EP1215711A2 - Spectromètre de masse et méthodes associées - Google Patents

Spectromètre de masse et méthodes associées Download PDF

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Publication number
EP1215711A2
EP1215711A2 EP01310018A EP01310018A EP1215711A2 EP 1215711 A2 EP1215711 A2 EP 1215711A2 EP 01310018 A EP01310018 A EP 01310018A EP 01310018 A EP01310018 A EP 01310018A EP 1215711 A2 EP1215711 A2 EP 1215711A2
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EP
European Patent Office
Prior art keywords
ions
mass
mode
lens
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.)
Granted
Application number
EP01310018A
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German (de)
English (en)
Other versions
EP1215711B1 (fr
EP1215711A3 (fr
Inventor
Martin Green
Michael Jackson
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Micromass UK Ltd
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Micromass UK Ltd
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Publication date
Priority claimed from GBGB0029040.3A external-priority patent/GB0029040D0/en
Application filed by Micromass UK Ltd filed Critical Micromass UK Ltd
Priority to EP06021007.7A priority Critical patent/EP1768164B1/fr
Priority to EP04010779A priority patent/EP1460674B1/fr
Publication of EP1215711A2 publication Critical patent/EP1215711A2/fr
Publication of EP1215711A3 publication Critical patent/EP1215711A3/fr
Application granted granted Critical
Publication of EP1215711B1 publication Critical patent/EP1215711B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • 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

