WO1997047025A1 - Spectrometre de masse multipolaire a ejection axiale - Google Patents

Spectrometre de masse multipolaire a ejection axiale Download PDF

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Publication number
WO1997047025A1
WO1997047025A1 PCT/CA1997/000381 CA9700381W WO9747025A1 WO 1997047025 A1 WO1997047025 A1 WO 1997047025A1 CA 9700381 W CA9700381 W CA 9700381W WO 9747025 A1 WO9747025 A1 WO 9747025A1
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WIPO (PCT)
Prior art keywords
ions
rod set
field
voltage
rods
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Application number
PCT/CA1997/000381
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English (en)
Inventor
James W. Hager
Original Assignee
Mds, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mds, Inc. filed Critical Mds, Inc.
Priority to EP97923686A priority Critical patent/EP0902963B1/fr
Priority to DE69715190T priority patent/DE69715190T2/de
Priority to JP53747397A priority patent/JP3818671B2/ja
Priority to AU29461/97A priority patent/AU718774B2/en
Priority to CA002256028A priority patent/CA2256028C/fr
Publication of WO1997047025A1 publication Critical patent/WO1997047025A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/426—Methods for controlling ions
    • H01J49/427—Ejection and selection methods
    • 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
    • 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
    • H01J49/422—Two-dimensional RF ion traps
    • H01J49/4225—Multipole linear ion traps, e.g. quadrupoles, hexapoles

