EP0573579B1 - Procede de spectrometrie de masse utilisant des signaux de tension ac supplementaires - Google Patents

Procede de spectrometrie de masse utilisant des signaux de tension ac supplementaires Download PDF

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Publication number
EP0573579B1
EP0573579B1 EP92907848A EP92907848A EP0573579B1 EP 0573579 B1 EP0573579 B1 EP 0573579B1 EP 92907848 A EP92907848 A EP 92907848A EP 92907848 A EP92907848 A EP 92907848A EP 0573579 B1 EP0573579 B1 EP 0573579B1
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Prior art keywords
ions
supplemental
frequency
daughter
voltage
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EP92907848A
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German (de)
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EP0573579A1 (fr
EP0573579A4 (fr
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Paul E. Kelley
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TDY Industries LLC
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Teledyne Industries Inc
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    • 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
    • H01J49/0063—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction by applying a resonant excitation voltage
    • 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
    • H01J49/424—Three-dimensional ion traps, i.e. comprising end-cap and ring electrodes
    • 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
    • H01J49/4285—Applying a resonant signal, e.g. selective resonant ejection matching the secular frequency of ions

Definitions

  • the invention relates to mass spectrometry methods in which parent ions within an ion trap are dissociated, and resulting daughter ions are caused to resonate so that they can be detected. More particularly, the invention is a mass spectrometry method in which supplemental AC voltage signals are applied to an ion trap to dissociate parent ions within the trap and to resonate resulting daughter ions for detection.
  • ions (known as “parent ions") having mass-to-charge ratio within a selected range are isolated in an ion trap.
  • the trapped parent ions are then allowed, or induced, to dissociate (for example, by colliding with background gas molecules within the trap) to produce ions known as "daughter ions.”
  • the daughter ions are then ejected from the trap and detected.
  • U.S. Patent 4,736,101 issued April 5, 1988, to Syka, et al., discloses an MS/MS method in which ions (having a mass-to-charge ratio within a predetermined range) are trapped within a three-dimensional quadrupole trapping field.
  • the trapping field is then scanned to eject unwanted parent ions (ions other than parent ions having a desired mass-to-charge ratio) sequentially from the trap.
  • the trapping field is then changed again to become capable of storing daughter ions of interest.
  • the trapped parent ions are then induced to dissociate to produce daughter ions, and the daughter ions are ejected sequentially from the trap for detection.
  • U.S. 4,736,101 teaches that the trapping field should be scanned by sweeping the amplitude of the fundamental voltage which defines the trapping field.
  • U.S. 4,736,101 also teaches that a supplemental AC field can be applied to the trap during the period in which the parent ions undergo dissociation, in order to promote the dissociation process (see column 5, lines 43-62), or to eject a particular ion from the trap so that the ejected ion will not be detected during subsequent ejection and detection of sample ions (see column 4, line 60, through column 5, line 6).
  • U.S. 4,736,101 also suggests (at column 5, lines 7-12) that a supplemental AC field could be applied to the trap during an initial ionization period, to eject a particular ion (especially an ion that would otherwise be present in large quantities) that would otherwise interfere with the study of other (less common) ions of interest.
  • the invention is a mass spectrometry method in which at least one high power supplemental AC voltage signal (having "high” power in the sense that its amplitude is sufficiently large to resonate a selected ion to a degree enabling detection of the ion) is applied to an ion trap, and at least one low power supplemental AC voltage signal (having "low” power in the sense that its amplitude is sufficient to induce dissociation of a selected ion, but insufficient to resonate the ion to a degree enabling it to be detected) is also applied to the ion trap.
  • the frequency of each supplemental AC voltage signal is selected to match a resonance frequency of an ion having a desired mass-to-charge ratio.
  • Each low power supplemental voltage signal is applied for the purpose of dissociating specific ions (i.e., parent ions) within the trap, and each high power supplemental voltage signal is applied to resonate products of the dissociation process (i.e., daughter ions) so that they can be detected.
  • high power voltage signals resonate daughter ions out from the trap for detection by an external detector.
  • each high power voltage signal need only resonate the daughter ions to a degree sufficient for detection within the trap by the in-trap detector (which may comprise one or more of the electrodes which define the trapping field, or may be mounted integrally with such an electrode).
  • Figure 1 is a simplified schematic diagram of an apparatus useful for implementing a class of preferred embodiments of the invention.