Definitions

  • the present invention relates to mass spectrometers and methods of mass spectrometry.
  • Time to digital converters are used, for example, in time of flight mass analysers wherein packets of ions are ejected into a field-free drift region with essentially the same kinetic energy. In the drift region, ions with different mass-to-charge ratios in each packet of ions travel with different velocities and therefore arrive at an ion detector disposed at the exit of the drift region at different times. Measurement of the ion transit-time therefore determines the mass-to-charge ratio of that particular ion.
  • TDC time to digital converter
  • ion detectors in time of flight mass spectrometers are single ion counting detector in which an ion impacting a detecting surface produces a pulse of electrons by means of, for example, an electron multiplier.
  • the pulse of electrons is typically amplified by an amplifier and a resultant electrical signal is produced.
  • the electrical signal produced by the amplifier is used to determine the transit time of the ion which struck the detector by means of a time to digital converter which is started once a packet of ions is first accelerated into the drift region.
  • the ion detector and associated circuitry is therefore able to detect a single ion impacting onto the detector.
  • ion detectors exhibit a certain dead-time following an ion impact during which time the detector cannot respond to another ion impact.
  • a typical detector dead time may be of the order of 1-5 ns. If during acquisition of a mass spectrum ions arrive during the detector dead-time then they will consequently fail to be detected, and this will have a distorting effect on the resultant mass spectra.
  • dead time correction software It is known to use dead time correction software to correct for distortions in mass spectra.
  • software correction techniques are only able to provide a limited degree of correction.
  • ion signals resulting in more than one ion arrival on average per pushout event at a given mass to charge value will result in saturation of the ion detector and hence result in a non-linear response and inaccurate mass determination.
  • the mass spectrometer enables the dynamic range of the detector to be extended. In particular, it is possible to alternate between two or more sensitivity ranges during an acquisition. One range is tuned to have a high sensitivity. A second range is adjusted to be at a lower sensitivity than the first range by a factor of up to x100. Preferably, the difference in sensitivity between the first and second sensitivity modes is at least a factor x10, x20, x30, x40, x50, x60, x70, x80, x90 or x100.
  • Exact mass measurements can be made using a single point lock mass common to both high and low sensitivity ranges.
  • the sensitivity is changed by the operation of a z-lens
  • other embodiments are also contemplated wherein in a more general arrangement, the ion optical system between the ion source and the mass analyser is altered or changed so that ions passing therethrough are focused/defocused thereby altering the ion transmission efficiency.
  • a y-focusing lens which may be an Einzel lens
  • altering a z-focusing lens which may be an Einzel lens
  • using a stigmatic focusing lens preferably having a circular aperture, which focuses/defocuses an ion beam in both the y- and z-directions
  • a dc quadrupole lens which can focus/defocus in the y-direction and/or the z-direction as desired.
  • z-focusing is preferred to other ways of altering the ion transmission efficiency since it has been found to minimise any change in resolution, mass position and spectral skew which otherwise seem to be associated with focussing/deflecting the ion beam in the y-direction.
  • the ion beam may be altered in the y-direction either instead of the z-direction or in addition to the z-direction.
  • At least an order of magnitude increase in the dynamic range can be achieved with the preferred embodiment. It has been demonstrated that the dynamic range can be extended from about 3.25 orders of magnitude to about 4.25 orders of magnitude with a GC (gas chromatography) peak width of about 1.5s at half height.
  • the ion source is a continuous ion source.
  • the ion source is selected from the group comprising: (i) an electron impact (“EI") ion source; (ii) a chemical ionisation (“CI”) ion source; and (iii) a field ionisation (“FI”) ion source. All these ion sources may be coupled to a gas chromatography (GC) source. Alternatively, and particularly when using a liquid chromatography (LC) source either an electrospray or an atmospheric pressure chemical ionisation (“APCI”) ion source may be used.
  • EI electron impact
  • CI chemical ionisation
  • FI field ionisation
  • the mass analyser comprises a time to digital converter.
  • the mass analyser is selected from the group comprising: (i) a quadrupole mass analyser; (ii) a magnetic sector mass analyser; (iii) an ion trap mass analyser; and (iv) a time of flight mass analyser, preferably an orthogonal acceleration time of flight mass analyser.
  • the mass spectrometer further comprises control means arranged to alternately or otherwise regularly switch the z-lens, or more generally the ion optics, back and forth between at least first and second modes.
  • two data streams are stored as two discrete functions presenting two discrete data sets.
  • the data can be used to yield linear quantitative calibration curves over four orders of magnitude.
  • the system can be arranged so that exact mass data can be extracted from either trace. Therefore, if a particular eluent produces a mass spectral peak which is saturated in the high sensitivity data set and therefore exhibits poor mass measurement accuracy, the same mass spectral peak may be unsaturated and correctly mass measured in the lower sensitivity trace.
  • exact mass measurements may be produced over a wide range of sample concentration.
  • the relative dwell times in the high and low sensitivity modes may either be the same, or in one embodiment more time may be spent in the higher sensitivity mode than in the lower sensitivity mode.
  • the relative time spent in a high sensitivity mode compared with a low sensitivity mode may be at least 50:50, 60:40, 70:30, 80:20, or 90:10. In otherwords, at least 50%, 60%, 70%, 80% or 90% of the time may be spent in the higher sensitivity mode compared with the lower sensitivity mode.
  • control means may be arranged to switch the z-lens, or more generally the ion optics, from the first mode to the second mode when the detector is approaching or experiencing saturation and/or to switch the z-lens, or more generally the ion optics, from the second mode to the first mode when a higher sensitivity is possible without the detector substantially saturating in the first mode.
  • low mass peaks may be ignored in the determination of whether or not to switch sensitivities and in one embodiment it is only if mass peaks falling within a specific mass to charge range (e.g. m/z ⁇ 50, or 75, or 100) saturate or approach saturation that the control means switches sensitivity modes.
