EP1505635B1 - Spectromètres de masse et méthodes de spectrométrie de masse. - Google Patents
Spectromètres de masse et méthodes de spectrométrie de masse. Download PDFInfo
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- EP1505635B1 EP1505635B1 EP04026520A EP04026520A EP1505635B1 EP 1505635 B1 EP1505635 B1 EP 1505635B1 EP 04026520 A EP04026520 A EP 04026520A EP 04026520 A EP04026520 A EP 04026520A EP 1505635 B1 EP1505635 B1 EP 1505635B1
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- mbar
- vacuum chamber
- ion guide
- mass spectrometer
- ion
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- 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
- H01J49/065—Ion guides having stacked electrodes, e.g. ring stack, plate stack
Definitions
- the present invention relates to mass spectrometers and methods of mass spectrometry.
- Ion guides comprising rf-only multipole rod sets such as quadrupoles, hexapoles and octopoles are well known.
- An alternative type of ion guide known as an "ion funnel” has recently been proposed by Smith and coworkers at Pacific Northwest National Laboratory.
- An ion funnel comprises a stack of ring electrodes of constant external diameter but which have progressively smaller internal apertures.
- a dc voltage/potential gradient is applied along the length of the ion guide in order to urge ions through the ion funnel which would otherwise act as an ion mirror.
- a variant of the standard ion funnel arrangement is disclosed in Anal. Chem. 2000, 72, 2247-2255 and J. Am. Soc. Mass Spectrom. 2000, 11, 19-23 (Belov) and comprises an initial drift section comprising ring electrodes having constant internal diameters and a funnel section comprising ring electrodes having uniformly decreasing internal diameters. A dc voltage gradient is applied across both sections in order to urge ions through the ion funnel.
- ion funnels suffer from a narrow bandpass transmission efficiency i.e. the ion funnel may, for example, only efficiently transmit ions having mass to charge ratios ("m/z") falling within a narrow range e.g. 100 ⁇ m/z ⁇ 200.
- m/z mass to charge ratios
- pages 2249 and 2250 of Anal. Chem 2000, 72, 2247-2255 which similarly recognises that ion funnels suffer from an undesirably narrow m/z transmission window.
- ion funnel ion guides require both an rf voltage and a dc voltage gradient to be applied to the ring electrodes.
- the design and manufacture of a reliable power supply capable of supplying both an rf voltage and a dc voltage gradient which is decoupled from the rf voltage is a non-trivial matter and increases the overall manufacturing cost of the mass spectrometer.
- US-5818055 discloses a method and device for injection of ions into an ion trap.
- the preferred embodiment comprises a plurality of electrodes wherein most if not all of the electrodes have apertures which are substantially the same size.
- the apertures are preferably circular in shape, and the outer circumference of the electrodes may also be circular.
- the electrodes may comprise ring or annular electrodes.
- the outer circumference of the electrodes does not need to be circular and embodiments of the present invention are contemplated wherein the outer profile of the electrodes may take on other shapes.
- the preferred embodiment wherein the internal apertures of each of the electrodes are either identical or substantially similar is referred to hereinafter as an "ion tunnel" in contrast to ion funnels which have ring electrodes with internal apertures which become progressively smaller in size.
- One advantage of the preferred embodiment is that the ion guide does not suffer from a narrow or limited mass to charge ratio transmission efficiency which appears to be inherent with ion funnel arrangements.
- Another advantage of the preferred embodiment is that a dc voltage gradient is not and does not need to be applied to the ion guide.
- the resulting power supply for the ion guide can therefore be significantly simplified compared with that required for an ion funnel thereby saving costs and increasing reliability.
- An additional advantage of the preferred embodiment is that it has been found to exhibit an approximately 75% improvement in ion transmission efficiency compared with a conventional multipole, e.g. hexapole, ion guide. The reasons for this enhanced ion transmission efficiency are not fully understood, but it is thought that the ion tunnel may have a greater acceptance angle and a greater acceptance area than a comparable multipole rod set ion guide.
- the preferred ion guide therefore represents a significant improvement over other known ion guides.
- ion optical devices other than an ion tunnel ion guide
- multipole rod sets Einzel lenses, segmented multipoles, short (solid) quadrupole pre/post filter lenses ("stubbies"), 3D quadrupole ion traps comprising a central doughnut shaped electrode together with two concave end cap electrodes, and linear (2D) quadrupole ion traps comprising a multipole rod set with entrance and exit ring electrodes.
- stubbies 3D quadrupole ion traps comprising a central doughnut shaped electrode together with two concave end cap electrodes
- 2D linear quadrupole ion traps comprising a multipole rod set with entrance and exit ring electrodes
- the input vacuum chamber is arranged to be maintained at a relatively high pressure i.e. at least a few mbar.
- the input vacuum chamber may be arranged to be maintained at a pressure above a minimum value of 0.1 mbar and less than or equal to a maximum value such as 20 or 30 mbar.
- Embodiments of the present invention are also contemplated, wherein if the AC-only ion guide is considered to have a length L and is maintained in the input vacuum chamber at a pressure P, then the pressure-length product p x L is selected from the group comprising: (i) ⁇ 1 mbar cm; (ii) ⁇ 2 mbar cm; (iii) ⁇ 5 mbar cm; (iv) ⁇ 10 mbar cm; (v) ⁇ 15 mbar cm; (vi) ⁇ 20 mbar cm; (vii) ⁇ 25 mbar cm; (viii) ⁇ 30 mbar cm; (ix) ⁇ 40 mbar cm; (x) ⁇ 50 mbar cm; (xi) ⁇ 60 mbar cm; (xii) ⁇ 70 mbar cm; (xiii) ⁇ 80 mbar cm; (xiv) ⁇ 90 mbar cm; (xv) ⁇ 100 mbar cm; (xvi) ⁇ 110
- the electrodes are preferably relatively thin e.g. ⁇ 2 mm, further preferably ⁇ 1 mm, further preferably 0.5 ⁇ 0.2 mm, further preferably 0.7 ⁇ 0.1 mm thick. According to a particularly preferred embodiment the electrodes have a thickness within the range 0.5-0.7 mm in contrast to multipole rod sets which are typically > 10 cm long.
