CN101536137A - Mass spectrometer - Google Patents

Mass spectrometer Download PDF

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Publication number
CN101536137A
CN101536137A CNA2007800297586A CN200780029758A CN101536137A CN 101536137 A CN101536137 A CN 101536137A CN A2007800297586 A CNA2007800297586 A CN A2007800297586A CN 200780029758 A CN200780029758 A CN 200780029758A CN 101536137 A CN101536137 A CN 101536137A
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China
Prior art keywords
ion
mass analyzer
electrode
gradually
ion guides
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Granted
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CNA2007800297586A
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Chinese (zh)
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CN101536137B (en
Inventor
约翰·布赖恩·霍耶斯
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Micromass UK Ltd
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Micromass UK Ltd
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Priority claimed from US11/483,961 external-priority patent/US7405401B2/en
Priority claimed from PCT/GB2006/002728 external-priority patent/WO2007010272A2/en
Priority claimed from GB0704923A external-priority patent/GB0704923D0/en
Application filed by Micromass UK Ltd filed Critical Micromass UK Ltd
Priority claimed from PCT/GB2007/002561 external-priority patent/WO2008007069A2/en
Publication of CN101536137A publication Critical patent/CN101536137A/en
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Publication of CN101536137B publication Critical patent/CN101536137B/en
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Abstract

A mass analyser (2) is provided comprising a plurality of electrodes having apertures through which ions are transmitted in use. A plurality of pseudo-potential corrugations are created along the axis of the mass ((analyser 2). The amplitude or depth of the pseudo-potential corrugations is inversely proportional to the mass to charge ratio of an ion. One or more transient DC voltages are applied to the electrodes of the mass analyser (2) in order to urge ions along the length of the mass analyser (2). The amplitude of the transient DC voltages applied to the electrodes is increased with time and ions are caused to be emitted from the mass analyser (2) in reverse order of their mass to charge ratio. Two AC or RF voltages are applied to the electrodes. The first AC or RF voltage is arranged to provide optimal pseudo-potential corrugations whilst the second AC' or RF voltage is arranged to provide optimal radial confinement of ions within the mass analyser (2).

Description

Mass spectrometer
Technical field
The present invention relates to a kind of mass analyzer and a kind of method of ion being carried out quality analysis.
Background technology
Usually be necessary ion is transferred to the mass analyzer that is maintained at relatively low pressure from the mass spectrometric ionized region that can be maintained at relatively high pressure.The one or more radio frequencies of known use (RF) ion guides device is transported to mass analyzer with ion from ionized region.The known radio frequency ion guides device that makes is about 10 -3The middle pressure of-1mbar is work down.
Thereby also known charged particle or the time average power on the ion when having non-homogeneous interchange or rf electric field makes charged particle or ion quicken to arrive the more weak district of electric field.The minimum value of electric field is commonly referred to pseudo-potential well or pseudo-potential trough.Known radio frequency ion guides device utilizes this phenomenon by carrying out following layout: generate or produce pseudo-potential well or pseudo-potential trough along the central shaft of radio frequency ion guides device, thereby radially limit ion in radio frequency ion guides device center.
Known radio frequency ion guides device is used as the device that limits ion efficiently and ion is transported to another district from a district.Along the gesture distribution substantial constant of the central shaft of known radio frequency ion guides device, therefore known radio frequency ion guides device is with the delay of minimum and to all ions of ion indistinction not of the same race ground conveying.
Summary of the invention
Be desirable to provide a kind of improved mass analyzer.
According to an aspect of the present invention, provide a kind of mass analyzer, this mass analyzer comprises:
The ion guides device that comprises a plurality of electrodes;
Be used for to have that first of the first frequency and first amplitude exchanges or radio-frequency voltage puts at least some electrodes of described a plurality of electrodes so that produce one or more axially devices of time averaging or pseudo-potential barrier, gesture ripple or potential well along at least a portion of the axial length of ion guides device in use;
Be used for to have that second of the second frequency and second amplitude exchanges or radio-frequency voltage puts on one or more electrodes of described a plurality of electrodes so that radially limit the device of ion in the ion guides device in use; And
Be used for driving or driving ion and/or driving or drive ion at least a portion by the axial length of ion guides device so that withdraw from the ion guides device and device in the ion guides device is axially caught or be limited to the ion of mass-to-charge ratio in second different range by a plurality of axially time averaging or pseudo-potential barrier, gesture ripple or potential wells at the ion of mass-to-charge ratio in first scope under the mode of operation along at least a portion of the axial length of ion guides device.
Should be appreciated that mass analyzer relates to a kind of equipment that comes isolating ions with the rate of change of electric field strength such as ionic mobility or ionic mobility according to mass-to-charge ratio rather than certain other characteristic of ion.
First frequency can be significantly different with second frequency.Alternatively, first frequency can be substantially the same with second frequency.
First frequency preferably is selected from: (i)<and 100kHz; (ii) 100-200kHz; (iii) 200-300kHz; (iv) 300-400kHz; (v) 400-500kHz; (vi) 0.5-1.0MHz; (vii) 1.0-1.5MHz; (viii) 1.5-2.0MHz; (ix) 2.0-2.5MHz; (x) 2.5-3.0MHz; (xi) 3.0-3.5MHz; (xii) 3.5-4.0MHz; (xiii) 4.0-4.5MHz; (xiv) 4.5-5.0MHz; (xv) 5.0-5.5MHz; (xvi) 5.5-6.0MHz; (xvii) 6.0-6.5MHz; (xviii) 6.5-7.0MHz; (xix) 7.0-7.5MHz; (xx) 7.5-8.0MHz; (xxi) 8.0-8.5MHz; (xxii) 8.5-9.0MHz; (xxiii) 9.0-9.5MHz; (xxiv) 9.5-10.0MHz; And (xxv)〉10.0MHz.Second frequency preferably is selected from: (i)<and 100kHz; (ii) 100-200kHz; (iii) 200-300kHz; (iv) 300-400kHz; (v) 400-500kHz; (vi) 0.5-1.0MHz; (vii) 1.0-1.5MHz; (viii) 1.5-2.0MHz; (ix) 2.0-2.5MHz; (x) 2.5-3.0MHz; (xi) 3.0-3.5MHz; (xii) 3.5-4.0MHz; (xiii) 4.0-4.5MHz; (xiv) 4.5-5.0MHz; (xv) 5.0-5.5MHz; (xvi) 5.5-6.0MHz; (xvii) 6.0-6.5MHz; (xviii) 6.5-7.0MHz; (xix) 7.0-7.5MHz; (xx) 7.5-8.0MHz; (xxi) 8.0-8.5MHz; (xxii) 8.5-9.0MHz; (xxiii) 9.0-9.5MHz; (xxiv) 9.5-10.0MHz; And (xxv)〉10.0MHz.
