WO1992015392A1 - Mass spectrometry method using supplemental ac voltage signals - Google Patents
Mass spectrometry method using supplemental ac voltage signals Download PDFInfo
- Publication number
- WO1992015392A1 WO1992015392A1 PCT/US1992/001104 US9201104W WO9215392A1 WO 1992015392 A1 WO1992015392 A1 WO 1992015392A1 US 9201104 W US9201104 W US 9201104W WO 9215392 A1 WO9215392 A1 WO 9215392A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- voltage signal
- ions
- daughter
- frequency
- electrodes
- Prior art date
Links
Classifications
-
- 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
- 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
- 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.
- Figure 1 is a simplified schematic diagram of an apparatus useful for implementing a class of
- 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.
- 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 are common mode grounded through coupling transformer 32.
- Supplemental AC voltage generator 35 can be switched on to apply a desired supplemental AC
- 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
- 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.
- Such 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).
- 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
- 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) .
- 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 l
- 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.
- 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
- 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
- Each such frequency component should have frequency and amplitude characteristics of the type described above with reference to Figure 2.
- 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 "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.
- the frequency of each daughter ion (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) following application of the low power supplemental AC voltage signal and before application of the daughter supplemental AC voltage signal.
- the frequency of each daughter ion (the frequency at which each daughter ion moves in the trapping field) 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
- 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 "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
- all or some of the supplemental AC voltage signals have two or more different frequency components within a selected frequency range. Each such frequency
- the first step of this embodiment (which occurs during period "A") is to store parent ions in a trap. This can be
- 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).
- 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 ).
- 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.
- 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).
- 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
- the ion signal does have a peak representing sample ions detected during application of the fourth supplemental signal.
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electron Tubes For Measurement (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4507289A JP2743034B2 (en) | 1991-02-28 | 1992-02-11 | Mass spectrometry using supplemental AC voltage signals |
EP92907848A EP0573579B1 (en) | 1991-02-28 | 1992-02-11 | Mass spectrometry method using supplemental ac voltage signals |
DE69219113T DE69219113T2 (en) | 1991-02-28 | 1992-02-11 | MASS SPECTROMETRY METHOD USING ADDITIONAL AC VOLTAGE SIGNALS |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US66219191A | 1991-02-28 | 1991-02-28 | |
US662,191 | 1991-02-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992015392A1 true WO1992015392A1 (en) | 1992-09-17 |
Family
ID=24656746
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/001104 WO1992015392A1 (en) | 1991-02-28 | 1992-02-11 | Mass spectrometry method using supplemental ac voltage signals |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0573579B1 (en) |
JP (1) | JP2743034B2 (en) |
AT (1) | ATE151915T1 (en) |
CA (1) | CA2101152C (en) |
DE (1) | DE69219113T2 (en) |
DK (1) | DK0573579T3 (en) |
ES (1) | ES2106177T3 (en) |
WO (1) | WO1992015392A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2691835A1 (en) * | 1992-05-29 | 1993-12-03 | Finnigan Corp | Method of using an ion trap mass spectrometer |
EP0601118A1 (en) * | 1991-08-30 | 1994-06-15 | Teledyne Industries, Inc. | Mass spectrometry method using supplemental ac voltage signals |
EP0736221A1 (en) * | 1993-05-25 | 1996-10-09 | Teledyne Industries, Inc. | Mass spectrometry method with two applied trapping fields having same spatial form |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4736101A (en) * | 1985-05-24 | 1988-04-05 | Finnigan Corporation | Method of operating ion trap detector in MS/MS mode |
US4749860A (en) * | 1986-06-05 | 1988-06-07 | Finnigan Corporation | Method of isolating a single mass in a quadrupole ion trap |
-
1992
- 1992-02-11 DK DK92907848.3T patent/DK0573579T3/en active
- 1992-02-11 AT AT92907848T patent/ATE151915T1/en not_active IP Right Cessation
- 1992-02-11 ES ES92907848T patent/ES2106177T3/en not_active Expired - Lifetime
- 1992-02-11 EP EP92907848A patent/EP0573579B1/en not_active Expired - Lifetime
- 1992-02-11 JP JP4507289A patent/JP2743034B2/en not_active Expired - Fee Related
- 1992-02-11 CA CA002101152A patent/CA2101152C/en not_active Expired - Lifetime
- 1992-02-11 WO PCT/US1992/001104 patent/WO1992015392A1/en active IP Right Grant
- 1992-02-11 DE DE69219113T patent/DE69219113T2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4736101A (en) * | 1985-05-24 | 1988-04-05 | Finnigan Corporation | Method of operating ion trap detector in MS/MS mode |
US4749860A (en) * | 1986-06-05 | 1988-06-07 | Finnigan Corporation | Method of isolating a single mass in a quadrupole ion trap |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0601118A1 (en) * | 1991-08-30 | 1994-06-15 | Teledyne Industries, Inc. | Mass spectrometry method using supplemental ac voltage signals |
EP0601118A4 (en) * | 1991-08-30 | 1995-08-23 | Teledyne Mec | Mass spectrometry method using supplemental ac voltage signals. |
FR2691835A1 (en) * | 1992-05-29 | 1993-12-03 | Finnigan Corp | Method of using an ion trap mass spectrometer |
EP0736221A1 (en) * | 1993-05-25 | 1996-10-09 | Teledyne Industries, Inc. | Mass spectrometry method with two applied trapping fields having same spatial form |
EP0736221A4 (en) * | 1993-05-25 | 1997-03-19 | Teledyne Ind | Mass spectrometry method with two applied trapping fields having same spatial form |
Also Published As
Publication number | Publication date |
---|---|
JPH06508469A (en) | 1994-09-22 |
ATE151915T1 (en) | 1997-05-15 |
EP0573579A1 (en) | 1993-12-15 |
DE69219113D1 (en) | 1997-05-22 |
EP0573579A4 (en) | 1995-08-09 |
CA2101152A1 (en) | 1992-08-29 |
EP0573579B1 (en) | 1997-04-16 |
DE69219113T2 (en) | 1997-11-20 |
ES2106177T3 (en) | 1997-11-01 |
JP2743034B2 (en) | 1998-04-22 |
DK0573579T3 (en) | 1997-10-20 |
CA2101152C (en) | 1999-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5134286A (en) | Mass spectrometry method using notch filter | |
EP0601118B1 (en) | Mass spectrometry method using supplemental ac voltage signals | |
US5274233A (en) | Mass spectrometry method using supplemental AC voltage signals | |
EP0736221B1 (en) | Mass spectrometry method with two applied trapping fields having same spatial form | |
US5196699A (en) | Chemical ionization mass spectrometry method using notch filter | |
US5206507A (en) | Mass spectrometry method using filtered noise signal | |
US5451782A (en) | Mass spectometry method with applied signal having off-resonance frequency | |
US5105081A (en) | Mass spectrometry method and apparatus employing in-trap ion detection | |
US5173604A (en) | Mass spectrometry method with non-consecutive mass order scan | |
EP0573579B1 (en) | Mass spectrometry method using supplemental ac voltage signals | |
EP0765190B1 (en) | Quadrupole with applied signal having off-resonance frequency |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2101152 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1992907848 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1992907848 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1992907848 Country of ref document: EP |