Definitions

  • This invention relates to a multipole elongated rod ion trap mass spectrometer with axial ejection.
  • Conventional ion traps are generally composed of three electrodes, namely a ring electrode, and a pair of end caps, with appropriate RF and DC voltages applied to these electrodes to establish a three-dimensional field which traps ions within a mass range of interest in the relatively small volume between the ring electrode and the end caps.
  • the electrodes may be hyperbolic, producing a theoretically perfect three-dimensional quadrupole field, or they may deviate from hyperbolic geometry, giving rise to additional multipole fields superimposed on the quadrupole field and which can produce improved results.
  • ion trap mass spectrometers are filled in an essentially mass-independent manner and are emptied mass-dependently by manipulating the RF and DC voltages applied to one or more of the electrodes.
  • the ion storage and fast scanning capabilities of the ion trap are advantageous in analytical mass spectrometry.
  • High analysis efficiency compared to typical beam-type mass spectrometers, can be achieved if the time to eject and detect ions from the trap is smaller than the time required to fill a trap. If this condition is met, then very few ions are wasted.
  • an inherent disadvantage of ion traps is that ion transport into the trap is usually of very low efficiency, e.g.
  • the relatively small volume of the ion trap means that the number of ions that can be accepted before space charge effects become serious is also relatively small.
  • Increasing the radial dimension of the volume of the trapping chamber of a conventional ion trap partially overcomes this limitation, but with the additional disadvantages of reduced analytical utility and/or increased costs (e.g. reduced mass range, larger power supplies).
  • the small volume of the ion trapping chamber will also tend to limit the linear response range (i.e. dynamic range), again because of the effects of space charge at high ion densities.
  • ions can be trapped and stored very efficiently in a two-dimensional RF quadrupole.
  • ions have been admitted into and then trapped in a two-dimensional quadrupole for purposes of releasing them into a conventional ion trap, as shown in U.S. patent 5,179,278.
  • More generally ions have been admitted into a pressurized linear cell or a two-dimensional RF quadrupole for the purpose of studying ion molecule reactions.
  • the ions enter the device from a mass selective source such as a resolving quadrupole, are trapped for a specified period of time, and then are ejected mass- independently for subsequent mass analysis.
  • U.S. patent 5,420,425 teaches that ions can be trapped and stored in a two-dimensional RF quadrupole and scanned out mass- dependently, using the technique of mass selective instability.
  • the device disclosed therein was conceived in order to improve ion sensitivities, detection limits, and dynamic range, by increasing the volume of the trapping chamber in the axial dimension.
  • the mass selective instability mode of ion ejection (and all other mass analysis scanning modes described in U.S. patent 5,420,425) involve ejecting ions out of the trapping chamber in a direction orthogonal to the center axis of the device, i.e. radially.
  • radial ejection of ions from a two-dimensional RF quadrupole there are several disadvantages of radial ejection of ions from a two-dimensional RF quadrupole.
  • One disadvantage is that radial ejection expels ions through or between the quadrupole (or higher order multipole) rods. This forces the ions through regions of space for which there are significant RF field imperfections. The effect of these imperfections is to eject ions at points not predicted by the normal stability diagram.
  • Radial ejection from a two-dimensional RF quadrupole has the further disadvantage of providing a poor match between the dimensions of the plug of ejected ions and conventional ion detectors.
  • radially ejected ions will exit throughout the length of the device, i.e. with a rectangular cross-section of length corresponding to the rods themselves.
  • Most conventional ion detectors have relatively small circular acceptance apertures (e.g. less than 2 cm 2 ) that are not well-suited for elongated ion sources.
  • Mass selective instability for radial ion ejection of ions from a two-dimensional RF quadrupole has additional problems. Ions ejected radially from such a device will exit with a diverging spatial profile with a characteristic solid angle. Some of the ejected ions will hit the rods and be lost. In addition, radially ejected ions will leave the trapping structure in opposite directions. Multiple ion detectors would be required to collect all of the ions made unstable by this and similar techniques. Ions ejected away from the detector(s) or which encounter one of the electrodes are lost and therefore do not contribute to the measured ion signal. Therefore only a small fraction of trapped ions would normally be collected, despite the very high storage ability of this device.
  • the invention provides a method of operating a mass spectrometer having an elongated rod set, said rod set having an entrance end and an exit end and a longitudinal axis, said method comprising:
  • Fig. 1 is a diagrammatic view of a simple mass spectrometer apparatus with which the present invention may be used;
  • Fig. la is an end view of a rod set of Fig. 1 and showing electrical connections to such rod set;
  • Fig. 2 is a diagrammatic view of a modification of a part of the apparatus of Fig. 1;
  • Fig. 3 is a diagrammatic view of a further modification of the apparatus of Fig. 1;
  • Fig. 4 is a diagrammatic view of another modification of the
  • Fig. 5 is a graph showing results obtained with the apparatus of Fig. 4.
  • Fig. 6 is a graph showing further results obtained with the Fig. 4 apparatus
  • Fig. 7 is an end view of rods which can be used as an exit lens.
  • Fig. 8 is a plan view of a modified exit lens.
  • Fig. 1 shows a mass analyzer system 10 with which the invention may be used.
  • the system 10 includes a sample source 12 (normally a liquid sample source such as a liquid chromatograph) from which sample is supplied to a conventional ion source 14.
  • Ion source 14 may be an electrospray, an ion spray, or a corona discharge device, or any other known ion source.
  • An ion spray device of the kind shown in U.S. patent 4,861,988 issued August 29, 1989 to Cornell Research Foundation Inc. is suitable.
  • Ions from ion source 14 are directed through an aperture 16 in an aperture plate 18.
  • Plate 18 forms one wall of a gas curtain chamber 19 which is supplied with curtain gas from a curtain gas source 20.
  • the curtain gas can be argon, nitrogen or other inert gas and is described in the above-mentioned U.S. patent 4,861,988.