First amplitude can be significantly different with second amplitude.Alternatively, first amplitude can be substantially the same with second amplitude.
First amplitude preferably is selected from: (i)<and the 50V peak-to-peak value; (ii) 50-100V peak-to-peak value; (iii) 100-150V peak-to-peak value; (iv) 150-200V peak-to-peak value; (v) 200-250V peak-to-peak value; (vi) 250-300V peak-to-peak value; (vii) 300-350V peak-to-peak value; (viii) 350-400V peak-to-peak value; (ix) 400-450V peak-to-peak value; (x) 450-500V peak-to-peak value; And (xi)〉500V peak-to-peak value.Second amplitude preferably is selected from: (i)<and the 50V peak-to-peak value; (ii) 50-100V peak-to-peak value; (iii) 100-150V peak-to-peak value; (iv) 150-200V peak-to-peak value; (v) 200-250V peak-to-peak value; (vi) 250-300V peak-to-peak value; (vii) 300-350V peak-to-peak value; (viii) 350-400V peak-to-peak value; (ix) 400-450V peak-to-peak value; (x) 450-500V peak-to-peak value; And (xi)〉500V peak-to-peak value.
First interchange or radio-frequency voltage exchange with second or radio-frequency voltage between phase difference choosing preferably from: (i) 0-10 °; (ii) 10-20 °; (iii) 20-30 °; (iv) 30-40 °; (v) 40-50 °; (vi) 50-60 °; (vii) 60-70 °; (viii) 70-80 °; (ix) 80-90 °; (x) 90-100 °; (xi) 100-110 °; (xii) 110-120 °; (xiii) 120-130 °; (xiv) 130-140 °; (xv) 140-150 °; (xvi) 150-160 °; (xvii) 160-170 °; (xviii) 170-180 °; (xix) 180-190 °; (xx) 190-200 °; (xxi) 200-210 °; (xxii) 210-220 °; (xxiii) 220-230 °; (xxiv) 230-240 °; (xxv) 240-250 °; (xxvi) 250-260 °; (xxvii) 260-270 °; (xxviii) 270-280 °; (xxix) 280-290 °; (xxx) 290-300 °; (xxxi) 300-310 °; (xxxii) 310-320 °; (xxxiii) 320-330 °; (xxxiv) 330-340 °; (xxxv) 340-350 °; And (xxxvi) 350-360 °.
First interchange or radio-frequency voltage exchange with second or radio-frequency voltage between phase difference can be selected from: (i) 0 °; (ii) 90 °; (iii) 180 °; And (iv) 270 °.
The ion guides device preferably includes a plurality of first electrode groups, and wherein each first electrode group comprises at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 electrode or a plurality of electrode.The ion guides device preferably includes m the first electrode group, and wherein m is selected from: (i) 1-10; (ii) 11-20; (iii) 21-30; (iv) 31-40; (v) 41-50; (vi) 51-60; (vii) 61-70; (viii) 71-80; (ix) 81-90; (x) 91-100; And (xi)〉100.According to the preferred embodiment, at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 electrode in one or more or each first electrode group or a plurality of electrode are supplied first and exchange or the phase homophase of radio-frequency voltage.
The axial length of at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the first electrode group preferably is selected from: (i)<and 1mm; (ii) 1-2mm; (iii) 2-3mm; (iv) 3-4mm; (v) 4-5mm; (vi) 5-6mm; (vii) 6-7mm; (viii) 7-8mm; (ix) 8-9mm; (x) 9-10mm; (xi) 10-11mm; (xii) 11-12mm; (xiii) 12-13mm; (xiv) 13-14mm; (xv) 14-15mm; (xvi) 15-16mm; (xvii) 16-17mm; (xviii) 17-18mm; (xix) 18-19mm; (xx) 19-20mm; And (xxi)〉20mm.
Axially spaced-apart between at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the first electrode group preferably is selected from: (i)<and 1mm; (ii) 1-2mm; (iii) 2-3mm; (iv) 3-4mm; (v) 4-5mm; (vi) 5-6mm; (vii) 6-7mm; (viii) 7-8mm; (ix) 8-9mm; (x) 9-10mm; (xi) 10-11mm; (xii) 11-12mm; (xiii) 12-13mm; (xiv) 13-14mm; (xv) 14-15mm; (xvi) 15-16mm; (xvii) 16-17mm; (xviii) 17-18mm; (xix) 18-19mm; (xx) 19-20mm; And (xxi)〉20mm.
According to an embodiment, preferably form the regular periodicity row of axial pseudo-potential barrier, gesture ripple or potential well, these regular periodicity row preferably with the electrode that constitutes the ion guides device between axially spaced-apart have identical periodicity.Yet, can consider that also wherein axial pseudo-potential barrier, gesture ripple or potential well can have more preferred embodiments of different cycles.
One or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells preferably have along the axial length of ion guides device, preferably with the corresponding minimum value in centre or center of the first electrode group.
One or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells preferably have along the axial length of ion guides device, preferably with the first electrode group between axial distance or the maximum of 50% corresponding axial location basically of spacing.
One or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells preferably have for the ion with specific mass-to-charge ratio minimum value and/or the maximum for substantially the same height, the degree of depth or amplitude.This minimum value and/or maximum preferably have and the axial arranged of the first electrode group or periodically substantially the same periodicity.
According to the preferred embodiment, the ion guides device preferably includes a plurality of second electrode groups, and wherein each second electrode group comprises at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 electrode or a plurality of electrode.The ion guides device preferably includes n the second electrode group, and wherein n is selected from: (i) 1-10; (ii) 11-20; (iii) 21-30; (iv) 31-40; (v) 41-50; (vi) 51-60; (vii) 61-70; (viii) 71-80; (ix) 81-90; (x) 91-100; And (xi)〉100.
At least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 electrode in one or more or each second electrode group or a plurality of electrode preferably are supplied second and exchange or the phase homophase of radio-frequency voltage.
The axial length of at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the second electrode group preferably is selected from: (i)<and 1mm; (ii) 1-2mm; (iii) 2-3mm; (iv) 3-4mm; (v) 4-5mm; (vi) 5-6mm; (vii) 6-7mm; (viii) 7-8mm; (ix) 8-9mm; (x) 9-10mm; (xi) 10-11mm; (xii) 11-12mm; (xiii) 12-13mm; (xiv) 13-14mm; (xv) 14-15mm; (xvi) 15-16mm; (xvii) 16-17mm; (xviii) 17-18mm; (xix) 18-19mm; (xx) 19-20mm; And (xxi)〉20mm.