  • control means may switch sensitivity modes based upon whether specific, preferably predetermined, mass peaks are approaching saturation or are saturated, or if an improved mass spectrum including that specific mass peak could be obtained by switching to a different sensitivity mode.
  • the mass spectrometer further comprises a power supply capable of supplying from -100 to +100V dc to the z-lens.
  • the z-lens may be a three part Einzel lens wherein the front and rear electrodes are maintained at substantially the same dc voltage, e.g. for positive ions around -40V dc, and an intermediate electrode may be varied, for positive ions, from approximately -100V dc in the high sensitivity (focusing) mode anywhere up to approximately +100V dc in the low sensitivity (defocusing) mode.
  • a voltage of -50V dc, +0V dc, +25V dc, +50V dc or +100V dc may be applied to the central electrode.
  • the beam of ions is diverged to have a profile or area which substantially exceeds the profile or area of an entrance aperture to the mass analyser by at least a factor x2, x4, x10, x25, x50, x75, or x100.
  • At least 85%, 90%, 95%, 96%, 97%, 98%, 99% or substantially 100% of the ions are arranged to pass through the entrance aperture.
  • the second mode less than or equal to 15%, 10%, 5%, 4%, 3%, 2%, or 1% of the ions are arranged to pass through the entrance aperture.
  • the difference in sensitivity between the first and second mode is at least x10, x20, x30, x40, x50, x60, x70, x80, x90 or x100.
  • a mass spectrometer as claimed in claim 27.
  • the ion optical system is arranged and adapted to be operated in at least three different sensitivity modes. In yet further embodiments four, five, six etc. up to practically an indefinite number of sensitivity modes may be provided.
  • FIG. 1 shows an ion source 1, preferably an electron impact or chemical ionisation ion source.
  • An ion beam 2 emitted from the ion source 1 travels along an axis commonly referred to as the x-axis.
  • the ions in the beam 2 are focused in a first y-direction as shown in the Figure by y-focusing and collimating lenses 3.
  • a z-lens 4, preferably downstream of the y-lens 3, is arranged to deflect or focus the ions in a second z-direction which is perpendicular to both the first y-direction and to the x-axis.
  • the z-lens 4 may comprise a number of electrodes, and may in one embodiment comprise an Einzel lens wherein the front and rear electrodes are maintained at substantially the same fixed dc voltage, and the dc voltage applied to an intermediate electrode may be varied to alter the degree of focusing/defocusing of an ion beam 2 passing therethrough.
  • An Einzel lens may also be used for the y-lens 3. In less preferred arrangements, either a z-lens 4 or a y-lens 3 (but not both) may be provided.
  • Figs. 2(a) and (b) show side views of a mass spectrometer.
  • the beam of ions 2 emitted from an ion source 1 is shown passing through the y-focusing and collimating lens 3.
  • the z-lens 4 operating in a first (higher sensitivity) mode focuses the beam 2 substantially within the acceptance area and acceptance angle of an entrance slit 10 of the mass analyser 9 so that a substantial proportion of the ions (i.e. normal intensity) subsequently enter the analyser 9 which is positioned downstream of the entrance slit 10.
  • Fig. 2(b) shows the z-lens 4 operating in a second (lower sensitivity) mode wherein the z-lens 4 defocuses the beam of ions 2 so that the beam of ions 2 has a much larger diameter or area than that of the entrance slit 10 to the mass analyser 9. Accordingly, a much smaller proportion of the ions (i.e. reduced intensity) will subsequently enter the analyser 9 in this mode of operation compared with the mode of operation shown in Fig. 2(a) since a large percentage of the ions will fall outside of the acceptance area and acceptance angle of the entrance slit 10.
  • Fig. 3 shows a plan view of a preferred embodiment.
  • a removable ion source 1 is shown together with a gas chromatography interface or reentrant tube 7 which communicates with a gas chromatography oven 6.
  • a lock mass inlet is typically present but is not shown.
  • a beam of ions 2 emitted by the ion source 1 passes through lens stack and collimating plates 3,4 which includes a switchable z-lens 4.
  • the z-focusing lens 4 is arranged in a field free region of the optics and is connected to a fast switching power supply capable of supplying from -100 to +100V DC. With positive ions, -100 V dc will focus an ion beam 2 passing therethrough and a more positive voltage, e.g. up to +100V dc, will substantially defocus a beam of ions 2 passing therethrough and thereby reduce the intensity of the ions entering the analyser 9.
  • the system may be tuned to full (high) sensitivity.
  • the z-focusing lens voltage may then be varied, preferably manually, until the desired lower sensitivity is reached.
  • acquisition then results in fast switching of the z-lens power supply between two (or more) pre-determined voltages so as to repetitively switch between high and low sensitivity modes of operation.
  • High and low sensitivity spectra may be stored as separate functions to be post processed.
  • the z-lens 4 only switches between higher and lower sensitivity modes (and vice versa) when either the detector 13 is being saturated in one mode or the sensitivity can be improved in another mode without saturation.
  • ion optics 3,4 Downstream of ion optics 3,4 is an automatic pneumatic isolation valve 8.
  • the beam of ions 2 having passed through ion optics 3,4 then passes through an entrance slit or aperture 10 into the analyser 9.
  • Packets of ions are then injected into the drift region of the preferably orthogonal acceleration time of flight mass analyser 9 by pusher plate 11. Packets of ions are then preferably reflected by reflectron 12.
  • the ions contained in a packet are temporally separated in the drift region and are then detected by detector 13 which preferably incorporates a time to digital converter in its associated circuitry.
  • Fig. 4 shows experimental data illustrating that the dynamic range can be extended from about 3.25 orders of magnitude to about 4.25 orders of magnitude (for a GC peak width of 1.5s at half height) using a combination of data from both the high and low sensitivity data sets.
  • the system was tuned to give a ratio of approximately 80:1 between the high and low sensitivity data sets.
  • the experiment allowed equal acquisition time for both data sets by alternating between the two sensitivity ranges between spectra.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)
EP01310018A 2000-11-29 2001-11-29 Spectromètre de masse et méthode associée Expired - Lifetime EP1215711B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP06021007.7A EP1768164B1 (fr) 2000-11-29 2001-11-29 Spectromètre de masse et méthodes de spectrométrie de masse
EP04010779A EP1460674B1 (fr) 2000-11-29 2001-11-29 Spectromètre de masse et méthode associé