  • the ions then pass through an orifice 22 in an orifice plate 24 into a first stage vacuum chamber 26 evacuated by a pump 28 to a pressure of about 1 Torr.
  • the ions then pass through a skimmer orifice 30 in a skimmer plate 32 and into a main vacuum chamber 34 evacuated to a pressure of about 2 milli-Torr by a pump 36.
  • the main vacuum chamber 34 contains a set of four linear conventional quadrupole rods 38.
  • an exit lens 42 Located about 2mm past the exit ends 40 of the rods 38 is an exit lens 42.
  • the lens 42 is simply a plate with an aperture 44 therein, allowing passage of ions through aperture 44 to a conventional detector 46 (which may for example be a channel electron multiplier of the kind conventionally used in mass spectrometers).
  • the rods 38 are connected to the main power supply 50 which applies a DC rod offset to all the rods 38 and also applies RF in conventional manner between the rods.
  • the power supply 50 is also connected (by connections not shown) to the ion source 14, the aperture and orifice plates 18 and 24, the skimmer plate 32, and to the exit lens 42.
  • the ion source 14 may typically be at +5,000 volts, the aperture plate 18 may be at +1,000 volts, the orifice plate 24 may be at +250 volts, and the skimmer plate 32 may be at ground (zero volts).
  • the DC offset applied to rods 38 may be -5 volts.
  • the axis of the device, which is the path of ion travel, is indicated at 52.
  • ions of interest which are admitted into the device from ion source 14 move down a potential well and are allowed to enter the rods 38.
  • Ions that are stable in the applied main RF field applied to the rods 38 travel the length of the device undergoing numerous momentum dissipating collisions with the background gas.
  • a trapping DC voltage typically -2 volts DC
  • the exit lens 42 Normally the ion transmission efficiency between the skimmer 32 and the exit lens 42 is very high and may approach 100%.
  • Ions that enter the main vacuum chamber 34 and travel to the exit lens 42 are thermalized due to the numerous collisions with the background gas and have little net velocity in the direction of axis 52.
  • the ions also experience forces from the main RF field which confines them radially.
  • the RF voltage applied is in the order of about 450 volts (unless it is scanned with mass) and is of a frequency of the order of about 816 kHz. No resolving DC field is applied to rods 38.
  • ions in region 54 in the vicinity of the exit lens 42 will experience fields that are not entirely quadrupolar, due to the nature of the termination of the main RF and DC fields near the exit lens. Such fields, commonly referred to as fringing fields, will tend to couple the radial and axial degrees of freedom of the trapped ions. This means that there will be axial and radial components of ion motion that are not mutually orthogonal. This is in contrast to the situation at the center of rod structure 38 further removed from the exit lens and fringing fields, where the axial and radial components of ion motion are not coupled or are minimally coupled.
  • ions may be scanned out of the ion trap constituted by rods 38, by the application to the exit lens 42 of a low voltage auxiliary AC field of appropriate frequency.
  • the auxiliary AC field may be provided by an auxiliary AC supply 56, which for illustrative purposes is shown as forming part of the main power supply 50.
  • the auxiliary AC field is an addition to the trapping DC voltage supplied to exit lens 42 and couples to both the radial and axial secular ion motions.
  • the auxiliary AC field is found to excite the ions sufficiently that they surmount the axial DC potential barrier at the exit lens 42, so that they can leave axially in the direction of arrow 58.
  • the deviations in the field in the vicinity of the exit lens 42 lead to the above described coupling of axial and radial ion motions enabling the axial ejection at radial secular frequencies. This is in contrast to the situation existing in a conventional ion trap, where excitation of radial secular motion will generally lead to radial ejection and excitation of axial secular motion will generally lead to axial ejection, unlike the situation described above.
  • ion ejection in a sequential mass dependent manner can be accomplished by scanning the frequency of the low voltage auxiliary AC field.
  • the frequency of the auxiliary AC field matches a radial secular frequency of an ion in the vicinity of the exit lens 42, the ion will absorb energy and will now be capable of traversing the potential barrier present on the exit lens due to the radial /axial motion coupling.
  • the ion exits axially, it will be detected by detector 46.
  • other ions upstream of the region 54 in the vicinity of the exit lens are energetically permitted to enter the region 54 and be excited by subsequent AC frequency scans.
  • Ion ejection by scanning the frequency of the auxiliary AC voltage applied to the exit lens is desirable because it does not empty the trapping volume of the entire elongated rod structure 38.
  • the RF voltage on the rods would be ramped and ions would be ejected from low to high masses along the entire length of the rods when the q value for each ion reaches a value of 0.907. After each mass selective instability scan, time is required to refill the trapping volume before another analysis can be performed.
  • auxiliary AC voltage when an auxiliary AC voltage is applied to the exit lens as described above, ion ejection will normally only happen in the vicinity of the exit lens because this is where the coupling of the axial and radial ion motions occurs and where the auxiliary AC voltage is applied.
  • the upstream portion 60 of the rods serves to store other ions for subsequent analysis.
  • the time required to refill the volume 54 in the vicinity of the exit lens with ions will always be shorter than the time required to refill the entire trapping volume. Therefore fewer ions will be wasted.
  • the auxiliary AC voltage on end lens 42 instead of scanning the auxiliary AC voltage applied to end lens 42, the auxiliary AC voltage on end lens 42 can be fixed and the main RF voltage applied to rods 38 can be scanned in amplitude, as will be described.
  • a q of only about 0.2 to 0.3 is needed for axial ejection, while a q of about 0.8 to 0.907 is needed for radial ejection. Therefore, as will be explained, few if any ions are lost to radial ejection if the RF voltage is scanned through an appropriate amplitude range, except possibly for very low mass ions.
  • a further supplementary or auxiliary AC dipole voltage may be applied to rods 38 (as indicated by dotted connection 57 in Fig. 1) and scanned, to produce varying fringing fields which will eject ions axially in the manner described.