Axially spaced-apart between at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the second electrode group preferably is selected from: (i)<and 1mm; (ii) 1-2mm; (iii) 2-3mm; (iv) 3-4mm; (v) 4-5mm; (vi) 5-6mm; (vii) 6-7mm; (viii) 7-8mm; (ix) 8-9mm; (x) 9-10mm; (xi) 10-11mm; (xii) 11-12mm; (xiii) 12-13mm; (xiv) 13-14mm; (xv) 14-15mm; (xvi) 15-16mm; (xvii) 16-17mm; (xviii) 17-18mm; (xix) 18-19mm; (xx) 19-20mm; And (xxi)〉20mm.
According to the preferred embodiment, axially adjacent electrode is supplied the mutually anti-phase of second interchange or radio-frequency voltage.
One or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells preferably have along the axial length of ion guides device, preferably with the corresponding minimum value in centre or center of the second electrode group.
One or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells preferably have along the axial length of ion guides device, preferably with the second electrode group between axial distance or the maximum of 50% corresponding axial location basically of spacing.
One or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells preferably have for the ion with specific mass-to-charge ratio minimum value and/or the maximum for substantially the same height, the degree of depth or amplitude.This minimum value and/or maximum preferably have and the axial arranged of the second electrode group or periodically substantially the same periodicity.
According to the preferred embodiment, first scope preferably is selected from: (i)<100; (ii) 100-200; (iii) 200-300; (iv) 300-400; (v) 400-500; (vi) 500-600; (vii) 600-700; (viii) 700-800; (ix) 800-900; (x) 900-1000; And (xi)〉1000.Second scope preferably is selected from: (i)<100; (ii) 100-200; (iii) 200-300; (iv) 300-400; (v) 400-500; (vi) 500-600; (vii) 600-700; (viii) 700-800; (ix) 800-900; (x) 900-1000; And (xi)〉1000.
Be used for exchanging or device that radio-frequency voltage puts at least some electrodes of a plurality of electrodes preferably is arranged to and is adapted such that along at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of the axial length of ion guides device produce one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells with first.
Preferably produce or provide one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells along at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of the center longitudinal axis of ion guides device.
One or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells are preferably being extended rmm at least away from the center longitudinal axis of ion guides device in the radial direction, and wherein r is selected from: (i)<1; (ii) 1-2; (iii) 2-3; (iv) 3-4; (v) 4-5; (vi) 5-6; (vii) 6-7; (viii) 7-8; (ix) 8-9; (x) 9-10; And (xi)〉10.
Drop on ion in scope 1-100,100-200,200-300,300-400,400-500,500-600,600-700,700-800,800-900 or the 900-1000 for mass-to-charge ratio, amplitude, height or the degree of depth of at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% axial time averaging or pseudo-potential barrier, gesture ripple or potential well preferably are selected from: (i)<and 0.1V; (ii) 0.1-0.2V; (iii) 0.2-0.3V; (iv) 0.3-0.4V; (v) 0.4-0.5V; (vi) 0.5-0.6V; (vii) 0.6-0.7V; (viii) 0.7-0.8V; (ix) 0.8-0.9V; (x) 0.9-1.0V; (xi) 1.0-1.5V; (xii) 1.5-2.0V; (xiii) 2.0-2.5V; (xiv) 2.5-3.0V; (xv) 3.0-3.5V; (xvi) 3.5-4.0V; (xvii) 4.0-4.5V; (xviii) 4.5-5.0V; (xix) 5.0-5.5V; (xx) 5.5-6.0V; (xxi) 6.0-6.5V; (xxii) 6.5-7.0V; (xxiii) 7.0-7.5V; (xxiv) 7.5-8.0V; (xxv) 8.0-8.5V; (xxvi) 8.5-9.0V; (xxvii) 9.0-9.5V; (xxviii) 9.5-10.0V; And (xxix)〉10.0V.
Preferably provide or produce at least 1,2,3,4,5,6,7,8,9 or 10 axial time averaging or pseudo-potential barrier, gesture ripple or potential well for every centimetre along the axial length of ion guides device in use.
According to the preferred embodiment, described a plurality of electrodes comprise a plurality of electrodes with hole, and wherein ion passes the hole in use.Preferably, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the described electrode has circle, rectangle, square or oval-shaped hole basically.Preferably, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the described electrode has the hole that size is substantially the same or area is substantially the same.According to another embodiment, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the described electrode has at size or area on the direction of the axle of ion guides device and becomes hole big and/or that diminish gradually.
According to an embodiment, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the described electrode has the hole that its interior diameter or yardstick are selected from following interior diameter or yardstick: (i)≤and 1.0mm; (ii)≤2.0mm; (iii)≤3.0mm; (iv)≤4.0mm; (v)≤5.0mm; (vi)≤6.0mm; (vii)≤7.0mm; (viii)≤8.0mm; (ix)≤9.0mm; (x)≤10.0mm; And (xi)〉10.0mm.Preferably, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the described electrode is spaced from each other and is selected from the axial distance of following axial distance: (i) be less than or equal to 5mm; (ii) be less than or equal to 4.5mm; (iii) be less than or equal to 4mm; (iv) be less than or equal to 3.5mm; (v) be less than or equal to 3mm; (vi) be less than or equal to 2.5mm; (vii) be less than or equal to 2mm; (viii) be less than or equal to 1.5mm; (ix) be less than or equal to 1mm; (x) be less than or equal to 0.8mm; (xi) be less than or equal to 0.6mm; (xii) be less than or equal to 0.4mm; (xiii) be less than or equal to 0.2mm; (xiv) be less than or equal to 0.1mm; And (xv) be less than or equal to 0.25mm.
According to the preferred embodiment, at least some electrodes in described a plurality of electrodes comprise the hole, and the ratio of the center to center axially spaced-apart between the interior diameter of its mesopore or yardstick and the adjacent electrode is selected from: (i)<1.0; (ii) 1.0-1.2; (iii) 1.2-1.4; (iv) 1.4-1.6; (v) 1.6-1.8; (vi) 1.8-2.0; (vii) 2.0-2.2; (viii) 2.2-2.4; (ix) 2.4-2.6; (x) 2.6-2.8; (xi) 2.8-3.0; (xii) 3.0-3.2; (xiii) 3.2-3.4; (xiv) 3.4-3.6; (xv) 3.6-3.8; (xvi) 3.8-4.0; (xvii) 4.0-4.2; (xviii) 4.2-4.4; (xix) 4.4-4.6; (xx) 4.6-4.8; (xxi) 4.8-5.0; And (xxii)〉5.0.