- Each, or at least a majority of the electrodes forming the AC-only ion guide may comprise either a plate having an aperture therein, or a wire or rod bent to form a closed ring or a nearly closed ring.
- the outer profile of the electrodes may or may not be circular.
- alternate electrodes are connected together and to one of the output connections of a single AC generator.
- the AC-only ion guide preferably comprises at least 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 electrodes.
- the electrodes forming the AC-only ion guide may have internal diameters or dimensions selected from the group comprising: (i) ⁇ 5.0 mm; (ii) ⁇ 4.5 mm; (iii) ⁇ 4.0 mm; (iv) ⁇ 3.5 mm; (v) ⁇ 3.0 mm; (vi) ⁇ 2.5 mm; (vii) 3.0 ⁇ 0.5 mm; (viii) ⁇ 10.0 mm; (ix) ⁇ 9.0 mm; (x) ⁇ 8.0 mm; (x) ⁇ 7.0 mm; (xii) ⁇ 6.0 mm; (xiii) 5.0 t 0.5 mm; and (xiv) 4-6 mm.
- the length of the AC-only ion guide may be selected from the group comprising: (i) ⁇ 100 mm; (ii) ⁇ 120 mm; (iii) ⁇ 150 mm; (iv) 130 ⁇ 10 mm; (v) 100-150 mm; (vi) ⁇ 160 mm; (vii) ⁇ 180 mm; (viii) ⁇ 200 mm; (ix) 130-150 mm; (x) 120-180 mm; (xi) 120-140 mm; (xii) 130 mm ⁇ 5, 10, 15, 20, 25 or 30 mm; (xiii) 50-300 mm; (xiv) 150-300 mm; (xv) ⁇ 50 mm; (xvi) 50-100 mm; (xvii) 60-90 mm; (xviii) ⁇ 75 mm; (xix) 50-75 mm; and (xx) 75-100 mm.
- An intermediate vacuum chamber is disposed between the input vacuum chamber and the analyzer vacuum chamber, the intermediate vacuum chamber comprising an AC-only ion guide for transmitting ions through the intermediate vacuum chamber.
- the AC-only ion guide arranged in the intermediate vacuum chamber preferably comprises a plurality of electrodes having apertures, the apertures being aligned so that ions travel through them as they are transmitted by the ion guide.
- At least one further differential pumping apertured electrode is provided through which ions may pass.
- the further differential pumping apertured electrode is disposed between the vacuum chambers to allow the intermediate vacuum chamber to be maintained at a lower pressure than the input vacuum chamber, and the analyzer vacuum chamber to be maintained at a lower pressure than the intermediate vacuum chamber.
- An alternating current (AC) generator is connected to an intermediate chamber reference potential for providing AC potentials to the AC-only ion guide in the intermediate vacuum chamber.
- At least 90%, and preferably 100%, of the apertures of the electrodes forming the AC-only ion guide in the intermediate vacuum chamber are substantially the same size, and at least 90%, and preferably 100%, of the plurality of the electrodes forming the AC-only ion guide in the intermediate vacuum chamber are connected to the AC generator connected to the intermediate chamber reference potential in such a way that at any instant during an AC cycle of the output of the AC generator, adjacent ones of the electrodes forming the AC-only ion guide arranged in the intermediate vacuum chamber are supplied respectively with approximately equal positive and negative potentials relative to the intermediate chamber reference potential.
- the AC-only ion guide in the intermediate vacuum chamber comprises at least 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 electrodes.
- the intermediate vacuum chamber is arranged to be maintained at a pressure selected from the group comprising: (i) 10 -3 -10 -2 mbar; (ii) ⁇ 2 x 10 -3 mbar; (iii) ⁇ 5 x 10 -3 mbar; (iv) ⁇ 10 -2 mbar; (v) 10 -3 -5 x 10 -3 mbar; and (vi) 5 x 10 -3 -10 -2 mbar.
- the electrodes forming the AC-only ion guide in the intermediate vacuum chamber have internal diameters or dimensions selected from the group comprising: (i) ⁇ 5.0 mm; (ii) ⁇ 4.5 mm; (iii) ⁇ 4.0 mm; (iv) ⁇ 3.5 mm; (v) ⁇ 3.0 mm; (vi) ⁇ 2.5 mm; (vii) 3.0 ⁇ 0.5 mm; (viii) ⁇ 10.0 mm; (ix) ⁇ 9.0 mm; (x) ⁇ 8.0 mm; (xi) ⁇ 7.0 mm; (xii) ⁇ 6.0 mm; (xiii) 5.0 ⁇ 0.5 mm; and (xiv) 4-6 mm.
- the individual electrodes in the AC-only ion guide in the input vacuum chamber and/or the AC-only ion guide in the intermediate vacuum chamber preferably have a substantially circular aperture having a diameter selected from the group comprising: (i) 0.5-1.5 mm; (ii) 1.5-2.5 mm; (iii) 2.5-3.5 mm; (iv) 3.5-4.5 mm; (v) 4.5-5.5 mm; (vi) 5.5-6.5 mm; (vii) 6.5-7.5 mm; (viii) 7.5-8.5 mm; (ix) 8.5-9.5 mm; (x) 9.5-10.5 mm; and (xi) ⁇ 10mm.