  • the dipole voltage is usually applied between an opposed pair of the rods 38, as indicated in Fig. la.
  • a combination of some or all of the above three approaches can be used to eject ions axially and mass dependency past the DC potential barrier present at the end lens 42.
  • the device illustrated may be operated in a continuous fashion, in which ions entering the main RF containment field applied to rods 38 are transported by their own residual momentum toward the exit lens 42 and ultimate axial ejection.
  • the ions which have reached the extraction volume in the vicinity of the exit lens have been preconditioned by their numerous collisions with background gas, eliminating the need for an explicit cooling time (and the attendant delay) as is required in most conventional ion traps.
  • ions are being ejected axially from region 54 in the mass dependent manner described.
  • the extraction volume 54 in the vicinity of the exit lens is quite small.
  • the exit lens 42 is normally placed very close to the ends of the rods 38, e.g. 2mm from the rod ends (as mentioned).
  • the penetration of the fringing fields from the exit lens 42 into the space between the rods 38 is believed to be very small, typically of the order of between 0.5mm and 1.0mm, so the extent of volume or region 54 is exaggerated in Fig. 1, for clarity of illustration.
  • the DC offset applied to all four rods 38 can be modulated at the same frequency as the AC which would have been applied to exit lens 42.
  • no AC is needed on exit lens 42 since modulating the DC offset is equivalent to applying an AC voltage to the exit lens, in that it creates an AC field in the fringing region.
  • the DC potential barrier is still applied to the exit lens 42.
  • the amplitude of the modulation of the DC offset will be the same as the amplitude of the AC voltage which otherwise would have been applied to the exit lens 42, i.e. it is set to optimize the axially ejected ion signal.
  • the RF amplitude is scanned to bring ions sequentially into resonance with the AC field created by the DC modulation, or else the frequency of the modulation is scanned so that again, when such frequency matches a radial secular frequency of an ion in the fringing fields in the vicinity of the exit lens, the ion will absorb energy and be ejected axially for detection.
  • the rod offset would not be modulated until after ions have been injected and trapped within the rods, since the modulation would otherwise interfere with ion injection, so this process would be a batch process. This is in contrast to the continuous process possible when AC is placed on the exit lens, in which case ions can be ejected from the extraction region 54 at the same time as ions are entering region 60 (because the AC field on exit lens 42 does not affect ion injection).
  • the desired mass /charge ratio are injected into the rods and travel along them to the exit lens 42.
  • Ion ejection processes can require some tens of milliseconds.
  • the time required for ions to travel from one end to the other of the rods 38 depends on the lengths of the rods themselves, the initial energy of the ions, and the pressure in the vacuum chamber 34. In some cases the end-to-end transit time will dominate, but more often the time required to extract the ions from the region in the vicinity of the exit lens 42 will be more important.
  • One method of matching the time required for ions to travel from one end to the other of the rods 38 to the time required to eject the ions is to apply an axial field along the rods 38. Methods for imposing axial fields of this kind are described in copending application serial no. 08/514,372 filed August 5, 1995 and entitled "Spectrometer with Axial Field" assigned to the assignee of this application.
  • An applied axial field in the direction of the exit lens 42 will tend to concentrate ions in the region of rods 38 in the vicinity of lens 42, i.e. in the volume 54 of the device from which the ions are extracted.
  • An applied axial field in the opposite direction will tend to deplete ions from the extraction volume 54, and may also be desirable in some cases.
  • Fig. 2 One typical electrode geometry which may be used is that depicted in Fig. 2, where primed reference numerals indicate parts corresponding to those of Fig. 1.
  • the rods 38 ' are divided into segments 38-1 ' to 38-5 ' , with DC offsets VI to V6 which increase in negative value applied to successive segments from 38-1 to 38-6.
  • This arrangement will provide an axial field as described in said application.
  • Such an arrangement will strongly concentrate ions in the volume near the exit lens 42 ' and will increase the coupling of axial and radial ion motion.
  • the axial field can be oscillated as described in the above mentioned copending application. Such oscillation may enhance axial ejection of ions trapped in the volume near the exit lens 42. It can also be used for ion dissociation as described in said application, by oscillating the ion population trapped in the rod structure about their equilibrium positions.
  • the system described can be considered as being an open- ended three-dimensional ion trap, where the open end is an integrated high efficiency ion injection device (supplied by ion source 14).
  • the ions in the vicinity of the exit lens 42 experience a three-dimensional trapping field comprised of radial and axial components. Radially the ions are contained by the main RF field applied to the linear rods 38. Axially the ions are contained at the exit end of the device by the DC potential on the exit lens 42, and are contained at the entrance end of the device by the potential gradient from the applied axial field (or from the skimmer 32). The ions are also to some extent contained in the trapping region or volume 54 by the field created by the build-up of charge density upstream of that region.
  • the actual trapping volume 54 is variable along the axial or Z direction.
  • the RF on the rods 38 can be scanned to eject ions mass dependently, while keeping a DC potential barrier on end lens 42 but with no AC field on end lens 42, no modulation of the DC offset on rods 38, and no dipole AC field on rods 38.
  • ions in the fringing fields at the downstream ends of rods 38 will leave axially and be detected, but most of the ions between rods 38 (those in region 60) will leave radially and will be wasted.
  • the wastage can be reduced by segmenting rods 38 as shown in Fig. 2, making the last set of segments 38-5 ' very short (e.g. less than 1cm), and scanning the RF for ejection only on segments 38-5 . In this way, a higher proportion of the ions between rods 38-5 will be ejected axially mass dependency, for detection.
  • ions from conventional ion sources are of little or no analytical utility.