At least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the described electrode preferably has thickness or the axial length that is selected from following thickness or axial length: (i) be less than or equal to 5mm; (ii) be less than or equal to 4.5mm; (iii) be less than or equal to 4mm; (iv) be less than or equal to 3.5mm; (v) be less than or equal to 3mm; (vi) be less than or equal to 2.5mm; (vii) be less than or equal to 2mm; (viii) be less than or equal to 1.5mm; (ix) be less than or equal to 1mm; (x) be less than or equal to 0.8mm; (xi) be less than or equal to 0.6mm; (xii) be less than or equal to 0.4mm; (xiii) be less than or equal to 0.2mm; (xiv) be less than or equal to 0.1mm; And (xv) be less than or equal to 0.25mm.
According to another embodiment, the ion guides device comprises segmented poles collection ion guides device.The ion guides device can for example comprise segmentation four utmost points, sextupole or ends of the earth ion guides device or contain the ion guides device of eight above segmented poles collection.The ion guides device can comprise a plurality of electrodes with the cross section that is selected from following cross section: (i) be similar to or circular basically cross section; The (ii) approximate or face of hyperbolical basically; The cross section of (iii) arc or part circular; The cross section of (iv) approximate or substantial rectangular; And (v) approximate or foursquare basically cross section.
According to another embodiment, the ion guides device can comprise a plurality of electrode groups, and wherein said electrode group is axially spaced apart along the axial length of ion guides device, and wherein each electrode group comprises a plurality of plate electrodes.Each electrode group preferably includes first plate electrode and second plate electrode, and wherein first plate electrode and second plate electrode are arranged on the same plane basically and are arranged in the either side of the center longitudinal axis of ion guides device.
According to this embodiment, preferably be provided for direct voltage or electromotive force are put on first plate electrode and second plate electrode so that limit the device of ion in the ion guides device in the radial direction first.
Each electrode group preferably also comprises the 3rd plate electrode and the 4th plate electrode, wherein the 3rd plate electrode preferably be arranged on the same plane basically with the 4th plate electrode with first plate electrode and second plate electrode and with the arranged in orientation different with second plate electrode with first plate electrode in the either side of the center longitudinal axis of ion guides device.
Being used to apply second exchanges or the device of radio-frequency voltage preferably is arranged to exchange or radio-frequency voltage puts on the 3rd plate electrode and the 4th plate electrode so that preferably limiting ion in the radial direction in the ion guides device with second of the first radial direction quadrature second.
Being used for applying first exchanges or the device of radio-frequency voltage preferably is arranged to exchange or radio-frequency voltage puts at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode of described a plurality of electrodes first.
Being used for applying second exchanges or the device of radio-frequency voltage preferably is arranged to exchange or radio-frequency voltage puts at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode of described a plurality of electrodes second.
The ion guides device preferably has the length that is selected from following length: (i)<and 20mm; (ii) 20-40mm; (iii) 40-60mm; (iv) 60-80mm; (v) 80-100mm; (vi) 100-120mm; (vii) 120-140mm; (viii) 140-160mm; (ix) 160-180mm; (x) 180-200mm; And (xi)〉200mm.
According to the preferred embodiment, the ion guides device comprises at least: (i) 10-20 electrode; (ii) 20-30 electrode; (iii) 30-40 electrode; (iv) 40-50 electrode; (v) 50-60 electrode; (vi) 60-70 electrode; (vii) 70-80 electrode; (viii) 80-90 electrode; (ix) 90-100 electrode; (x) 100-110 electrode; (xi) 110-120 electrode; (xii) 120-130 electrode; (xiii) 130-140 electrode; (xiv) 140-150 electrode; Or (xv)〉150 electrodes.
According to an embodiment, the device that is used to drive or drive ion comprises the device that is used for generating along at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of ion guides device the linear axial DC electric field.
According to an embodiment, the device that is used to drive or drive ion comprises the device that is used for generating along at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of ion guides device non-linear or step axial DC electric field.
Mass analyzer preferably also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce the device of axial DC electric field.
According to an embodiment, the device that is used for driving or drive ion preferably includes the device that is used for polyphase ac or radio-frequency voltage are put at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode of described electrode.
According to an embodiment, the device that is used to drive or drive ion comprises and is arranged in use to drive or to drive ion and/or driving or drive the airflow apparatus of ion by at least a portion of the axial length of ion guides device by air-flow or differential pressure effect at least a portion along the axial length of ion guides device.
According to the preferred embodiment, the device that is used for driving or drive ion comprises the device that is used for one or more transient state direct voltages or electromotive force or one or more direct voltage or potential waveform are put at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode of described electrode.One or more transient state direct voltages or electromotive force or one or more direct voltage or potential waveform preferably produce one or more gesture mound, potential barrier or potential well.One or more transient state direct voltages or potential waveform preferably include repetitive pattern or square wave.
A plurality of axial DC gesture mound, potential barrier or potential well be preferably along the length translation of ion guides device, perhaps a plurality of transient state DC potential or voltage preferably along the axial length of ion guides device by progression put on electrode.
Mass analyzer preferably also comprises first device, first device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or the alternate manner increase or with step, gradually or alternate manner reduce amplitude, height or the degree of depth of one or more transient state direct voltages or electromotive force or one or more direct voltage or potential waveform.
First device preferably is arranged to and is suitable in time period t 1In with amplitude, height or the degree of depth of one or more transient state direct voltages or electromotive force or one or more direct voltage or potential waveform increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or the alternate manner increase or with step, gradually or alternate manner reduce x 1V.Preferably, x 1Be selected from: (i)<0.1V; (ii) 0.1-0.2V; (iii) 0.2-0.3V; (iv) 0.3-0.4V; (v) 0.4-0.5V; (vi) 0.5-0.6V; (vii) 0.6-0.7V; (viii) 0.7-0.8V; (ix) 0.8-0.9V; (x) 0.9-1.0V; (xi) 1.0-1.5V; (xii) 1.5-2.0V; (xiii) 2.0-2.5V; (xiv) 2.5-3.0V; (xv) 3.0-3.5V; (xvi) 3.5-4.0V; (xvii) 4.0-4.5V; (xviii) 4.5-5.0V; (xix) 5.0-5.5V; (xx) 5.5-6.0V; (xxi) 6.0-6.5V; (xxii) 6.5-7.0V; (xxiii) 7.0-7.5V; (xxiv) 7.5-8.0V; (xxv) 8.0-8.5V; (xxvi) 8.5-9.0V; (xxvii) 9.0-9.5V; (xxviii) 9.5-10.0V; And (xxix)〉10.0V.Preferably, t 1Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
Mass analyzer preferably also comprises second device, second device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or the alternate manner increase or with step, gradually or alternate manner reduce to apply the speed or the speed of one or more transient state direct voltages or electromotive force or one or more DC potential or voltage waveform to electrode.