- the length of the ion guide in the intermediate vacuum chamber is selected from the group comprising: (i) ⁇ 100 mm; (ii) ⁇ 120 mm; (iii) ⁇ 150 mm; (iv) 130 ⁇ 10 mm; (v) 100-150 mm; (vi) ⁇ 160 mm; (vii) ⁇ 180 mm; (viii) ⁇ 200 mm; (ix) 130-150 mm; (x) 120-180 mm; (xi) 120-140 mm; (xii) 130 mm ⁇ 5, 10, 15, 20, 25 or 30 mm; (xiii) 50-300 mm; (xiv) 150-300 mm; (xv) ⁇ 50 mm; (xvi) 50-100 mm; (xvii) 60-90 mm; (xviii) ⁇ 75 mm; (xix) 50-75 mm; and (xx) 75-100 mm.
- the ion source is an atmospheric pressure ion source.
- the ion source is a continuous ion source.
- An Electrospray (“ES”) ion source or an Atmospheric Pressure Chemical Ionisation (“APCI”) ion source is particularly preferred.
- the ion source is either an Inductively Coupled Plasma (“ICP”) ion source or a Matrix Assisted Laser Desorption Ionisation (“MALDI”) ion source at low vacuum or at atmospheric pressure.
- ICP Inductively Coupled Plasma
- MALDI Matrix Assisted Laser Desorption Ionisation
- the ion mass analyser is selected from the group comprising: (i) a time-of-flight mass analyser, preferably an orthogonal time of flight mass analyser; (ii) a quadrupole mass analyser; and (iii) a quadrupole ion trap.
- the AC-only ion guide comprises two interleaved comb arrangements, each comb arrangement comprising a longitudinally extending bar or spine having a plurality of electrodes having apertures depending therefrom.
- the input vacuum chamber has a length and the combs arrangements extend at least x% of the length, x% selected from the group comprising: (i) ⁇ 50%; (ii) ⁇ 60%; (iii) ⁇ 70%; (iv) ⁇ 80%; (v) ⁇ 90%; and (vi) ⁇ 95%.
- a preferred ion tunnel 15 comprises a plurality of electrodes 15a,15b each having an aperture.
- the outer profile of the electrodes 15a,15b is circular.
- the outer profile of the electrodes 15a,15b does not need to be circular.
- the preferred embodiment may be considered to comprise a plurality of ring or annular electrodes, electrodes having other shapes are also contemplated as falling within the scope of the present invention.
- Adjacent electrodes 15a,15b are connected to opposite phases of an AC power supply.
- the first, third, fifth etc. ring electrodes 15a may be connected to the 0° phase supply 16a
- the second, fourth, sixth etc. ring electrodes 15b may be connected to the 180° phase supply 16b.
- the AC power supply may be a RF power supply.
- the present invention is not intended to be limited to RF frequencies.
- "AC" is intended to mean simply that the waveform alternates and hence embodiments of the present invention are also contemplated wherein non-sinusoidal waveforms including square waves are provided. Ions from an ion source pass through the ion tunnel 15 and are efficiently transmitted by it.
- the dc reference potential about which the AC signal oscillates is substantially the same for each electrode.
- blocking dc potentials are not applied to either the entrance or exit of the ion tunnel 15.
- Fig. 2 shows a conventional mass spectrometer.
- An Electrospray (“ES”) ion source 1 or an Atmospheric Pressure Chemical lonisation (“APCI”) 1,2 ion source emits ions which enter a vacuum chamber 17 pumped by a rotary or mechanical pump 4 via a sample cone 3 and a portion of the gas and ions passes through a differential pumping aperture 21 preferably maintained at 50-120V into a vacuum chamber 18 housing an rf-only hexapole ion guide 6. Vacuum chamber 18 is pumped by a rotary or mechanical pump 7.
- Ions are transmitted by the rf-only hexapole ion guide 6 through the vacuum chamber 18 and pass through a differential pumping aperture 8 into a further vacuum chamber 19 pumped by a turbo-molecular pump 10.
- This vacuum chamber 19 houses another rf-only hexapole ion guide 9.
- Ions are transmitted by rf-only hexapole ion guide 9 through vacuum chamber 19 and pass through differential pumping aperture 11 into a yet further vacuum chamber 20 which is pumped by a turbo-molecular pump 14.
- Vacuum chamber 20 houses a prefilter rod set 12, a quadrupole mass filter/analyser 13 and may include other elements such as a collision cell (not shown), a further quadrupole mass filter/analyser together with an ion detector (not shown) or a time of flight analyser (not shown).
- Fig. 3 illustrates an embodiment of the present invention wherein hexapole ion guide 6 has been replaced with an ion tunnel 15 according to the preferred embodiment.
- the other components of the mass spectrometer are substantially the same as described in relation to Fig. 2 and hence will not be described again.
- the ion tunnel 15 exhibits an improved transmission efficiency of approximately 75% compared with using hexapole ion guide 6 and the ion tunnel 15 does not suffer from as narrow a m/z bandpass transmission efficiency as is reported with ion funnels.
- the reference potential of the ion tunnel 15 is preferably maintained at 0-2 V dc above the dc potential of the wall forming the differential pumping aperture 11 which is preferably either at ground (0 V dc) or around 40-240 V dc depending upon the mass analyser used.
- the wall forming differential pumping aperture 11 may, of course, be maintained at other dc potentials.