  • examples of such ions are low mass solvent and cluster ions. These ions simply serve to increase the overall charge density within the ion trap at the expense of optimum performance.
  • Various techniques may be used to eliminate such unwanted ions from the linear ion trap described.
  • One such method is to operate the main RF voltage from power supply 50 at a level where the analytes of interest are stable within the rod structure 38, but the unwanted ions are unstable. For example if the unwanted ions are in the mass to charge range 10 to 100, and the ions of interest are in the mass to charge range 200 to 1,000, then the main RF voltage can be operated at 214 volts peak to peak.
  • Another method of eliminating unwanted ions from the ion trap is to apply an additional auxiliary AC voltage between opposite pairs of the rods 38, to resonantly eject the unwanted ions radially out of the rod set.
  • This technique is well known, as mentioned.
  • an auxiliary AC voltage of magnitude equal to about 10% of the level of the main RF voltage and of much lower frequency, is typically applied between opposite pairs of rods.
  • the auxiliary AC voltage of appropriate amplitude and frequency, may be scanned to resonantly eject unwanted ions radially.
  • rods 38 have been divided into three sets of rods 38a, 38b and 38c.
  • Rods 38a are used to pre-trap ions from the continuous ion source 14 " .
  • the rods 38b are used as an RF rod mirror that can reflect or transmit ions, by changing the DC offset of rods 38b.
  • the rods 38c and lens 42 " serve as the open-ended ion trap previously described, for analysis of ions which are injected into rods 38c through the rods 38b.
  • the RF and DC voltages on rod set 38a are set to accept ions within a mass range of interest, while the AC and DC voltages on rod set 38b are set to reflect ions, so that a population of ions accumulates in rod set 38a.
  • the operation is exactly as described for rod set 44 in U.S. patent 5,179,278.
  • the voltages on rod set 38b are changed to allow passage of the accumulated ions in rod set 38a through rod set 38b to rod set 38c.
  • the RF voltage and DC offset voltage applied to rod set 38c, and the AC and DC voltages applied to lens 42 " are set such that rod set 38c operates as an ion trap with axial ejection as described in connection with Fig. 1.
  • ions are axially ejected in a mass dependent manner from rod set 38c, as previously described, for detection in detector 46 " .
  • the voltages on rod set 38b return to the ion reflection mode and further ions from the source 14 " are stored in rod set 38a.
  • An advantage of this configuration is that while ions are being analyzed in rod set 38c, ions from the continuous source are accumulated for subsequent analysis in the pre-trapping region, i.e. rod set 38a, and are not lost.
  • O.l ⁇ M micro moles
  • reserpine having mass to charge ratio 609
  • a conventional mass spectrometer model API 300 produced by Sciex Division of MDS Health Group Limited of Concord, Ontario, Canada.
  • a simplified diagrammatic view of the model API 300 ion optical path is shown in Fig. 4, where the gas curtain entrance plate is indicated at 70, the gas curtain exit plate is indicated at 72, the skimmer plate is shown at 74, and four sets of rods are indicated as Q0, Ql, Q2 and Q3, with orifice plates IQ1 between rod sets Q0 and Ql, IQ2 between Q2 and Q3, and IQ3 between Q2 and Q3.
  • the exit lens is indicated at 76 and the detector (a channel electron multiplier) is indicated at 78.
  • the pressures were 2.2 Torr in chamber 80, 8 milli-Torr in chamber 82 and 2 x IO" 5 Torr in the remainder of the vacuum chamber 84.
  • the applied DC voltages were: ground at skimmer plate 80; -5 volts DC at Q0, -7 volts DC at IQ1, -10 volts at Ql, -20 volts at IQ2, -7 volts DC at Q2, -3 volts DC at IQ3 (which served as the equivalent of the exit lens 42); -15 volts DC on Q3, and 0 volts on the final exit plate 76. All resolving DC voltages were removed from the quadrupoles.
  • auxiliary AC voltage was applied to the exit lens IQ3.
  • the auxiliary AC power supply could produce 100 volts peak to peak, at frequency one-ninth that of the main RF frequency, and was phase locked to the main RF frequency.
  • the main RF frequency was 816 kHz so that of the auxiliary AC voltage was 91.67 kHz.
  • the auxiliary AC voltage was held at 47 volts peak to peak, its frequency was held constant at 91.67 kHz for the experiment, and the RF voltage applied to the Q2 rods was scanned to obtain a mass spectrum.
  • the sequence of events in the experiment was: (a) A short pulse of ions was allowed to pass from Q0 into Q2 (Ql performed no function except as an ion pipe during this experiment) by changing the DC lens voltage on IQ1 from +20 volts (which stopped ions) to - 7 volts (for ion transmission).
  • Ions that were trapped in Q2 were then scanned out axially by ramping the RF applied to the Q2 rods, typically from 924 volts peak to peak to 960 volts peak to peak.
  • Ions within Q2 were excited by setting the RF rod voltage to 897.8 volts peak to peak for 50 ms. This was an excitation step. Ions in Q2 which were in resonance with the applied AC field (on IQ3) were excited (absorbed power) and, because of their increased kinetic energy, were either ejected from the trap or fragmented due to collisions with the background gas. 3. Immediately after the 50 ms excitation step, ions in Q2 were scanned out axially by scanning the Q2 RF rod voltage from 800 volts peak to peak to 1,422 volts peak to peak. This step simply took a "snapshot" of the ions that had remained in the trap after the excitation step. The observed ions are shown at peaks 104, 106, 108 in Fig. 6.
  • Peak 108 is the parent ion at m/z 587 (triply charged), while the fragment ions m/z 697 and m/z 720 are shown at 106, 108 (they have higher m/z ratios because they are only doubly charged).
  • collisional fragmentation can readily be performed in the linear trap described, and the fragment ions can be scanned axially in a mass dependent manner for detection and analysis.
  • exit lens 42 has been described as a plate with an aperture, other configurations of exit lenses may be used, for example a short RF-only rod array such as that indicated at 102 in Fig. 7 and having A and B poles 102a, 102b.
  • the rod offsets of the A and B poles 102a, 102b may then be resonated at the resonance frequency of the ion to be ejected, producing axial ejection as was achieved by the auxiliary AC field applied to exit lens 42.
  • the end lens 110 may be a segmented plate having wedge-shaped segments 110-1, 110-2, 110-3, 110-4 and an aperture 112. This allows different fields to be applied to each segment, to optimize the results, while still limiting the quantity of gas which can leave the part of the vacuum chamber upstream of lens 110.