  • Figure 2 is a diagram representing signals generated during performance of a first preferred embodiment of the invention.
  • Figure 3 is a diagram representing signals generated during performance of a second preferred embodiment of the invention.
  • Figure 4 is a diagram representing signals generated during performance of a third preferred embodiment of the invention.
  • the quadrupole ion trap apparatus shown in Figure 1 is useful for implementing a class of preferred embodiments of the invention.
  • the Figure 1 apparatus includes ring electrode 11 and end electrodes 12 and 13.
  • a three-dimensional quadrupole trapping field is produced in region 16 enclosed by electrodes 11-13, when fundamental voltage generator 14 is switched on to apply a fundamental RF voltage (having a radio frequency component and optionally also a DC component) between electrode 11 and electrodes 12 and 13.
  • Ion storage region 16 has radius r o and vertical dimension z o .
  • Electrodes 11, 12, and 13 are common mode grounded through coupling transformer 32.
  • Supplemental AC voltage generator 35 can be switched on to apply a desired supplemental AC voltage signal across end electrodes 12 and 13.
  • the supplemental AC voltage signal is selected (in a manner to be explained below in detail) to resonate desired trapped ions at their axial resonance frequencies.
  • Filament 17 when powered by filament power supply 18, directs an ionizing electron beam into region 16 through an aperture in end electrode 12.
  • the electron beam ionizes sample molecules within region 16, so that the resulting ions can be trapped within region 16 by the quadrupole trapping field.
  • Cylindrical gate electrode and lens 19 is controlled by filament lens control circuit 21 to gate the electron beam off and on as desired.
  • end electrode 13 has perforations 23 through which ions can be ejected from region 16 for detection by an externally positioned electron multiplier detector 24.
  • Electrometer 27 receives the current signal asserted at the output of detector 24, and converts it to a voltage signal, which is summed and stored within circuit 28, for processing within processor 29.
  • an in-trap detector is substituted.
  • an in-trap detector can comprise the trap's end electrodes themselves.
  • one or both of the end electrodes could be composed of (or partially composed of) phosphorescent material (which emits photons in response to incidence of ions at one of its surfaces).
  • the in-trap ion detector is distinct from the end electrodes, but is mounted integrally with one or both of them (so as to detect ions that strike the end electrodes without introducing significant distortions in the shape of the end electrode surfaces which face region 16).
  • in-trap ion detector is a Faraday effect detector in which an electrically isolated conductive pin is mounted with its tip flush with an end electrode surface (preferably at a location along the z-axis in the center of end electrode 13).
  • in-trap ion detectors can be employed, such as ion detectors which do not require that ions directly strike them to be detected (examples of this latter type of detector include resonant power absorption detection means, and image current detection means).
  • the output of each in-trap detector is supplied through appropriate detector electronics to processor 29.
  • Control circuit 31 generates control signals for controlling fundamental voltage generator 14, filament control circuit 21, and supplemental AC voltage generator 35. Circuit 31 sends control signals to circuits 14, 21, and 35 in response to commands it receives from processor 29, and sends data to processor 29 in response to requests from processor 29.
  • the first step of this method (which occurs during period "A") is to store parent ions in a trap. This can be accomplished by applying a fundamental voltage signal to the trap (by activating generator 14 of the Figure 1 apparatus) to establish a quadrupole trapping field, and introducing an ionizing electron beam into ion storage region 16. Alternatively, the parent ions can be externally produced and then injected into storage region 16.
  • the fundamental voltage signal is chosen so that the trapping field will store (within region 16) parent ions (for example, parent ions resulting from interactions between sample molecules and the ionizing electron beam) as well as daughter ions (which may be produced during period "B") having mass-to-charge ratio within a desired range.
  • parent ions for example, parent ions resulting from interactions between sample molecules and the ionizing electron beam
  • daughter ions which may be produced during period "B” having mass-to-charge ratio within a desired range.
  • Other ions produced in the trap during period A which have mass-to-charge ratio outside the desired range will escape from region 16, possibly saturating detector 24 as they escape, as indicated by the value of the "ion signal" in Figure 2 during period A.
  • the ionizing electron beam is gated off.
  • a first supplemental AC voltage signal is applied to the trap (such as by activating generator 35 of the Figure 1 apparatus).
  • This voltage signal has a frequency selected to resonantly excite selected daughter ions, and has amplitude (and hence power) sufficiently large to resonate the resonantly excited daughter ions to a degree sufficient to enable them to be detected by an in-trap detector (or by a detector mounted outside the trap).