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBGB0029040.3A GB0029040D0 (en) 2000-11-29 2000-11-29 Orthogonal time of flight mass spectrometer
GB0029040 2000-11-29
GB0108187A GB2369721B (en) 2000-11-29 2001-04-02 Mass spectrometer and method of mass spectrometry
GB0108187 2001-04-02

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP06021007.7A Division EP1768164B1 (fr) 2000-11-29 2001-11-29 Spectromètre de masse et méthodes de spectrométrie de masse
EP04010779A Division EP1460674B1 (fr) 2000-11-29 2001-11-29 Spectromètre de masse et méthode associé

Publications (3)

Publication Number Publication Date
EP1215711A2 true EP1215711A2 (fr) 2002-06-19
EP1215711A3 EP1215711A3 (fr) 2004-04-28
EP1215711B1 EP1215711B1 (fr) 2007-01-17

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EP01310018A Expired - Lifetime EP1215711B1 (fr) 2000-11-29 2001-11-29 Spectromètre de masse et méthode associée

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EP (1) EP1215711B1 (fr)
AT (2) ATE368937T1 (fr)
CA (1) CA2343582C (fr)
DE (2) DE60129751T2 (fr)
GB (1) GB2382921B (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6878929B2 (en) * 2000-11-29 2005-04-12 Micromass Uk Limited Mass spectrometer and methods of mass spectrometry
GB2413006A (en) * 2004-04-05 2005-10-12 Micromass Ltd Mass spectrometer with ion beam attenuator
EP1365437A3 (fr) * 2002-05-17 2006-01-04 Micromass UK Limited Spectromètre de masse et méthode associée
US7038197B2 (en) 2001-04-03 2006-05-02 Micromass Limited Mass spectrometer and method of mass spectrometry
US7095015B2 (en) 2001-10-22 2006-08-22 Micromass Uk Limited Mass spectrometer
DE102010006731A1 (de) 2009-02-04 2010-08-19 Nu Instruments Ltd., Wrexham Detektionseinrichtungen in Massenspektrometern und Detektionsverfahren
WO2012080268A1 (fr) 2010-12-17 2012-06-21 Thermo Fisher Scientific (Bremen) Gmbh Système et procédé de détection d'ions
CN109767971A (zh) * 2019-03-08 2019-05-17 昆山禾信质谱技术有限公司 二维离子束偏转装置
CN118692889A (zh) * 2024-06-25 2024-09-24 四川紫璞科技有限责任公司 一种稀有气体同位素质谱仪离子源