- the hexapole ion guide 9 may be replaced by an ion tunnel 15' with hexapole ion guide 6 being maintained.
- Fig. 4 shows a particularly preferred embodiment of the present invention wherein both hexapole ion guides 6,9 have been replaced with ion tunnels 15,15'.
- the ion tunnels 15,15' are about 13 cm in length and preferably comprise approximately 85 ring electrodes.
- the ion tunnel 15 in vacuum chamber 18 is preferably maintained at a pressure ⁇ 1 mbar and is supplied with an rf-voltage at a frequency - 1 MHz
- the ion tunnel 15' in vacuum chamber 19 is preferably maintained at a pressure of 10 -3 -10 -2 mbar and is supplied with an rf-voltage at a frequency - 2 MHz.
- Rf frequencies of 800 kHz - 3 MHz could also be used for both ion tunnels 15,15' according to further embodiments of the present invention.
- the ion tunnel 15' exhibits an improved transmission efficiency of approximately 25%, and hence the combination of ion tunnels 15,15' exhibit an improved transmission efficiency of approximately 100% compared with using hexapole ion guide 6 in combination with hexapole ion guide 9.
- Figs. 5 and 6 show a particularly preferred embodiment of the present invention.
- the AC-only ion guide comprises two interleaved comb-like arrangements of electrodes.
- Each comb comprises a plurality of electrodes 15a;15b, each electrode 15a;15b having an aperture.
- One of the combs is shown in more detail in Fig. 5 .
- the comb comprises a longitudinally extending bar or spine from which a number of electrodes 15a;15b depend therefrom.
- the electrodes 15a;15b are integral with the bar or spine.
- Each electrode 15a;15b preferably has a substantially circular aperture. However, as can be seen from Fig.
- each electrode 15a;15b in cross-section is preferably a truncated circular shape.
- Fig. 6 shows in more detail how the two combs are interleaved. Various insulating rings are also shown which help to hold the assembly together.
- the comb like arrangement of electrodes 15a;15b may be provided in input vacuum chamber 18 and/or intermediate vacuum chamber 19. For the avoidance of any doubt, the arrangements shown in Figs. 5 and 6 are intended to fall within the scope of the claims.
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Claims (30)
- Spectromètre de masse comprenant :une source d'ions (1) pour générer des ions ;une chambre à vide d'entrée (18) comprenant au moins un guide d'ions à c.a. pour transmettre lesdits ions, les électrodes adjacentes formant ledit guide d'ions à c.a. étant reliées à des phases opposées d'une alimentation en c.a. ;une chambre à vide d'analyse (20) comprenant un analyseur de masse (13) disposé pour recevoir des ions après qu'ils ont été transmis par ledit guide d'ions à c.a. ;une chambre à vide intermédiaire (19) disposée entre ladite chambre à vide d'entrée (18) et ladite chambre à vide d'analyse (20), ladite chambre à vide intermédiaire (19) comprenant un guide d'ions à c.a. pour transmettre des ions à travers ladite chambre à vide intermédiaire (19) ;au moins une électrode à ouverture de pompage différentiel (8) à travers laquelle des ions peuvent passer, ladite au moins une électrode à ouverture de pompage différentiel (8) étant disposée entre ladite chambre à vide d'entrée (18) et ladite chambre à vide intermédiaire (19) pour permettre à ladite chambre à vide intermédiaire (19) d'être maintenue à une pression inférieure à celle de ladite chambre à vide d'entrée (18) ; etau moins une autre électrode à ouverture de pompage différentiel (11) à travers laquelle des ions peuvent passer, disposée entre ladite chambre à vide intermédiaire (19) et ladite chambre à vide d'analyse (20) pour permettre à ladite chambre à vide d'analyse (20) d'être maintenue à une pression inférieure à celle de ladite chambre à vide intermédiaire (19) ;caractérisé en ce que :ledit guide d'ions à c.a. installé dans ladite chambre à vide d'entrée (18) comprend deux structures de peigne imbriquées, chacune desdites structures de peigne comprenant une barre ou colonne s'étendant longitudinalement ayant une pluralité d'électrodes comportant des ouvertures dépendant de celle-ci, lesdites électrodes étant intégrées à ladite barre ou colonne.
- Spectromètre de masse selon la revendication 1, dans lequel au moins 90 % ou 100 % desdites ouvertures sont sensiblement de la même taille.