  • generator 35 While generator 35 continues to apply the first supplemental AC voltage to the trap, generator 35 (or a second supplemental AC voltage generator connected to the appropriate electrode or electrodes) is caused to apply a second supplemental AC voltage signal to the trap.
  • the power (output voltage applied) of the second supplemental AC signal is lower than that of the first supplemental voltage signal (typically, the power of the second supplemental signal is on the order of 100 mV while the power of the first supplemental signal is on the order of 1 V).
  • the second supplemental AC voltage signal has a frequency selected to induce dissociation of a particular parent ion (to produce daughter ions therefrom), but has amplitude (and hence power) sufficiently low that it does not resonate significant numbers of the ions excited thereby out of the trap for detection (in embodiments employing an in-trap ion detection means, the second supplemental signal should have sufficient power to resonantly induce dissociation of selected parent ions, but should have sufficiently low power that it does not cause the trajectories of significant numbers of the ions it excites to become large enough for in-trap detection).
  • the frequency of the second supplemental AC signal is changed to induce dissociation of different parent ions.
  • Each daughter ion produced during this frequency scan that happens to have a resonance frequency matching the frequency of the first supplemental signal will be resonated out of the trap for detection (or will be resonated sufficiently for detection by an in-trap detector comprising, or integrally mounted with, a trap electrode).
  • the "ion signal" portion shown within period B of Figure 2 has four peaks, each representing detected daughter ions (having a common resonance frequency) resulting from sequential dissociation of four different types of parent ions.
  • An alternative way to induce dissociation of several different parent ions is to keep the frequency of the second supplemental AC signal fixed, but to change the trapping field parameters (i.e., one or more of the frequency or amplitude of the AC component of the fundamental RF voltage, or the amplitude of the DC component of the fundamental RF voltage).
  • the trapping field parameters i.e., one or more of the frequency or amplitude of the AC component of the fundamental RF voltage, or the amplitude of the DC component of the fundamental RF voltage.
  • the first or the second supplemental AC voltage signal (or both of them) has two or more different frequency components within a selected frequency range. Each such frequency component should have frequency and amplitude characteristics of the type described above with reference to Figure 2.
  • the first step of this embodiment (which occurs during period "A") is to store parent ions in a trap.
  • This can be accomplished by applying a fundamental voltage signal to the trap (by activating generator 14 of the Figure 1 apparatus) to establish a quadrupole trapping field, and introducing an ionizing electron beam into ion storage region 16.
  • the quadrupole trapping field is established and externally produced parent ions are injected into storage region 16.
  • the fundamental voltage signal is chosen so that the trapping field will store (within region 16) daughter ions (which may be produced within the trap after period A) as well as parent ions, all having mass-to-charge ratio within a desired range.
  • Other ions including ions resulting from interactions with the electron beam during period A), having mass-to-charge ratio outside the desired range, will escape from region 16 (possibly saturating detector 24 as they escape, as indicated by the value of the "ion signal" in Figure 3 during period A).
  • the ionizing electron beam is gated off.
  • a first supplemental AC voltage signal is applied to the trap (such as by activating generator 35 of the Figure 1 apparatus).
  • This voltage signal has a frequency (f P1 ) selected to induce dissociation of a first parent ion (P1), but has amplitude (and hence power) sufficiently low that it does not resonate significant numbers of the ions excited thereby to a degree sufficient for in-trap or out-of-trap detection.
  • the first supplemental AC voltage signal is switched off, and a "daughter" supplemental AC voltage signal is applied to the trap to resonate daughters of the first parent ion out of the trap for detection (or to resonate them sufficiently to enable them to be detected by an in-trap detector).
  • the "ion signal" portion shown within period B of Figure 3 has a peak representing detected daughter ions resulting from dissociation of the first parent ion during application of the first supplemental signal.
  • a set of two or more daughter supplemental AC voltage signals can be applied to the trap during period B.
  • Each signal in this set should have a frequency selected to resonate a different daughter of the first parent ion for detection (by an in-trap or out-of-trap detector).
  • An identical set of daughter supplemental AC voltage signals can be applied to the trap during each of periods C, D, and E (to be discussed below).
  • each daughter ion will differ from the frequency of its parent ion.