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  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
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Abstract

La présente invention concerne un procédé permettant d'utiliser un spectromètre de masse muni d'un jeu de tiges allongées multipolaires, dans lequel un champ RF bidimensionnel contient radialement des ions piégés dans une masse de façon à charger une portée massique considérée, et dans lequel un champ barrière contient axialement les ions sur une lentille de sortie, un courant continu basse tension leur étant appliqué. On profite du mélange des degrés de liberté induits par les effets de frange et autres perturbations dans le voisinage de la lentille de sortie pour éjecter axialement et avec une sélectivité de masse les ions piégés. De cette manière, les ions sont éjectés avec une sélectivité de masse à l'extrémité de sortie en même temps que des ions sont admis à l'extrémité d'entrée du jeu de tiges, ce qui permet de tirer un meilleur parti du flux d'ions provenant d'une source d'ions continue. On effectue l'éjection axiale à sélectivité de masse en appliquant une tension de courant alternatif auxiliaire à l'extrémité de sortie, et en balayant l'ensemble de tiges avec la tension de courant alternatif auxiliaire ou la tension RF. On peut concentrer les ions piégés près de l'extrémité de sortie en appliquant un champ axial dans la direction de la lentille, et on peut les éloigner en appliquant le champ axial dans la direction opposée. On peut faire osciller le champ axial afin de dissocier les ions piégés.
PCT/CA1997/000381 1996-06-06 1997-06-02 Spectrometre de masse multipolaire a ejection axiale WO1997047025A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP97923686A EP0902963B1 (fr) 1996-06-06 1997-06-02 Spectrometre de masse multipolaire a ejection axiale
DE69715190T DE69715190T2 (de) 1996-06-06 1997-06-02 Multipolmassenspektrometer mit axialem ausstoss
JP53747397A JP3818671B2 (ja) 1996-06-06 1997-06-02 多重極子質量分光計の軸方向射出方法
AU29461/97A AU718774B2 (en) 1996-06-06 1997-06-02 Axial ejection in a multipole mass spectrometer
CA002256028A CA2256028C (fr) 1996-06-06 1997-06-02 Spectrometre de masse multipolaire a ejection axiale