- Spectromètre de masse selon la revendication 1 ou 2, dans lequel ladite pluralité d'électrodes formant ledit guide d'ions à c.a. installé dans ladite chambre à vide d'entrée (18) est reliée à un alternateur d'une manière telle qu'à tout instant durant un cycle de c.a. de la sortie dudit alternateur, les électrodes adjacentes parmi lesdites électrodes sont respectivement alimentées avec des potentiels positifs et négatifs approximativement égaux par rapport à un potentiel de référence de chambre d'entrée.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite chambre à vide d'entrée (18) a une certaine longueur et lesdites structures de peigne s'étendent sur au moins x % de ladite longueur, les x % étant choisis dans le groupe constitué par : (i) ≥ 50 % ; (ii) ≥ 60 % ; (iii) ≥70% ; (iv) ≥ 80% ; (v) ≥ 90% ; et (vi) ≥ 95%.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel les électrodes alternées parmi lesdites électrodes sont reliées les unes aux autres et à l'une des connexions de sortie d'un seul alternateur.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel le guide d'ions à c.a. installé dans ladite chambre à vide d'entrée (18) comprend au moins 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90 ou 100 électrodes.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel lesdites électrodes ont des diamètres ou dimensions internes choisis dans le groupe constitué par : (1) ≤ 5,0 mm ; (ii) ≤ 4,5 mm ; (iii) ≤ 4,0 mm ; (iv) ≤ 3,5 mm ; (v) ≤ 3,0 mm ; (vi) ≤ 2,5 mm ; (vii) 3,0 ± 0,5 mm ; (viii) ≤ 10,0 mm ; (ix) ≤ 9,0 mm ; (x) ≤ 8,0mm ; (xi) ≤ 7,0 mm ; (xii) ≤ 6,0 mm ; (xiii) 5,0 ± 0,5mm ; et (xiv) 4-6 mm.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel la longueur dudit guide d'ions à c.a. installé dans ladite chambre à vide d'entrée (18) est choisie dans le groupe constitué par : (i) ≥ 100 mm ; (ii) ≥ 120 mm ; (iii) ≥ 150 mm ; (iv) 130 ± 10 mm ; (v) 100-150 mm ; (vi) ≤ 160 mm ; (vii) ≤ 180 mm ; (viii) ≤ 200 mm ; (ix) 130-150 mm ; (x) 120-180 mm ; (xi) 120-140 mm ; (xii) 130 mm ± 5, 10, 15, 20, 25 ou 30 mm ; (xiii) 50-300 mm ; (xiv) 150-300 mm ; (xv) ≥ 50 mm ; (xvi) 50-100 mm ; (xvii) 60-90 mm ; (xviii) ≥ 75 mm ; (xix) 50-75 mm ; (xx) 75-100 mm ; (xxi) 150-200 mm ; (xxii) ≥ 200 mm ; et (xxiii) 50-200 mm.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit guide d'ions à c.a. installé dans ladite chambre à vide intermédiaire (19) comprend une pluralité d'électrodes comportant des ouvertures, les ouvertures étant alignées de telle sorte que les ions se déplacent à travers elles quand ils sont transmis par ledit guide d'ions à c.a. dans ladite chambre à vide intermédiaire (19) ;
ledit spectromètre de masse comprenant en outre un alternateur relié à un potentiel de référence de chambre intermédiaire pour fournir des potentiels en c.a. audit guide d'ions à c.a. dans ladite chambre à vide intermédiaire (19). - Spectromètre de masse selon la revendication 9, dans lequel au moins 90 % ou 100 % des ouvertures des électrodes formant ledit guide d'ions à c.a. dans ladite chambre à vide intermédiaire (19) sont sensiblement de la même taille ; et
au moins 90 % ou 100 % de ladite pluralité d'électrodes formant ledit guide d'ions à c.a. dans ladite chambre à vide intermédiaire (19) sont reliés à l'alternateur relié audit potentiel de référence de chambre intermédiaire d'une manière telle qu'à tout instant durant un cycle de c.a. de la sortie de l'alternateur, les électrodes adjacentes parmi lesdites électrodes formant ledit guide d'ions à c.a. installé dans ladite chambre à vide intermédiaire (19) sont respectivement alimentées avec des potentiels positifs et négatifs approximativement égaux par rapport audit potentiel de référence de chambre intermédiaire. - Spectromètre de masse selon la revendication 9 ou 10, dans lequel le guide d'ions à c.a. dans ladite chambre à vide intermédiaire (19) comprend au moins 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90 ou 100 électrodes.
- Spectromètre de masse selon l'une quelconque des revendications 9, 10 ou 11, dans lequel ladite chambre à vide intermédiaire (19) est disposée pour être maintenue à une pression choisie dans le groupe constitué par : (i) 10-3-10-2 mbar ; (ii) ≥ 2.10-3 mbar ; (iii) ≥ 5.10-3 mbar ; (iv) ≤ 10-2 mbar ; (v) 10-3-5.10-3 mbar ; et (vi) 5.10-3-10-2 mbar.
- Spectromètre de masse selon l'une quelconque des revendications 9 à 12, dans lequel les électrodes formant ledit guide d'ions à c.a. dans ladite chambre à vide intermédiaire (19) ont des diamètres ou dimensions internes choisis dans le groupe constitué par : (i) ≤ 5,0 mm ; (ii) ≤ 4,5 mm ; (iii) ≤ 4,0 mm ; (iv) ≤ 3,5 mm ; (v) ≤ 3,0 mm ; (vi) ≤ 2,5 mm ; (vii) 3,0 ± 0,5 mm ; (viii) ≤ 10,0 mm ; (ix) ≤ 9,0 mm ; (x) ≤ 8,0 mm ; (xi) ≤ 7,0 mm ; (xii) ≤ 6,0 mm ; (xiii) 5,0 ± 0,5 mm ; et (xiv) 4-6 mm.
- Spectromètre de masse selon l'une quelconque des revendications 9 à 13, dans lequel la longueur dudit guide d'ions à c.a. dans ladite chambre à vide intermédiaire (19) est choisie dans le groupe constitué par : (1) ≥ 100 mm ; (ii) ≥ 120 mm ; (iii) ≥ 150 mm ; (iv) 130 ± 10 mm ; (v) 100-150 mm ; (vi) ≤ 160 mm ; (vii) ≤ 180 mm ; (viii) ≤ 200 mm ; (ix) 130-150 mm ; (x) 120-180 mm ; (xi) 120-140 mm ; (xii) 130 mm ± 5, 10, 15, 20, 25 ou 30 mm ; (xiii) 50-300 mm ; (xiv) 150-300 mm ; (xv) ≥ 50 mm ; (xvi) 50-100 mm ; (xvii) 60-90 mm ; (xviii) ≥ 75 mm ; (xix) 50-75 mm ; (xx) 75-100 mm ; (xxi) 150-200 mm ; (xxii) ≥ 200 mm ; et (xxiii) 50-200 mm.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite source d'ions (1) est une source d'ions à pression atmosphérique.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite source d'ions (1) est une source d'ions continue.