  • the frequency of each daughter supplemental AC voltage signal will differ from the frequency of the low power supplemental AC voltage signal (i.e., the "first" supplemental AC voltage signal mentioned above, or the "second,” “third,” or “fourth” supplemental AC voltage signal to be discussed with reference to periods “C,” “D,” and “E” of Figure 3) applied to dissociate the parent of the daughter ion to be resonated by the daughter supplemental AC voltage signal.
  • the trapping field parameters i.e., one or more of the frequency or amplitude of the AC component of the fundamental RF voltage, or the amplitude of the DC component of the fundamental RF voltage
  • the frequency of each daughter ion is correspondingly changed, and indeed the frequency of each daughter ion can be caused to match the frequency of the low power supplemental AC signal.
  • both the daughter supplemental AC voltage signal and the low power supplemental AC voltage signal can have the same frequency (although these two supplemental AC voltage signals are applied to "different" trapping fields).
  • a second supplemental AC voltage signal is applied to the trap (such as by activating generator 35 of the Figure 1 apparatus).
  • This voltage signal has a different frequency (f P2 ) selected to induce dissociation of a second parent ion (P2), but has amplitude sufficiently low that it does not resonate significant numbers of the ions excited thereby to a degree sufficient for in-trap or out-of-trap detection.
  • the second supplemental voltage signal is switched off, and the daughter supplemental AC voltage signal (or set of daughter supplemental AC voltage signals) is again applied to the trap to resonate daughters of the second parent ion for detection by an in-trap or out-of-trap detector.
  • Figure 3 reflects the possibility that no such daughter ions of interest will have been produced in response to application of the second supplemental signal.
  • the ion signal portion shown within period C of Figure 3 has no peak representing detected daughter ions produced by dissociation of second parent ions during application of the second supplemental signal.
  • a third supplemental AC voltage signal is applied to the trap (such as by activating generator 35 of the Figure 1 apparatus).
  • This voltage signal has a frequency (f P3 ) selected to induce dissociation of a third parent ion (P3), but has amplitude (and hence power) sufficiently low that it does not resonate significant numbers of the ions excited thereby to a degree sufficient for in-trap or out-of-trap detection.
  • the third supplemental voltage signal is switched off, and the daughter supplemental AC voltage signal (or set of daughter supplemental AC voltage signals) is again applied to the trap to resonate daughters of the third parent ion for detection by an in-trap or out-of-trap detector.
  • the "ion signal" portion shown within period D of Figure 3 has a peak representing detected daughter ions resulting from dissociation of the third parent ions during application of the third supplemental signal.
  • a fourth supplemental AC voltage signal is applied to the trap (such as by activating generator 35 of the Figure 1 apparatus).
  • This voltage signal has a different frequency (f P4 ) selected to induce dissociation of a fourth parent ion (P4), but has amplitude sufficiently low that it does not resonate significant numbers of the ions it excites to a degree sufficient for them to be detected.
  • the fourth supplemental voltage signal is switched off, and the daughter supplemental AC voltage signal (or set of daughter supplemental AC voltage signals) is again applied to the trap to resonate daughters of the fourth parent ions out of the trap for detection (or to resonate them sufficiently for detection by an in-trap detector).
  • Figure 3 reflects the possibility that no such daughter ions will have been produced in response to application of the fourth supplemental signal.
  • the ion signal portion shown within period E of Figure 3 has no peak representing detected daughter ions.
  • all or some of the supplemental AC voltage signals have two or more different frequency components within a selected frequency range. Each such frequency component should have frequency and amplitude characteristics of the type described above with reference to Figure 3.
  • the first step of this embodiment (which occurs during period "A") is to store parent ions in a trap.
  • This can be accomplished by applying a fundamental voltage signal to the trap (by activating generator 14 of the Figure 1 apparatus) to establish a quadrupole trapping field, and introducing an ionizing electron beam into ion storage region 16.
  • the quadrupole trapping field is established and externally produced parent ions are injected into storage region 16.
  • the fundamental voltage signal is chosen so that the trapping field will store (within region 16) daughter ions (which may be produced within the trap after period A) as well as parent ions, all having mass-to-charge ratio within a desired range.
  • Other ions including ions resulting from interactions with the electron beam during period A), having mass-to-charge ratio outside the desired range, will escape from region 16 (possibly saturating detector 24 as they escape, as indicated by the value of the "ion signal" in Figure 4 during period A).
  • the ionizing electron beam is gated off.
