
- 2005-11-18 US US11/719,665 patent/US8952320B2/en active Active
- 2005-11-18 GB GB0523569A patent/GB2421842B/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10319577B2 (en) | 2006-11-15 | 2019-06-11 | Micromass Uk Limited | Combined mass-to-charge ratio and charge state selection in tandem mass spectrometry |
| US9685313B2 (en) * | 2006-11-15 | 2017-06-20 | Micromass Uk Limited | Combined mass-to-charge ratio and charge state selection in tandem mass spectrometry |
| US20100108879A1 (en) * | 2006-11-15 | 2010-05-06 | Micromass Uk Limited | Mass Spectrometer |
| EP2126961B1 (en) * | 2007-02-24 | 2014-06-18 | Sociedad Europea De Analisis Diferencial De Movilidad S.L. | Method to accurately discriminate gas phase ions with several filtering devices in tandem |
| US8299429B2 (en) | 2007-07-20 | 2012-10-30 | The George Washington University | Three-dimensional molecular imaging by infrared laser ablation electrospray ionization mass spectrometry |
| US8487244B2 (en) | 2007-07-20 | 2013-07-16 | The George Washington University | Laser ablation electrospray ionization (LAESI) for atmospheric pressure, in vivo, and imaging mass spectrometry |
| US8487246B2 (en) | 2007-07-20 | 2013-07-16 | The George Washington University | Three-dimensional molecular imaging by infrared laser ablation electrospray ionization mass spectrometry |
| US8809774B2 (en) | 2007-07-20 | 2014-08-19 | The George Washington University | Laser ablation electrospray ionization (LAESI) for atmospheric pressure, in vivo, and imaging mass spectrometry |
| US8901487B2 (en) | 2007-07-20 | 2014-12-02 | George Washington University | Subcellular analysis by laser ablation electrospray ionization mass spectrometry |
| US8067730B2 (en) | 2007-07-20 | 2011-11-29 | The George Washington University | Laser ablation electrospray ionization (LAESI) for atmospheric pressure, In vivo, and imaging mass spectrometry |
| US7964843B2 (en) | 2008-07-18 | 2011-06-21 | The George Washington University | Three-dimensional molecular imaging by infrared laser ablation electrospray ionization mass spectrometry |
| US8829426B2 (en) | 2011-07-14 | 2014-09-09 | The George Washington University | Plume collimation for laser ablation electrospray ionization mass spectrometry |
| US9362101B2 (en) | 2011-07-14 | 2016-06-07 | The George Washington University | Plume collimation for laser ablation electrospray ionization mass spectrometry |
| US9881781B2 (en) | 2014-02-04 | 2018-01-30 | Micromass Uk Limited | Optimized multiple reaction monitoring or single ion recording method |
| DE112015000644B4 (de) | 2014-02-04 | 2022-09-08 | Micromass Uk Limited | Verfahren zur Massenspektrometrie und Massenspektrometer |
Also Published As
| Publication number | Publication date |
|---|---|
| US20090194688A1 (en) | 2009-08-06 |
| GB0523569D0 (en) | 2005-12-28 |
| EP1812950A2 (en) | 2007-08-01 |
| JP2008521189A (ja) | 2008-06-19 |
| US8952320B2 (en) | 2015-02-10 |
| GB2421842B (en) | 2007-08-01 |
| WO2006054101A3 (en) | 2007-01-18 |
| GB2421842A (en) | 2006-07-05 |
| CA2586519A1 (en) | 2006-05-26 |
| GB0425426D0 (en) | 2004-12-22 |
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