- Spectromètre de masse selon la revendication 15 ou 16, dans lequel ladite source d'ions (1) est une source d'ions à électronébulisation (« ES ») ou une source d'ions à ionisation chimique à pression atmosphérique (« APCI »).
- Spectromètre de masse selon la revendication 15 ou 16, dans lequel ladite source d'ions (1) est une source d'ions à plasma à couplage inductif (« ICP »).
- Spectromètre de masse selon l'une quelconque des revendications 1 à 14, dans lequel ladite source d'ions (1) est une source d'ions à ionisation par désorption laser assistée par matrice (« MALDI »).
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit analyseur de masse est choisi dans le groupe constitué par : (i) un analyseur de masse à temps de vol ; (ii) un analyseur de masse à temps de vol orthogonal ; (iii) un analyseur de masse quadripolaire ; et (iv) un piège à ions quadripolaire.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite chambre à vide d'entrée (18) est disposée pour être maintenue à une pression choisie dans le groupe constitué par : (i) ≥ 0,1 mbar ; (ii) ≥ 0,5 mbar ; (iii) ≥ 0,7 mbar ; (iv) ≥ 1,0 mbar ; (v) ≥ 1,3 mbar ; (vi) ≥ 1,5 mbar ; (vii) ≥ 2,0 mbar ; (viii) ≥ 2,5 mbar ; (ix) ≥ 3,0 mbar ; (x) ≥ 3,5 mbar ; (xi) ≥ 4,0 mbar ; (xii) ≥ 4,5 mbar ; (xiii) ≥ 5,0 mbar ; (xiv) ≥ 6,0 mbar ; (xv) ≥ 7,0 mbar ; (xvi) ≥ 8,0 mbar ; (xvii) ≥ 9,0 mbar ; (xviii) ≥ 10,0 mbar ; (xix) 1-5 mbar ; (xx) 1-2 mbar ; et (xxi) 0,5-1,5 mbar.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite chambre à vide d'entrée (18) est disposée pour être maintenue à une pression choisie dans le groupe constitué par : (i) ≥ 20 mbar ; et (ii) ≤ 30 mbar.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel si le guide d'ions à c.a. installé dans ladite chambre à vide d'entrée (18) a une longueur L et est maintenu dans la chambre à vide d'entrée (18) à une pression P, alors le produit pression par longueur P x L est choisi dans le groupe constitué par : (i) ≥ 1 mbar.cm; (ii) ≥ 2 mbar.cm ; (iii) ≥ 5 mbar.cm ; (iv) ≥ 10 mbar.cm ; (v) ≥ 15 mbar.cm ; (vi) ≥ 20 mbar.cm ; (vii) ≥ 25 mbar.cm ; (viii) ≥ 30 mbar.cm ; (ix) ≥ 40 mbar.cm ; (x) ≥ 50 mbar.cm ; (xi) ≥ 60 mbar.cm ; (xii) ≥ 70 mbar.cm ; (xiii) ≥ 80 mbar.cm ; (xiv) ≥ 90 mbar.cm ; (xv) ≥ 100 mbar.cm ; (xvi) ≥ 110 mbar.cm ; (xvii) ≥ 120 mbar.cm ; (xviii) ≥ 130 mbar.cm ; (xix) ≥ 140 mbar.cm ; (xx) ≥ 150 mbar.cm ; (xxi) ≥ 160 mbar.cm ; (xxii) ≥ 170 mbar.cm ; (xxiii) ≥ 180 mbar.cm ; (xxiv) ≥ 190 mbar.cm ; et (xxv) ≥ 200 mbar.cm.
- Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel les électrodes formant le guide d'ions à c.a. installé dans ladite chambre à vide d'entrée (18) ont une épaisseur choisie dans le groupe constitué par : (i) ≤ 2 mm ; (ii) ≤ 1 mm ; (iii) 0,5 ± 0,2 mm ; (iv) 0,7 ± 0,1 mm ; et (v) 0,5-0,7 mm.
- Procédé de spectrométrie de masse, comprenant :la génération d'ions à partir d'une source d'ions ;la transmission d'au moins certains desdits ions à travers une chambre à vide d'entrée (18) comprenant au moins un guide d'ions à c.a. pour transmettre lesdits ions, les électrodes adjacentes formant ledit guide d'ions à c.a. étant reliées à des phases opposées d'une alimentation en c.a. ;l'acheminement desdits ions jusqu'à une chambre à vide d'analyse (20) comprenant un analyseur de masse (13) disposé pour recevoir des ions après qu'ils ont été transmis par ledit guide d'ions à c.a. ;la mise en place d'une chambre à vide intermédiaire (19) disposée entre ladite chambre à vide d'entrée (18) et ladite chambre à vide d'analyse (20), ladite chambre à vide intermédiaire (19) comprenant un guide d'ions à c.a. pour transmettre des ions à travers ladite chambre à vide intermédiaire (19) ;la mise en place d'au moins une électrode à ouverture de pompage différentiel (8) à travers laquelle des ions peuvent passer, ladite au moins une électrode à ouverture de pompage différentiel (8) étant disposée entre ladite chambre à vide d'entrée (18) et ladite chambre à vide intermédiaire (19) pour permettre à ladite chambre à vide intermédiaire (19) d'être maintenue à une pression inférieure à celle de ladite chambre à vide d'entrée (18) ; etla mise en place d'au moins une autre électrode à ouverture de pompage différentiel (11) à travers laquelle des ions peuvent passer, disposée entre ladite chambre à vide intermédiaire (19) et ladite chambre à vide d'analyse (20) pour permettre à ladite chambre à vide d'analyse (20) d'être maintenue à une pression inférieure à celle de ladite chambre à vide intermédiaire (19) ;caractérisé en ce que :ladite étape de transmission d'au moins certains desdits ions à travers ladite chambre à vide d'entrée (18) comprend la transmission desdits ions à travers ledit guide d'ions à c.a. comprenant deux structures de peigne imbriquées, chacune desdites structures de peigne comprenant une barre ou colonne s'étendant longitudinalement ayant une pluralité d'électrodes comportant des ouvertures dépendant de celle-ci, lesdites électrodes étant intégrées à ladite barre ou colonne.