  • a first supplemental AC voltage signal is applied to the trap (such as by activating generator 35 of the Figure 1 apparatus).
  • This voltage signal has a frequency (f P1-N ) selected to resonantly excite a first ion (having molecular weight P1-N), and has enough power (i.e., sufficient amplitude) to resonate the first ion to a degree enabling it to be detected (by an external detector or an in-trap detector).
  • the Figure 4 method is particularly useful for analyzing "neutral loss” daughter ions.
  • a neutral loss daughter ion results from dissociation of a parent ion into two components: a daughter molecule (for example, a water molecule) having zero (neutral) charge and a molecular weight N (N will sometimes be denoted herein as a "neutral loss mass”); and a neutral loss daughter ion having a molecular weight P-N, where P is the molecular weight of the parent ion.
  • the first supplemental signal resonates ions having the same mass-to-charge ratio as do neutral loss daughter ions later produced during application of the second supplemental voltage signal (having frequency f P1 ).
  • the first supplemental voltage signal is switched off, and a second supplemental AC voltage signal is applied to the trap.
  • the second supplemental AC voltage signal has frequency selected to induce dissociation of a first parent ion having molecular mass P1.
  • the power of the second supplemental AC signal is lower than that of the first supplemental voltage signal (typically, it is on the order of 100 mV, while the power of the first supplemental voltage signal is on the order of 1 V).
  • the power of the second supplemental AC voltage signal is sufficiently low that this signal does not resonate significant numbers of the ions it excites to a degree sufficient for them to be detected.
  • a third supplemental AC signal is applied to the trap.
  • the third supplemental AC signal has frequency (f P1-N ), and amplitude sufficient to resonate neutral loss daughter ions having molecular weight P1-N (produced earlier during period B during application of the second supplemental voltage signal) to a degree sufficient for in-trap or out-of-trap detection.
  • the ion signal portion present during period B of Figure 4 has two peaks, which occur during application of the first and third supplemental voltage signals.
  • the second peak can unambiguously be interpreted to represent neutral loss daughter ions produced during application of the second supplemental signal, even though the first peak cannot confidently be interpreted to represent neutral loss daughter ions resulting from dissociation of the first parent ion.
  • fourth, fifth, and sixth supplemental AC voltage signals are sequentially applied to the trap, to enable detection of neutral loss daughter ions (having molecular weight P2-N) resulting from dissociation of a second parent ion (having molecular weight P2).
  • the fourth and sixth supplemental voltage signals have frequency (f P2-N ) selected to resonantly excite a second ion (having molecular weight P2-N), and has enough power to resonate the second ion to a degree enabling it to be detected (by an external detector or an in-trap detector).
  • the fifth supplemental AC voltage signal has frequency selected to induce dissociation of a second parent ion having molecular mass P2.
  • the power of the fifth supplemental AC signal is lower than that of the fourth and sixth supplemental voltage signals (typically, it is on the order of 100 mV), and is sufficiently low that the fifth supplemental signal does not resonate significant numbers of the ions it excites to a degree sufficient for them to be detected.
  • the sixth supplemental AC signal is applied to the trap.
  • the sixth supplemental AC signal has frequency (f P2-N ), and amplitude sufficient to resonate neutral loss daughter ions having molecular weight P2-N (produced earlier during period C during application of the fourth supplemental voltage signal) to a degree enabling them to be detected.
  • Figure 4 reflects the possibility that no such neutral daughter ions will have been produced in response to application of the fifth supplemental signal.
  • the ion signal portion occurring during application of the sixth supplemental signal (within period C of Figure 4) has no peak representing detected neutral loss daughter ions produced by dissociation of the second parent ion during application of the fifth supplemental signal, although the ion signal does have a peak representing sample ions detected during application of the fourth supplemental signal.
  • seventh, eighth, and ninth supplemental AC voltage signals are sequentially applied to the trap, to enable detection of neutral loss daughter ions (having molecular weight P3-N) resulting from dissociation of a third parent ion (having molecular weight P3).
  • the seventh and ninth supplemental voltage signals have frequency (f P3-N ) selected to resonantly excite a third ion (having molecular weight P3-N), and each has enough power to resonate the third ion to a degree enabling it to be detected (by an external detector or an in-trap detector).
  • the eighth supplemental AC voltage signal has frequency selected to induce dissociation of a third parent ion having molecular mass P3.