Second device preferably is arranged to and is suitable in time period t 2In will increase gradually to speed or the speed that electrode applies one or more transient state direct voltages or electromotive force or one or more direct voltage or potential waveform, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 2M/s.Preferably, x 2Be selected from: (i)<1; (ii) 1-2; (iii) 2-3; (iv) 3-4; (v) 4-5; (vi) 5-6; (vii) 6-7; (viii) 7-8; (ix) 8-9; (x) 9-10; (xi) 10-11; (xii) 11-12; (xiii) 12-13; (xiv) 13-14; (xv) 14-15; (xvi) 15-16; (xvii) 16-17; (xviii) 17-18; (xix) 18-19; (xx) 19-20; (xxi) 20-30; (xxii) 30-40; (xxiii) 40-50; (xxiv) 50-60; (xxv) 60-70; (xxvi) 70-80; (xxvii) 80-90; (xxviii) 90-100; (xxix) 100-150; (xxx) 150-200; (xxxi) 200-250; (xxxii) 250-300; (xxxiii) 300-350; (xxxiv) 350-400; (xxxv) 400-450; (xxxvi) 450-500; And (xxxvii)〉500.Preferably, t2 is selected from: (i)<and 1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
Mass analyzer preferably includes the 3rd device, the 3rd device be arranged to be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on that first of electrode exchanges or the amplitude of radio-frequency voltage.
The 3rd device preferably is arranged to and is suitable in time period t 3In with first exchange or the amplitude of radio-frequency voltage increases gradually, reduces gradually, gradually changes, scans, linearly increases, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 3V.Preferably, x 3Be selected from: (i)<the 50V peak-to-peak value; (ii) 50-100V peak-to-peak value; (iii) 100-150V peak-to-peak value; (iv) 150-200V peak-to-peak value; (v) 200-250V peak-to-peak value; (vi) 250-300V peak-to-peak value; (vii) 300-350V peak-to-peak value; (viii) 350-400V peak-to-peak value; (ix) 400-450V peak-to-peak value; (x) 450-500V peak-to-peak value; And (xi)〉500V peak-to-peak value.Preferably, t 3Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
Mass analyzer preferably also comprises the 4th device, the 4th device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on first radio frequency of electrode or the frequency of alternating voltage.
The 4th device preferably is arranged to and is suitable in time period t 4In will put on first radio frequency of electrode or alternating voltage frequency increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 4MHz.Preferably, x 4Be selected from: (i)<100kHz; (ii) 100-200kHz; (iii) 200-300kHz; (iv) 300-400kHz; (v) 400-500kHz; (vi) 0.5-1.0MHz; (vii) 1.0-1.5MHz; (viii) 1.5-2.0MHz; (ix) 2.0-2.5MHz; (x) 2.5-3.0MHz; (xi) 3.0-3.5MHz; (xii) 3.5-4.0MHz; (xiii) 4.0-4.5MHz; (xiv) 4.5-5.0MHz; (xv) 5.0-5.5MHz; (xvi) 5.5-6.0MHz; (xvii) 6.0-6.5MHz; (xviii) 6.5-7.0MHz; (xix) 7.0-7.5MHz; (xx) 7.5-8.0MHz; (xxi) 8.0-8.5MHz; (xxii) 8.5-9.0MHz; (xxiii) 9.0-9.5MHz; (xxiv) 9.5-10.0MHz; And (xxv)〉10.0MHz.Preferably, t 4Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
Mass analyzer preferably includes the 5th device, the 5th device be arranged to be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on that second of electrode exchanges or the amplitude of radio-frequency voltage.
The 5th device preferably is arranged to and is suitable in time period t 5In with second exchange or the amplitude of radio-frequency voltage increases gradually, reduces gradually, gradually changes, scans, linearly increases, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 5V.Preferably, x 5Be selected from: (i)<the 50V peak-to-peak value; (ii) 50-100V peak-to-peak value; (iii) 100-150V peak-to-peak value; (iv) 150-200V peak-to-peak value; (v) 200-250V peak-to-peak value; (vi) 250-300V peak-to-peak value; (vii) 300-350V peak-to-peak value; (viii) 350-400V peak-to-peak value; (ix) 400-450V peak-to-peak value; (x) 450-500V peak-to-peak value; And (xi)〉500V peak-to-peak value.Preferably, t 5Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
Mass analyzer preferably also comprises the 6th device, the 6th device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on second radio frequency of electrode or the frequency of alternating voltage.
The 6th device preferably is arranged to and is suitable in time period t 6In will put on second radio frequency of electrode or alternating voltage frequency increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 6MHz.Preferably, x 6Be selected from: (i)<100kHz; (ii) 100-200kHz; (iii) 200-300kHz; (iv) 300-400kHz; (v) 400-500kHz; (vi) 0.5-1.0MHz; (vii) 1.0-1.5MHz; (viii) 1.5-2.0MHz; (ix) 2.0-2.5MHz; (x) 2.5-3.0MHz; (xi) 3.0-3.5MHz; (xii) 3.5-4.0MHz; (xiii) 4.0-4.5MHz; (xiv) 4.5-5.0MHz; (xv) 5.0-5.5MHz; (xvi) 5.5-6.0MHz; (xvii) 6.0-6.5MHz; (xviii) 6.5-7.0MHz; (xix) 7.0-7.5MHz; (xx) 7.5-8.0MHz; (xxi) 8.0-8.5MHz; (xxii) 8.5-9.0MHz; (xxiii) 9.0-9.5MHz; (xxiv) 9.5-10.0MHz; And (xxv)〉10.0MHz.Preferably, t 6Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
According to an embodiment, mass analyzer can also comprise the 7th device, the 7th device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on the direct voltage of at least some electrodes in the electrode of ion guides device or the amplitude of electromotive force, and be used for limiting ion in the radial direction in the ion guides device.
The 7th device preferably is arranged to and is suitable in time period t 7In will put on the direct voltage of at least some electrodes or electromotive force amplitude increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 7V.Preferably, x 7Be selected from: (i)<0.1V; (ii) 0.1-0.2V; (iii) 0.2-0.3V; (iv) 0.3-0.4V; (v) 0.4-0.5V; (vi) 0.5-0.6V; (vii) 0.6-0.7V; (viii) 0.7-0.8V; (ix) 0.8-0.9V; (x) 0.9-1.0V; (xi) 1.0-1.5V; (xii) 1.5-2.0V; (xiii) 2.0-2.5V; (xiv) 2.5-3.0V; (xv) 3.0-3.5V; (xvi) 3.5-4.0V; (xvii) 4.0-4.5V; (xviii) 4.5-5.0V; (xix) 5.0-5.5V; (xx) 5.5-6.0V; (xxi) 6.0-6.5V; (xxii) 6.5-7.0V; (xxiii) 7.0-7.5V; (xxiv) 7.5-8.0V; (xxv) 8.0-8.5V; (xxvi) 8.5-9.0V; (xxvii) 9.0-9.5V; (xxviii) 9.5-10.0V; And (xxix)〉10.0V.Preferably, t 7Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
According to an embodiment, mass analyzer can also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on the amplitude of first radio frequency of electrode or alternating voltage and put on second radio frequency of electrode or the device of the amplitude of alternating voltage.