- Procédé selon la revendication 25, comprenant en outre le maintien de ladite chambre à vide d'entrée à une pression choisie dans le groupe constitué par : (i) ≥ 0,1 mbar ; (ii) ≥ 0,5 mbar ; (iii) ≥ 0,7 mbar ; (iv) ≥ 1,0 mbar ; (v) ≥ 1,3 mbar ; (vi) ≥ 1,5 mbar ; (vii) ≥ 2,0 mbar ; (viii) ≥ 2,5 mbar ; (ix) ≥ 3,0 mbar ; (x) ≥ 3,5 mbar ; (xi) ≥ 4,0 mbar ; (xii) ≥ 4,5 mbar ; (xiii) ≥ 5,0 mbar ; (xiv) ≥ 6,0 mbar ; (xv) ≥ 7,0 mbar ; (xvi) ≥ 8,0 mbar ; (xvii) ≥ 9,0 mbar ; (xviii) ≥ 10,0 mbar ; (xix) 1-5 mbar ; (xx) 1-2 mbar ; et (xxi) 0,5-1,5 mbar.
- Procédé selon la revendication 25 ou 26, comprenant en outre le maintien de ladite chambre à vide d'entrée (18) à une pression choisie dans le groupe constitué par : (i) ≤ 20 mbar ; et (ii) ≤ 30 mbar.
- Procédé selon la revendication 25, 26 ou 27, dans lequel ledit guide d'ions à c.a. installé dans ladite chambre à vide intermédiaire (19) comprend une pluralité d'électrodes comportant des ouvertures, les ouvertures étant alignées de telle sorte que les ions se déplacent à travers elles quand ils sont transmis par ledit guide d'ions ;
ledit procédé comprenant en outre la mise en place d'un alternateur relié à un potentiel de référence de chambre intermédiaire pour fournir des potentiels en c.a. au guide d'ions à c.a. dans ladite chambre à vide intermédiaire (19). - Procédé selon la revendication 28, comprenant en outre le maintien de ladite chambre à vide intermédiaire (19) à une pression choisie dans le groupe constitué par : (i) 10-1-10-2 mbar ; (ii) ≥ 2.10-3 mbar ; (iii) ≥ 5.10-3 mbar ; (iv) ≤ 10-2 mbar ; (v) 10-3-5.10-3 mbar ; et (vi) 5.10-2 mbar.
- Procédé selon l'une quelconque des revendications 25 à 29, comprenant en outre le maintien du guide d'ions à c.a. ayant une longueur L dans la chambre à vide d'entrée (18) à une pression P, le produit pression par longueur P x L étant choisi dans le groupe constitué par : (i) ≥ 1 mbar.cm ; (ii) ≥ 2 mbar.cm ; (iii) ≥ 5 mbar.cm ; (iv) ≥ 10 mbar.cm ; (v) ≥ 15 mbar.cm ; (vi) ≥ 20 mbar.cm ; (vii) ≥ 25 mbar.cm ; (viii) ≥ 30 mbar.cm ; (ix) ≥ 40 mbar.cm ; (x) ≥ 50 mbar.cm ; (xi) ≥ 60 mbar.cm ; (xii) ≥ 70 mbar.cm ; (xiii) ≥ 80 mbar.cm ; (xiv) ≥ 90 mbar.cm ; (xv) ≥ 100 mbar.cm ; (xvi) ≥ 110 mbar.cm ; (xvii) ≥ 120 mbar.cm ; (xviii) ≥ 130 mbar.cm ; (xix) ≥ 140 mbar.cm ; (xx) ≥ 150 mbar.cm ; (xxi) ≥ 160 mbar.cm ; (xxii) ≥ 170 mbar.cm ; (xxiii) ≥ 180 mbar.cm ; (xxiv) ≥ 190 mbar.cm ; et (xxv) ≥ 200 mbar.cm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20100183535 EP2302661A1 (fr) | 2000-11-29 | 2001-11-29 | Spectromètre de masse ayant un guide d'ions de type tunnel à ions et méthode de spectrométrie de masse. |
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0029088.2A GB0029088D0 (en) | 2000-11-29 | 2000-11-29 | Ion tunnel |
GB0029088 | 2000-11-29 | ||
GBGB0109760.9A GB0109760D0 (en) | 2000-11-29 | 2001-04-20 | Mass spectrometers and methods of mass spectrometry |
GB0109760 | 2001-04-20 | ||
GB0110149 | 2001-04-25 | ||
GB0110149A GB0110149D0 (en) | 2000-11-29 | 2001-04-25 | Mass spectrometers and methods of mass spectrometry |
GB0120028 | 2001-08-16 | ||
GBGB0120028.6A GB0120028D0 (en) | 2000-11-29 | 2001-08-16 | Mass spectrometers and methods of mass spectrometry |
EP01310026A EP1215712B1 (fr) | 2000-11-29 | 2001-11-29 | Spectromètre de masse et méthodes associées |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP01310026A Division EP1215712B1 (fr) | 2000-11-29 | 2001-11-29 | Spectromètre de masse et méthodes associées |
EP01310026.8 Division | 2001-11-29 |
Related Child Applications (1)
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EP10183535.3 Division-Into | 2010-09-30 |
Publications (3)
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EP1505635A2 EP1505635A2 (fr) | 2005-02-09 |
EP1505635A3 EP1505635A3 (fr) | 2007-03-21 |
EP1505635B1 true EP1505635B1 (fr) | 2011-01-12 |
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EP20100183535 Withdrawn EP2302661A1 (fr) | 2000-11-29 | 2001-11-29 | Spectromètre de masse ayant un guide d'ions de type tunnel à ions et méthode de spectrométrie de masse. |