  • the power of the eighth supplemental AC signal is lower than that of the seventh and ninth supplemental voltage signals (typically, it is on the order of 100 mV), and is sufficiently low that the eighth supplemental signal does not resonate significant numbers of the ions it excites to a degree sufficient for them to be detected.
  • the ninth supplemental AC signal is applied to the trap.
  • the ninth supplemental AC signal has frequency (f P3-N ), and amplitude sufficient to resonate neutral loss daughter ions having molecular weight P3-N (produced during application of the seventh supplemental voltage signal) to a degree enabling them to be detected.
  • the ion signal portion occurring during application of the ninth supplemental signal (within period D of Figure 4) has a peak representing detected neutral loss daughter ions produced by dissociation of the third parent ion during application of the eighth supplemental signal, although the ion signal has no peak representing ions detected during application of the seventh supplemental signal.
  • each neutral loss daughter ion will differ from the frequency of its parent ion.
  • the frequency of each high power supplemental AC voltage signal applied during one of periods "B,” “C,” or “D” of Figure 4 will differ from the frequency of the low power supplemental AC voltage signal applied during the same period of Figure 4.
  • the frequency of each neutral loss daughter ion (the frequency at which each neutral loss daughter ion moves in the trapping field) is correspondingly changed, and indeed the frequency of each neutral loss daughter ion can be caused to match the frequency of the low power supplemental AC signal.
  • both the high power supplemental AC voltage signal and the low power supplemental AC voltage signal can have the same frequency (although these two supplemental AC voltage signals are applied to "different" trapping fields).
  • granddaughter ions are produced in ion region 16 and then detected (rather than daughter ions).
  • the second (low power) supplemental AC voltage signal can consist of an earlier portion followed by a later portion: the earlier portion having frequency selected to induce production of a daughter ion (by dissociating the parent ion); and the later portion having frequency selected to induce production of a granddaughter ion (by dissociating the daughter ion).
  • the frequency of the first (high power) supplemental AC voltage signal applied in period B is selected to match a resonance frequency of the granddaughter ion (rather than the daughter ion).
  • the first (low power) supplemental AC voltage signal consists of an earlier portion followed by a later portion: the earlier portion having frequency selected to induce production of a daughter ion (by dissociating the first parent ion); and the later portion having frequency selected to induce production of a granddaughter ion (by dissociating the daughter ion).
  • the frequency of the second (high power) supplemental AC voltage signal applied in period B is selected to match a resonance frequency of the granddaughter ion (rather than the daughter ion).
  • aughter ion is intended to denote granddaughter ions (second generation daughter ions) and subsequent (third or later) generation daughter ions, as well as “first generation” daughter ions.
  • At least one of the "daughter" supplemental AC voltage signals is applied twice: once immediately prior to one of the first, second, third, or fourth (low power) supplemental AC voltage signals, and again immediately after the same one of the first, second, third, or fourth (low power) supplemental AC voltage signals.
  • the purpose of each such "preliminary" application of the daughter signal (or set of signals) is to resonate ions having the same mass-to-charge ratio as do daughter ions to be produced later during application of the immediately following low power supplemental voltage signal (as in the embodiment of the invention described with reference to Figure 4).

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Claims (16)

  1. Procédé de spectrométrie de masse incluant les étapes :
    d'établissement d'un premier champ de piégeage (16) et de piégeage d'ions pères qui s'y trouvent ;
    d'application d'une tension supplémentaire à des électrodes (12, 13) du champ de piégeage (16) ;
    d'obtention d'un spectre de masse à partir d'ions dans le piège ;
       caractérisé en ce que ladite tension supplémentaire est une tension alternative supplémentaire à basse puissance et une tension alternative supplémentaire à haute puissance, la tension alternative supplémentaire à basse puissance étant d'une fréquence propre à dissocier les ions pères et, si on le souhaite, également des ions fils, et la tension alternative supplémentaire à haute puissance étant d'une fréquence propre à exciter de façon résonnante les ions fils et, si on le souhaite, également des ions petits-fils, et d'une amplitude suffisante pour permettre la détection de ces ions fils et petits-fils.
  2. Procédé de spectrométrie de masse selon la revendication 1, incluant les étapes :
    a) d'application de la tension alternative supplémentaire à basse puissance avec une première fréquence correspondant à une fréquence de résonance de premiers ions pères ; et
    b) d'application de la tension alternative supplémentaire à haute puissance avec une deuxième fréquence correspondant à la fréquence de résonance des premiers ions fils ;
    c) de modification de la fréquence de la tension alternative supplémentaire à basse puissance pour induire une dissociation de seconds ions pères ;
    d) d'application de la tension alternative supplémentaire à haute puissance avec la deuxième fréquence pour faire résonner des ions fils produits pendant l'étape c) à un degré suffisant pour leur détection.