Mass analyzer can also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on the frequency of first radio frequency of electrode or alternating voltage and put on second radio frequency of electrode or the device of the frequency of alternating voltage.
Mass analyzer can also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on first radio frequency or the alternating voltage of electrode and put on second radio frequency of electrode or the device of the phase difference between the alternating voltage.
According to an embodiment, mass analyzer also comprises and is used under mode of operation the ion guides device being maintained at the device that is selected from the pressure of downforce: (i)<1.0 * 10 -1Mbar; (ii)<1.0 * 10 -2Mbar; (iii)<1.0 * 10 -3Mbar; And (iv)<1.0 * 10 -4Mbar.According to an embodiment, mass analyzer also comprises and is used under mode of operation the ion guides device being maintained at the device that is selected from the pressure of downforce: (i)〉1.0 * 10 -3Mbar; (ii)〉1.0 * 10 -2Mbar; (iii)〉1.0 * 10 -1Mbar; (iv)〉1mbar; (v)〉10mbar; (vi)〉100mbar; (vii)〉5.0 * 10 -3Mbar; (viii)〉5.0 * 10 -2Mbar; (ix) 10 -4-10 -3Mbar; (x) 10 -3-10 -2Mbar; And (xi) 10 -2-10 -1Mbar.
According to an embodiment, mass analyzer also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce device by the air-flow of ion guides device.
Under mode of operation, ion is arranged to basically to withdraw from mass analyzer with the backward of mass-to-charge ratio, so that the high relatively ion of mass-to-charge ratio withdrawed from mass analyzer before the low relatively ion of mass-to-charge ratio.
Under mode of operation, ion preferably is arranged to be trapped in still not cracking basically in the ion guides device in the ion guides device.
According to an embodiment, mass analyzer also comprises and is used in the ion guides device collision cooling or the device of thermalized ions basically.
According to an embodiment, mass analyzer also comprises and is used under mode of operation in the ion guides device device of cracking ion basically.
Mass analyzer preferably also comprises the inlet that is arranged in the ion guides device and/or one or more electrodes in exit, and wherein ion enters and/or withdraw from the ion guides device with impulse form under mode of operation.
Mass analyzer preferably has the cycle time that is selected from following cycle time: (i)<and 1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
According to a further aspect in the invention, provide a kind of mass spectrometer of mass analyzer as mentioned above that comprises.
Mass spectrometer preferably also comprises and is selected from following ionogenic ion source: (i) electron spray ionisation (" ESI ") ion source; (ii) atmospheric pressure photo ionization (" APPI ") ion source; (iii) Atmosphere Pressure Chemical Ionization (APCI) (" APCI ") ion source; (iv) substance assistant laser desorpted ionized (" MALDI ") ion source; (v) laser desorption ionisation (" LDI ") ion source; (vi) atmospheric pressure ionization (" API ") ion source; (vii) desorption ionization (" DIOS ") ion source on the silicon; (viii) electron bombardment (" EI ") ion source; (ix) chemi-ionization (" CI ") ion source; (x) field ionization (FI) (" FI ") ion source; (xi) field desorption (" FD ") ion source; (xii) inductively coupled plasma (" ICP ") ion source; (xiii) fast atom bombardment (" FAB ") ion source; (xiv) liquid secondary ion mass spectroscopy (" LSIMS ") ion source; (xv) desorption electrospray ionization (" DESI ") ion source; (xvi) nickel-63 isotopic ion source; And (xvii) thermal spray ion source.
Ion source can comprise continuously or the pulsed ion source.
Mass spectrometer can also comprise the upstream that is arranged in mass analyzer and/or one or more mass filters in downstream.One or more mass filters can be selected from: (i) quadrupole rod collection mass filter; (ii) time of flight mass filter or mass analyzer; (iii) Wein filter; And (iv) fan-shaped mass filter of magnetic-type or mass analyzer.
Mass spectrometer can comprise the upstream that is arranged in mass analyzer and/or the one or more second ion guides devices or the ion trap device in downstream.
One or more second ion guides devices or ion trap device can be selected from:
(i) multipole bar collection or the multipole bar collection of segmentation ion guides device or ion trap device comprise quadrupole rod collection, sextupole bar collection, ends of the earth bar collection or contain eight bar collection with upper boom;
(ii) ion tunnel or ion funnel formula ion guides device or ion trap device, comprise a plurality of electrodes or at least 2 with hole that ion passed in use, 5,10,20,30,40,50,60,70,80,90 or 100 electrodes, wherein at least 1% in the electrode, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% electrode has substantially the same hole of size or area or size or area and becomes hole big and/or that diminish gradually;
(iii) plane, the heap or the row of tabular or mesh electrode, its midplane, heap or row tabular or mesh electrode comprise a plurality of or at least 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 planes, tabular or mesh electrode, or at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% plane, tabular or mesh electrode roughly is arranged on the plane that ion is advanced in use; And
(iv) ion trap device or ion guides device, comprise that wherein each electrode group comprises along the axial arranged a plurality of electrode groups of the length of ion trap device or ion guides device: (a) first and second electrodes and be used for direct voltage or electromotive force are put on first and second electrodes so that limit the device of ion in the ion guides device in the radial direction first; And (b) third and fourth electrode and be used for and exchange or radio-frequency voltage puts on third and fourth electrode so that limit the device of ion in the ion guides device in the radial direction second.
The second ion guides device or ion trap device can comprise ion tunnel or ion funnel formula ion guides device or ion trap device, and at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% electrode in the wherein said electrode has interior diameter or the yardstick that is selected from following interior diameter or yardstick: (i)≤and 1.0mm; (ii)≤2.0mm; (iii)≤3.0mm; (iv)≤4.0mm; (v)≤5.0mm; (vi)≤6.0mm; (vii)≤7.0mm; (viii)≤8.0mm; (ix)≤9.0mm; (x)≤10.0mm; And (xi)〉10.0mm.
The second ion guides device or ion trap device can also comprise that the second ion guides device exchanges or the radio-frequency voltage device, the second ion guides device exchanges or the radio-frequency voltage device is arranged to will exchange or radio-frequency voltage puts at least 1% in a plurality of electrodes of the second ion guides device or ion trap device with being suitable for, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% electrode is so that radially limit ion in the second ion guides device or ion trap device.