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2388704B (en) * 2002-05-17 2004-08-11 * Micromass Limited Mass spectrometer and method of mass spectrometry
US20050080571A1 (en) * 2003-10-10 2005-04-14 Klee Matthew S. Mass spectrometry performance enhancement
GB2428876B (en) * 2004-04-05 2008-10-01 Micromass Ltd Mass spectrometer
JP2006032109A (ja) * 2004-07-15 2006-02-02 Jeol Ltd 垂直加速型飛行時間型質量分析装置
GB0918629D0 (en) 2009-10-23 2009-12-09 Thermo Fisher Scient Bremen Detection apparatus for detecting charged particles, methods for detecting charged particles and mass spectometer
GB0918630D0 (en) 2009-10-23 2009-12-09 Thermo Fisher Scient Bremen Detection apparatus for detecting charged particles, methods for detecting charged particles and mass spectrometer

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5300774A (en) * 1991-04-25 1994-04-05 Applied Biosystems, Inc. Time-of-flight mass spectrometer with an aperture enabling tradeoff of transmission efficiency and resolution
JP3385327B2 (ja) * 1995-12-13 2003-03-10 株式会社日立製作所 三次元四重極質量分析装置

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6894275B2 (en) 2000-11-29 2005-05-17 Micromass Uk Limited Mass spectrometer and methods of mass spectrometry
US6878929B2 (en) * 2000-11-29 2005-04-12 Micromass Uk Limited Mass spectrometer and methods of mass spectrometry
US7038197B2 (en) 2001-04-03 2006-05-02 Micromass Limited Mass spectrometer and method of mass spectrometry
US7095015B2 (en) 2001-10-22 2006-08-22 Micromass Uk Limited Mass spectrometer
EP1365437A3 (fr) * 2002-05-17 2006-01-04 Micromass UK Limited Spectromètre de masse et méthode associée
GB2413006B (en) * 2004-04-05 2007-01-17 Micromass Ltd Mass spectrometer
GB2413006A (en) * 2004-04-05 2005-10-12 Micromass Ltd Mass spectrometer with ion beam attenuator
US7683314B2 (en) * 2004-04-05 2010-03-23 Micromass Uk Limited Mass spectrometer
DE102010006731A1 (de) 2009-02-04 2010-08-19 Nu Instruments Ltd., Wrexham Detektionseinrichtungen in Massenspektrometern und Detektionsverfahren
US8084751B2 (en) 2009-02-04 2011-12-27 Nu Instruments Limited Detection arrangements in mass spectrometers
DE102010006731B4 (de) * 2009-02-04 2014-05-15 Nu Instruments Ltd. Detektionseinrichtungen in Massenspektrometern und Detektionsverfahren
WO2012080268A1 (fr) 2010-12-17 2012-06-21 Thermo Fisher Scientific (Bremen) Gmbh Système et procédé de détection d'ions
CN109767971A (zh) * 2019-03-08 2019-05-17 昆山禾信质谱技术有限公司 二维离子束偏转装置
CN109767971B (zh) * 2019-03-08 2024-08-13 昆山禾信质谱技术有限公司 二维离子束偏转装置
CN118692889A (zh) * 2024-06-25 2024-09-24 四川紫璞科技有限责任公司 一种稀有气体同位素质谱仪离子源

Also Published As

Publication number Publication date
ATE352096T1 (de) 2007-02-15
DE60129751D1 (de) 2007-09-13
GB2382921A (en) 2003-06-11
CA2343582A1 (fr) 2002-05-29
EP1215711B1 (fr) 2007-01-17
DE60126048T2 (de) 2007-06-06
ATE368937T1 (de) 2007-08-15
EP1215711A3 (fr) 2004-04-28
GB2382921B (en) 2003-10-29
GB0228092D0 (en) 2003-01-08
DE60126048D1 (de) 2007-03-08
CA2343582C (fr) 2010-06-15
DE60129751T2 (de) 2008-04-30

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