  3. Procédé de spectrométrie de masse selon la revendication 2, dans lequel les tensions alternatives supplémentaires à haute et basse puissances sont appliquées simultanément, la tension alternative supplémentaire à haute puissance ayant des fréquences, chacune, choisies pour exciter de façon résonnante des ions fils choisis.
  4. Procédé de spectrométrie de masse selon la revendication 2, dans lequel les tensions alternatives supplémentaires à haute et basse puissances sont appliquées de manière successive, la tension alternative supplémentaire à basse puissance ayant des fréquences prévues pour dissocier des ions pères qui forment des classes différentes (P1, P2, P3, P4).
  5. Procédé de spectrométrie de masse selon l'une quelconque des revendications 1 à 4, dans lequel le premier champ de piégeage est changé en un second champ de piégeage dans lequel le premier ion fils a une deuxième fréquence de résonance qui est sensiblement égale à la fréquence de la tension alternative supplémentaire à haute puissance.
  6. Procédé de spectrométrie de masse selon la revendication 5, dans lequel la première fréquence de la tension alternative supplémentaire à basse puissance est différente de la deuxième fréquence.
  7. Procédé de spectrométrie de masse selon la revendication 5, dans lequel le premier champ de piégeage est changé après l'étape a) de la revendication 2, et dans lequel la première fréquence est sensiblement égale à la deuxième fréquence.
  8. Procédé de spectrométrie de masse selon l'une quelconque des revendications 1 à 7, dans lequel les ions fils sont éjectés de façon résonnante par la tension alternative supplémentaire à haute puissance de la région de piège (16) et sont détectés au droit d'un détecteur (24) placé à l'extérieur de la région de piège (16).
  9. Procédé de spectrométrie de masse selon l'une quelconque des revendications 1 à 7, dans lequel les ions fils sont excités de façon résonnante par la tension alternative supplémentaire à haute puissance jusqu'à un degré suffisant pour une détection interne au piège par un détecteur interne au piège.
  10. Procédé de spectrométrie de masse selon la revendication 1, incluant, en outre, les étapes :
    a) d'application d'un signal de tension alternative supplémentaire à haute puissance aux électrodes pour faire résonner des premiers ions ayant un premier rapport de masse-à-charge à un degré suffisant pour permettre la détection desdits premiers ions ;
    b) après l'étape a), d'application, aux électrodes, d'un signal de tension alternative supplémentaire à basse puissance pour induire la dissociation des premiers ions pères pour produire des premiers ions fils, le signal de tension alternative à basse puissance ayant une première fréquence correspondant à une fréquence de résonance des premiers ions pères, les ions fils ayant une première fréquence de résonance dans le champ de piégeage, et les premiers ions fils ayant un premier rapport de masse-à-charge ;
    c) après l'exécution de l'étape b), d'application, aux électrodes, d'un deuxième signal de tension alternative supplémentaire à haute puissance pour faire résonner les premiers ions fils à un degré suffisant pour permettre la détection des premiers ions fils, le deuxième signal de tension alternative supplémentaire à haute puissance ayant une deuxième fréquence correspondant à une fréquence de résonance des premiers ions fils ; et
    d) après l'étape a), mais avant l'étape b), de changement du champ de piégeage en un second champ de piégeage dans lequel les ions fils ont une deuxième fréquence de résonance, la deuxième fréquence de résonance étant sensiblement égale à la deuxième fréquence.
  11. Procédé selon la revendication 10, dans lequel les premiers ions pères ont un poids moléculaire (P1) ; et
       dans lequel les premiers ions et les premiers ions fils ont un poids moléculaire (P1 - N), où (N) est une masse de perte neutre.