The second ion guides device or ion trap device can be arranged to and be suitable for receive ion beam or group and conversion or divide ion beam or group from mass analyzer, so that be limited and/or be isolated from the second ion guides device or the ion trap device at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 independent ion packet of any special time, and wherein each ion packet is limited individually and/or is isolated from the independent axial potential well that forms in the second ion guides device or ion trap device.
Mass spectrometer can also comprise and is arranged to and is suitable under mode of operation upstream and/or at least 1% of the axial length of at least some ions by the second ion guides device or ion trap device driven in the downstream, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%, perhaps along at least 1% of this axial length, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% drives the device of at least some ions.
According to an embodiment, mass spectrometer can also comprise the transient state dc voltage device, the transient state dc voltage device is arranged to and is suitable for one or more transient state direct voltages or electromotive force or one or more transient state direct voltage or potential waveform are put on the electrode that constitutes the second ion guides device or ion trap device, so as downstream and/or the upstream along at least 1% of the axial length of the second ion guides device or ion trap device, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% drives at least some ions.
According to an embodiment, mass spectrometer can also comprise interchange or radio-frequency voltage device, exchange or the radio-frequency voltage device is arranged to and is suitable for two or more phase shift direct currents or radio-frequency voltage are put on the electrode that constitutes the second ion guides device or ion trap device, so as downstream and/or the upstream along at least 1% of the axial length of the second ion guides device or ion trap device, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% drives at least some ions.
Mass spectrometer can comprise and is arranged to and is suitable at least a portion of the second ion guides device or ion trap device is maintained at the device that is selected from the pressure of downforce: (i)〉0.0001mbar; (ii)〉0.001mbar; (iii)〉0.01mbar; (iv)〉0.1mbar; (v)〉1mbar; (vi)〉10mbar; (vii)〉1mbar; (viii) 0.0001-100mbar; And (ix) 0.001-10mbar.
Mass spectrometer can also comprise and is arranged to and is suitable for bringing out by collision collision, cracking or the consersion unit that dissociate (" CID ") comes the cracking ion.According to another embodiment, mass spectrometer can comprise collision, cracking or the consersion unit that is selected from following equipment: (i) (" the SID ") cracking apparatus that dissociates is brought out on the surface; (ii) electron transfer dissociation cracking apparatus; (iii) electron capture dissociation cracking apparatus; (iv) electron collision or the impact cracking apparatus that dissociates; (v) photo-induced dissociating (" PID ") cracking apparatus; (the vi) laser induced cracking apparatus that dissociates; (vii) infrared radiation brings out dissociation apparatus; (viii) ultra-violet radiation brings out dissociation apparatus; (ix) nozzle-knockout interface cracking apparatus; (x) endogenous cracking apparatus; (xi) cracking apparatus that dissociates is brought out in the ion source collision; (xii) heat or temperature source cracking apparatus; (xiii) electric field brings out cracking apparatus; (xiv) cracking apparatus is brought out in magnetic field; (xv) enzymic digestion or enzyme degraded cracking apparatus; (xvi) ion-ionic reaction cracking apparatus; (xvii) ion-molecule reaction cracking apparatus; (xviii) ion-atomic reaction cracking apparatus; (xix) ion-metastable ion reaction cracking apparatus; (xx) ion-metastable molecule reaction cracking apparatus; (xxi) ion-metastable atom reaction cracking apparatus; (xxii) be used to make ionic reaction to form the ion-ionic reaction equipment of adduction or product ion; (xxiii) be used to make ionic reaction to form the ion-molecule reaction equipment of adduction or product ion; (xxiv) be used to make ionic reaction to form the ion-atomic reaction equipment of adduction or product ion; (xxv) be used to make ionic reaction to form the ion-metastable ion consersion unit of adduction or product ion; (xxvi) be used to make ionic reaction to form the ion-metastable molecule consersion unit of adduction or product ion; And (xxvii) be used to make ionic reaction to form the ion-metastable atom consersion unit of adduction or product ion.
Mass spectrometer can also comprise be arranged to and be suitable in the cycle time of preferred mass analyzer or during increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce the device of the electrical potential difference between mass analyzer and collision, cracking or the reaction member.
According to an embodiment, mass spectrometer can also comprise the upstream that is arranged in mass analyzer and/or the another mass analyzer in downstream.This another mass analyzer can be selected from: (i) Fourier transform (" FT ") mass analyzer; (ii) Fourier Transform Ion cyclotron Resonance (" FTICR ") mass analyzer; (iii) flight time (" TOF ") mass analyzer; (iv) quadrature boost-phase time (" oaTOF ") mass analyzer; (v) axially boost-phase time mass analyzer; (the vi) fan-shaped mass spectrometer of magnetic-type; (vii) Borrow (Paul) or 3D four-electrode quality analyzer; (viii) 2D or linear four-electrode quality analyzer; (ix) Peng Ning (Penning) grabber mass analyzer; (x) ion trap device mass analyzer; (xi) Fourier transform orbital acquisition device; (xii) electrostatic ionic synchrometer; (xiii) static Fourier transform mass spectrometer; And (xiv) quadrupole rod collection mass filter or mass analyzer.
Mass spectrometer can also comprise be arranged to and be suitable in the cycle time of preferred mass analyzer or during synchronously increase gradually with the work of mass analyzer, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or the alternate manner mass-to-charge ratio that reduces this another analyzer transmit the device of window.
According to a further aspect in the invention, provide a kind of method that ion is carried out quality analysis, this method comprises:
The ion guides that comprises a plurality of electrodes device is provided;
To have that first of the first frequency and first amplitude exchanges or radio-frequency voltage puts at least some electrodes in described a plurality of electrode, so that produce one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells along at least a portion of the axial length of ion guides device;
To have that second of the second frequency and second amplitude exchanges or radio-frequency voltage puts on one or more electrodes in described a plurality of electrode, so that radially limit ion in the ion guides device; And
At least a portion along the axial length of ion guides device drives or drives ion and/or driving or drive ion at least a portion by the axial length of ion guides device, so that the ion of mass-to-charge ratio in first scope withdraws from the ion guides device and the ion of mass-to-charge ratio in second different range axially caught or be limited in the ion guides device by a plurality of axially time averaging or pseudo-potential barrier, gesture ripple or potential wells under mode of operation.
According to a further aspect in the invention, provide a kind of mass spectrometric analysis method, this method comprises the method for as mentioned above ion being carried out quality analysis.