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US65695496A 1996-06-06 1996-06-06
US08/656,954 1996-06-06

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WO1997047025A1 true WO1997047025A1 (fr) 1997-12-11

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JP (1) JP3818671B2 (fr)
AU (1) AU718774B2 (fr)
CA (1) CA2256028C (fr)
DE (1) DE69715190T2 (fr)
WO (1) WO1997047025A1 (fr)

Cited By (19)

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WO1999023686A1 (fr) * 1997-10-31 1999-05-14 Mds Inc. Procede de mise en oeuvre d'un spectrometre de masse comportant une entree c.c. pour resolution de bas niveau visant a ameliorer le rapport signal-bruit
WO1999063578A2 (fr) * 1998-06-01 1999-12-09 Mds Inc. Ejection axiale dans un spectrometre de masse a plusieurs poles
US6114691A (en) * 1997-05-12 2000-09-05 Mds Inc. RF-only mass spectrometer with auxiliary excitation
EP1057209A1 (fr) * 1998-01-23 2000-12-06 Analytica Of Branford, Inc. Spectrometrie de masse a guide d'ions multipolaire
WO2000073750A2 (fr) * 1999-05-27 2000-12-07 Mds Inc. Spectrometre de masse quadripolaire avec piege a ions permettant d'ameliorer la sensibilite
WO2001015201A2 (fr) * 1999-08-26 2001-03-01 University Of New Hampshire Spectrometre de masse a plusieurs etapes
EP1090412A1 (fr) * 1998-05-29 2001-04-11 Analytica Of Branford, Inc. Spectrometrie de masse avec guides d'ions multipolaires
WO2002009144A2 (fr) * 2000-07-21 2002-01-31 Mds Inc., Doing Business As Mds Sciex Spectrometre de masse a trois quadripoles pouvant realiser des operations d'analyse de masse multiples
US6770871B1 (en) 2002-05-31 2004-08-03 Michrom Bioresources, Inc. Two-dimensional tandem mass spectrometry
US7060972B2 (en) 2000-07-21 2006-06-13 Mds Inc. Triple quadrupole mass spectrometer with capability to perform multiple mass analysis steps
EP1763062A2 (fr) * 2005-09-13 2007-03-14 Agilent Technologies, Inc. Chambre de collision multipolaire de gradient augmentée pour un coefficient d'utilisation plus élevé
US7208729B2 (en) 2002-08-01 2007-04-24 Microsaic Systems Limited Monolithic micro-engineered mass spectrometer
DE102006016896A1 (de) * 2006-04-11 2007-10-18 Bruker Daltonik Gmbh Orthogonal-Flugzeitmassenspektrometer geringer Massendiskriminierung
EP2112683A1 (fr) * 2008-04-22 2009-10-28 IEE INTERNATIONAL ELECTRONICS & ENGINEERING S.A. Spectromètre à mobilité différentielle et son procédé de fonctionnement
US20100084549A1 (en) * 2006-11-13 2010-04-08 Alexei Victorovich Ermakov Electrostatic Ion Trap
USRE45386E1 (en) 1998-09-16 2015-02-24 Thermo Fisher Scientific (Bremen) Gmbh Means for removing unwanted ions from an ion transport system and mass spectrometer
USRE45553E1 (en) 2002-05-13 2015-06-09 Thermo Fisher Scientific Inc. Mass spectrometer and mass filters therefor
EP3005405A4 (fr) * 2013-06-02 2017-02-22 PerkinElmer Health Sciences, Inc. Cellules de collision et procédés utilisant ces cellules
JPWO2016114151A1 (ja) * 2015-01-15 2017-12-21 株式会社日立ハイテクノロジーズ 質量分析装置

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US6703607B2 (en) * 2002-05-30 2004-03-09 Mds Inc. Axial ejection resolution in multipole mass spectrometers
US7045797B2 (en) * 2002-08-05 2006-05-16 The University Of British Columbia Axial ejection with improved geometry for generating a two-dimensional substantially quadrupole field
JP4659395B2 (ja) * 2004-06-08 2011-03-30 株式会社日立ハイテクノロジーズ 質量分析装置及び質量分析方法
WO2006075182A2 (fr) * 2005-01-17 2006-07-20 Micromass Uk Limited Spectrometre de masse
EP1955359B1 (fr) * 2005-11-30 2015-04-01 DH Technologies Development Pte. Ltd. Procede et dispositif pour transport axial par selection de masse au moyen d'un champ axial pulse
GB0717146D0 (en) 2007-09-04 2007-10-17 Micromass Ltd Mass spectrometer
JPWO2010044370A1 (ja) * 2008-10-14 2012-03-15 株式会社日立製作所 質量分析装置および質量分析方法
US8368011B2 (en) 2009-04-17 2013-02-05 Hitachi, Ltd. Ion detector
JP5767843B2 (ja) 2011-04-01 2015-08-19 株式会社日立製作所 イオン検出装置