  12. Procédé selon la revendication 10, dans lequel la première fréquence est différente de la deuxième fréquence.
  13. Procédé selon la revendication 10, dans lequel les seconds ions pères ont aussi été piégés dans la région de piège, et comprenant aussi les étapes :
    e) après l'étape d), d'application, aux électrodes, d'un troisième signal de tension alternative supplémentaire à haute puissance pour faire résonner des seconds ions ayant un second rapport de masse-à-charge à un degré suffisant pour permettre la détection desdits seconds ions ;
    f) après l'étape e), d'application, aux électrodes, d'un second signal de tension alternative supplémentaire à basse puissance pour induire la dissociation des seconds ions pères pour produire des seconds ions fils, le second signal de tension alternative supplémentaire à basse puissance ayant une troisième fréquence correspondant à une fréquence de résonance des seconds ions pères, et les premiers ions fils ayant le second rapport de masse-à-charge ; et
    g) après l'exécution de l'étape f), d'application, aux électrodes, d'un quatrième signal de tension alternative supplémentaire à haute puissance pour faire résonner les seconds ions fils à un degré suffisant pour permettre la détection des seconds ions fils, le quatrième signal de tension alternative supplémentaire à haute puissance ayant une quatrième fréquence correspondant à une fréquence de résonance des seconds ions fils.
  14. Procédé selon la revendication 13, dans lequel les premiers ions pères ont un poids moléculaire (P1) dans lequel les premiers ions et les premiers ions fils ont un poids moléculaire (P1 - N), où (N) est une masse de perte neutre, les seconds ions pères ayant un poids moléculaire (P2) et les seconds ions et les seconds ions fils ayant un poids moléculaire (P2 - N).
  15. Procédé selon la revendication 10, comprenant en outre les étapes :
    e) après l'étape d), d'application, aux électrodes, d'un signal de tension alternative supplémentaire à basse puissance pour induire la dissociation d'un ion père piégé, le signal de tension alternative supplémentaire à basse puissance ayant une fréquence correspondant à une fréquence de résonance de l'ion père piégé ; et
    f) après l'étape e), d'application, aux électrodes, d'un signal de tension alternatif supplémentaire à haute puissance pour faire résonner un ion fixe à un degré suffisant pour permettre la détection des ions fils, le signal de tension alternative supplémentaire à haute puissance ayant une fréquence correspondant à une fréquence de résonance de l'ion fils.
  16. Procédé selon l'une quelconque des revendications 1 à 15, dans lequel le signal de tension alternative supplémentaire à basse puissance a une puissance de l'ordre de 100 millivolts, et le signal de tension alternative supplémentaire à haute puissance a une puissance de l'ordre de 1 volt.
EP92907848A 1991-02-28 1992-02-11 Procede de spectrometrie de masse utilisant des signaux de tension ac supplementaires Expired - Lifetime EP0573579B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US66219191A 1991-02-28 1991-02-28
PCT/US1992/001104 WO1992015392A1 (fr) 1991-02-28 1992-02-11 Procede de spectrometrie de masse utilisant des signaux de tension supplementaires
US662191 2000-09-14

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EP0573579A1 EP0573579A1 (fr) 1993-12-15
EP0573579A4 EP0573579A4 (fr) 1995-08-09
EP0573579B1 true EP0573579B1 (fr) 1997-04-16

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JP (1) JP2743034B2 (fr)
AT (1) ATE151915T1 (fr)
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US5200613A (en) * 1991-02-28 1993-04-06 Teledyne Mec Mass spectrometry method using supplemental AC voltage signals
US5381007A (en) * 1991-02-28 1995-01-10 Teledyne Mec A Division Of Teledyne Industries, Inc. Mass spectrometry method with two applied trapping fields having same spatial form
GB2267385B (en) * 1992-05-29 1995-12-13 Finnigan Corp Method of detecting the ions in an ion trap mass spectrometer

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DE3688215T3 (de) 1985-05-24 2005-08-25 Thermo Finnigan Llc, San Jose Steuerungsverfahren für eine Ionenfalle.
US4749860A (en) * 1986-06-05 1988-06-07 Finnigan Corporation Method of isolating a single mass in a quadrupole ion trap

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CA2101152C (fr) 1999-03-30
EP0573579A1 (fr) 1993-12-15
DE69219113T2 (de) 1997-11-20
JPH06508469A (ja) 1994-09-22
DK0573579T3 (da) 1997-10-20
WO1992015392A1 (fr) 1992-09-17
JP2743034B2 (ja) 1998-04-22
DE69219113D1 (de) 1997-05-22
ATE151915T1 (de) 1997-05-15
ES2106177T3 (es) 1997-11-01
EP0573579A4 (fr) 1995-08-09
CA2101152A1 (fr) 1992-08-29

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