EP04026520A Expired - Lifetime EP1505635B1 (fr) | 2000-11-29 | 2001-11-29 | Spectromètres de masse et méthodes de spectrométrie de masse. |
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EP20100183535 Withdrawn EP2302661A1 (fr) | 2000-11-29 | 2001-11-29 | Spectromètre de masse ayant un guide d'ions de type tunnel à ions et méthode de spectrométrie de masse. |
Country Status (4)
Country | Link |
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EP (2) | EP2302661A1 (fr) |
AT (2) | ATE495542T1 (fr) |
DE (2) | DE60143861D1 (fr) |
GB (2) | GB0029088D0 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2302661A1 (fr) * | 2000-11-29 | 2011-03-30 | Micromass UK Limited | Spectromètre de masse ayant un guide d'ions de type tunnel à ions et méthode de spectrométrie de masse. |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US8581177B2 (en) | 2011-04-11 | 2013-11-12 | Thermo Finnigan Llc | High duty cycle ion storage/ion mobility separation mass spectrometer |
GB201122178D0 (en) | 2011-12-22 | 2012-02-01 | Thermo Fisher Scient Bremen | Method of tandem mass spectrometry |
GB2497948A (en) | 2011-12-22 | 2013-07-03 | Thermo Fisher Scient Bremen | Collision cell for tandem mass spectrometry |
JP2015512554A (ja) | 2012-03-23 | 2015-04-27 | マイクロマス ユーケー リミテッド | イオンガイド構築法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19523859C2 (de) * | 1995-06-30 | 2000-04-27 | Bruker Daltonik Gmbh | Vorrichtung für die Reflektion geladener Teilchen |
DE19628179C2 (de) * | 1996-07-12 | 1998-04-23 | Bruker Franzen Analytik Gmbh | Vorrichtung und Verfahren zum Einschuß von Ionen in eine Ionenfalle |
GB0028586D0 (en) * | 2000-11-23 | 2001-01-10 | Univ Warwick | An ion focussing and conveying device |
GB0029088D0 (en) * | 2000-11-29 | 2001-01-10 | Micromass Ltd | Ion tunnel |
GB2370686B (en) * | 2000-11-29 | 2003-10-22 | Micromass Ltd | Mass spectrometers and methods of mass spectrometry |
US7067802B1 (en) * | 2005-02-11 | 2006-06-27 | Thermo Finnigan Llc | Generation of combination of RF and axial DC electric fields in an RF-only multipole |
-
2000
- 2000-11-29 GB GBGB0029088.2A patent/GB0029088D0/en not_active Ceased
-
2001
- 2001-04-20 GB GBGB0109760.9A patent/GB0109760D0/en not_active Ceased
- 2001-11-29 AT AT04026520T patent/ATE495542T1/de not_active IP Right Cessation
- 2001-11-29 DE DE60143861T patent/DE60143861D1/de not_active Expired - Lifetime
- 2001-11-29 EP EP20100183535 patent/EP2302661A1/fr not_active Withdrawn
- 2001-11-29 DE DE60143015T patent/DE60143015D1/de not_active Expired - Lifetime
- 2001-11-29 AT AT01310026T patent/ATE480865T1/de not_active IP Right Cessation
- 2001-11-29 EP EP04026520A patent/EP1505635B1/fr not_active Expired - Lifetime
Non-Patent Citations (2)
Title |
---|
GERLICH D.: "State-Selected and State-to-State Ion-Molecule Reaction Dynamics. Part 1: Experiment", INTERNET CITATION, XP002339690, Retrieved from the Internet <URL:www.tu-chemnitz.de/physik/ion/publications/ger92.pdf> * |
SHAFFER S.A. ET AL: "AN ION FUNNEL INTERFACE FOR IMPROVED ION FOCUSING AND SENSITIVITY USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY", ANALYTICAL CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US LNKD- DOI:10.1021/AC9802170, vol. 70, no. 19, 1 October 1998 (1998-10-01), pages 4111 - 4119, XP000790313, ISSN: 0003-2700 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2302661A1 (fr) * | 2000-11-29 | 2011-03-30 | Micromass UK Limited | Spectromètre de masse ayant un guide d'ions de type tunnel à ions et méthode de spectrométrie de masse. |
Also Published As
Publication number | Publication date |
---|---|
EP2302661A1 (fr) | 2011-03-30 |
GB0029088D0 (en) | 2001-01-10 |
ATE480865T1 (de) | 2010-09-15 |
GB0109760D0 (en) | 2001-06-13 |
EP1505635A3 (fr) | 2007-03-21 |
DE60143861D1 (de) | 2011-02-24 |
ATE495542T1 (de) | 2011-01-15 |
EP1505635A2 (fr) | 2005-02-09 |
DE60143015D1 (de) | 2010-10-21 |
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