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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6177668B1 (en) 1996-06-06 2001-01-23 Mds Inc. Axial ejection in a multipole mass spectrometer
US6114691A (en) * 1997-05-12 2000-09-05 Mds Inc. RF-only mass spectrometer with auxiliary excitation
WO1999023686A1 (fr) * 1997-10-31 1999-05-14 Mds Inc. Procede de mise en oeuvre d'un spectrometre de masse comportant une entree c.c. pour resolution de bas niveau visant a ameliorer le rapport signal-bruit
EP1057209B1 (fr) * 1998-01-23 2011-11-23 PerkinElmer Health Sciences, Inc. Spectrometrie de masse a guide d'ions multipolaire
EP1057209A1 (fr) * 1998-01-23 2000-12-06 Analytica Of Branford, Inc. Spectrometrie de masse a guide d'ions multipolaire
EP1090412A1 (fr) * 1998-05-29 2001-04-11 Analytica Of Branford, Inc. Spectrometrie de masse avec guides d'ions multipolaires
EP1090412B1 (fr) * 1998-05-29 2014-03-05 PerkinElmer Health Sciences, Inc. Spectrometrie de masse avec guides d'ions multipolaires
WO1999063578A3 (fr) * 1998-06-01 2000-01-27 Mds Inc Ejection axiale dans un spectrometre de masse a plusieurs poles
WO1999063578A2 (fr) * 1998-06-01 1999-12-09 Mds Inc. Ejection axiale dans un spectrometre de masse a plusieurs poles
USRE45386E1 (en) 1998-09-16 2015-02-24 Thermo Fisher Scientific (Bremen) Gmbh Means for removing unwanted ions from an ion transport system and mass spectrometer
WO2000073750A2 (fr) * 1999-05-27 2000-12-07 Mds Inc. Spectrometre de masse quadripolaire avec piege a ions permettant d'ameliorer la sensibilite
AU780291B2 (en) * 1999-05-27 2005-03-17 Mds Inc. Quadrupole mass spectrometer with ion traps to enhance sensitivity
WO2000073750A3 (fr) * 1999-05-27 2001-08-02 Mds Inc Spectrometre de masse quadripolaire avec piege a ions permettant d'ameliorer la sensibilite
US6504148B1 (en) 1999-05-27 2003-01-07 Mds Inc. Quadrupole mass spectrometer with ION traps to enhance sensitivity
JP2003501790A (ja) * 1999-05-27 2003-01-14 エムディーエス インコーポレーテッド 感度を向上するためのイオントラップを有する四重極質量分析計
WO2001015201A2 (fr) * 1999-08-26 2001-03-01 University Of New Hampshire Spectrometre de masse a plusieurs etapes
WO2001015201A3 (fr) * 1999-08-26 2002-02-21 Univ New Hampshire Spectrometre de masse a plusieurs etapes
US7060972B2 (en) 2000-07-21 2006-06-13 Mds Inc. Triple quadrupole mass spectrometer with capability to perform multiple mass analysis steps
US6720554B2 (en) 2000-07-21 2004-04-13 Mds Inc. Triple quadrupole mass spectrometer with capability to perform multiple mass analysis steps
WO2002009144A2 (fr) * 2000-07-21 2002-01-31 Mds Inc., Doing Business As Mds Sciex Spectrometre de masse a trois quadripoles pouvant realiser des operations d'analyse de masse multiples
WO2002009144A3 (fr) * 2000-07-21 2003-01-23 Mds Inc Dba Mds Sciex Spectrometre de masse a trois quadripoles pouvant realiser des operations d'analyse de masse multiples
USRE45553E1 (en) 2002-05-13 2015-06-09 Thermo Fisher Scientific Inc. Mass spectrometer and mass filters therefor
US6770871B1 (en) 2002-05-31 2004-08-03 Michrom Bioresources, Inc. Two-dimensional tandem mass spectrometry
US7208729B2 (en) 2002-08-01 2007-04-24 Microsaic Systems Limited Monolithic micro-engineered mass spectrometer
EP1763062A2 (fr) * 2005-09-13 2007-03-14 Agilent Technologies, Inc. Chambre de collision multipolaire de gradient augmentée pour un coefficient d'utilisation plus élevé
DE102006016896B4 (de) * 2006-04-11 2009-06-10 Bruker Daltonik Gmbh Orthogonal-Flugzeitmassenspektrometer geringer Massendiskriminierung
US7714279B2 (en) 2006-04-11 2010-05-11 Bruker Daltonik, Gmbh Orthogonal time-of-flight mass spectrometers with low mass discrimination
DE102006016896A1 (de) * 2006-04-11 2007-10-18 Bruker Daltonik Gmbh Orthogonal-Flugzeitmassenspektrometer geringer Massendiskriminierung
US20100084549A1 (en) * 2006-11-13 2010-04-08 Alexei Victorovich Ermakov Electrostatic Ion Trap
US9000364B2 (en) * 2006-11-13 2015-04-07 Mks Instruments, Inc. Electrostatic ion trap
GB2471631A (en) * 2008-04-22 2011-01-05 Iee Sarl Differential mobility spectrometer and operating method therefor
GB2471631B (en) * 2008-04-22 2011-09-28 Iee Sarl Differential mobility spectrometer and operating method therefor
WO2009130172A1 (fr) * 2008-04-22 2009-10-29 Iee International Electronics & Engineering S.A. Spectromètre de mobilité différentielle et son procédé d'exploitation
US8884219B2 (en) 2008-04-22 2014-11-11 Iee International Electronics & Engineering S.A. Differential mobility spectrometer with asymmetrically oscillating driving electrical field
EP2112683A1 (fr) * 2008-04-22 2009-10-28 IEE INTERNATIONAL ELECTRONICS & ENGINEERING S.A. Spectromètre à mobilité différentielle et son procédé de fonctionnement
EP3005405A4 (fr) * 2013-06-02 2017-02-22 PerkinElmer Health Sciences, Inc. Cellules de collision et procédés utilisant ces cellules
JPWO2016114151A1 (ja) * 2015-01-15 2017-12-21 株式会社日立ハイテクノロジーズ 質量分析装置

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Publication number Publication date
EP0902963A1 (fr) 1999-03-24
JP3818671B2 (ja) 2006-09-06
JP2000510638A (ja) 2000-08-15
AU718774B2 (en) 2000-04-20
CA2256028C (fr) 2007-01-16
DE69715190D1 (de) 2002-10-10
CA2256028A1 (fr) 1997-12-11
DE69715190T2 (de) 2003-04-30
EP0902963B1 (fr) 2002-09-04
AU2946197A (en) 1998-01-05

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