According to a further aspect in the invention, a kind of mass analyzer that comprises the ion guides device is provided, wherein have different amplitudes and/or frequency and/or phase place two in use and exchange or radio-frequency voltage is applied in the ion guides device, and wherein produce a plurality of axially time averaging or pseudo-potential barrier, gesture ripple or potential wells along at least a portion of the axial length of ion guides device.
According to a further aspect in the invention, provide a kind of method of analyzing ion, this method comprises:
The ion guides device is provided; And
To have different amplitudes and/or frequency and/or phase place two and exchange or radio-frequency voltage puts on the ion guides device, wherein at least a portion along the axial length of ion guides device produces a plurality of axially time averaging or pseudo-potential barrier, gesture ripple or potential wells.
The preferred embodiment relates to a kind of like this mass analyzer: it comprises the ion guides device that comes isolating ions according to the mass-to-charge ratio of ion, and this ion guides device does not come the known ion miter guide of isolating ions completely different according to the mass-to-charge ratio of ion with being arranged to transmit ion.This preferred mass analyzer particularly advantageous characteristics is: this preferred mass analyzer is worked comparing under the much higher pressure with conventional mass analyzer.
According to a preferred embodiment, mass analyzer comprises stacked rings or ion tunnel formula ion guides device.Stacked rings or ion tunnel formula ion guides device preferably include a plurality of electrodes with hole, and wherein ion passes described hole in use.
First exchanges or radio-frequency voltage preferably is applied in the electrode of mass analyzer, and is preferably such that along the axial length of mass analyzer and provides or produce a plurality of axial pseudopotential ripples or axially pseudopotential mound or potential well.Axially preferably take along the pseudopotential minimum value that replaces and the peaked form of the axle of mass analyzer on pseudopotential ripple or axial pseudopotential mound.
The pseudopotential minimum value preferably can have identical periodicity with the axially spaced-apart of electrode with maximum, or more preferably can have identical periodicity with the electrode group.
Pseudopotential minimum value and peaked relative amplitude preferably depend on the hole dimension of ring electrode and the ratio of the axially spaced-apart between the adjacent ring electrode.Preferably optimize this ratio to guarantee to produce axial pseudopotential ripple with big relatively amplitude, height or degree of depth.This may make it possible to provide high-resolution mass analyser.
Second interchange or radio-frequency voltage preferably are applied in the electrode of ion guides device, so that radially limit ion in the ion guides device with optimum way.Second interchange or radio-frequency voltage preferably are applied in electrode, so that the electrode that replaces preferably is connected to the mutually anti-phase of second interchange or radio-frequency voltage.
According to another preferred embodiment, mass analyzer can comprise straight line ion guides device.This ion guides device can comprise a plurality of electrode groups.Each electrode group can comprise four plate electrodes.Direct voltage or electromotive force preferably are applied in two in the plate electrode, so that limit ion in the radial direction in the ion guides device first.Interchange or radio-frequency voltage preferably are applied in two other plate electrodes, so that limit ion in the radial direction in the ion guides device second.Second radial direction preferably with the first radial direction quadrature.
According to the preferred embodiment, a crowdion that preferably will have different mass-to-charge ratioes is introduced in the mass analyzer.Be preferably such that then ion withdraws from mass analyzer according to their mass-to-charge ratio at different time.
This crowdion can side by side be introduced in the mass analyzer basically at the arrival end of mass analyzer.Ion preferably is arranged to occur from mass analyzer at the port of export of mass analyzer.Ion preferably occurs from mass analyzer with their backward of mass-to-charge ratio.
According to the preferred embodiment, be different from the conventional ion miter guide, along the axial pseudopotential fluctuation of the axle of mass analyzer or axially the pseudopotential ripple preferably have sizable amplitude and preferably can axially catch some ions.
Preferably by one or more transient state direct voltages or electromotive force being put on electrode or coming along the length drives of ion guides device or mass analyzer or drive ion by applying the Constant Direct Current axial electric field.Thus, be able to preferably along ion guides device or mass analyzer length, in face of axially effectively the periodicity ripple in the gesture drive ion.
According to the preferred embodiment, on purpose produce axial pseudopotential ripple by suitable selection electrode gap and by carefully applying suitable radio-frequency voltage with appropriate frequency and amplitude.Axially the pseudopotential ripple preferably has big relatively amplitude.
At any occurrence of the radio-frequency voltage that is applied, axially effectively the ripple that is produced in the gesture preferably is inversely proportional to the mass-to-charge ratio of ion.
Can adopt the whole bag of tricks to come scan ion so that ion withdraws from ion guides device or mass analyzer.According to various embodiment, scan ion is so that ion withdraws from ion guides device or mass analyzer by the following method: (i) scanning radio frequency amplitude makes Driving Field keep constant simultaneously; (ii) the turntable driving field makes the amplitude of radio-frequency voltage keep constant simultaneously; (iii) increase the value of the one or more transient state direct voltages that put on ion guides device or mass analyzer, make radio frequency amplitude keep constant simultaneously; (iv) scan the amplitude of radio-frequency voltage, make the amplitude of one or more transient state direct voltages keep constant simultaneously; Or (the v) combination of any said method.
Effectively the value of the ripple in the gesture preferably depends on the aspect ratio ratio of interval (width with) of the electrode that constitutes the ion guides device.According to an embodiment, the vibration radiofrequency potential of phase homophase preferably is applied in a plurality of adjacent electrodes so that produce a plurality of axial pseudopotential ripples.The aspect ratio of ion guides device or mass analyzer can be determined by the number of the adjacent electrode selecting to connect in this way.
Correspondingly, the periodicity in the vibration radiofrequency potential preferably is based upon between the radio frequency electrode group that constitutes electrode subset.The value of ripple that depends on mass-to-charge ratio is big more, and the gesture resolution of mass analyzer is just big more.Yet, for given rf frequency and voltage,, totally radially effectively limit gesture and reduce although increase the amplitude that aspect ratio has increased ripple.This may cause the loss of ion (high especially relatively mass-to-charge ratio ion) restriction.As a result, the mass charge ratio range of the work of preferred mass analyzer may reduce or may be limited relatively.
According to this preferred embodiment of the invention, additional or second ion trap vibration radiofrequency potential preferably is applied in electrode alternately.This second radiofrequency potential preferably is used for radially limiting ion substantially in the preferred mass analyzer.Correspondingly, for ion tunnel formula ion guides device or mass analyzer, the ring electrode that replaces preferably is connected to the mutually anti-phase of additional or second radiofrequency potential.For the ion guides device that comprises a plurality of plate electrode groups (wherein every group comprises two pairs of plate electrodes), the electrode group that replaces preferably is connected to the mutually anti-phase of additional or second radiofrequency potential.
Preferably put on electrode and can have different frequencies and/or amplitude so that produce the radiofrequency potential of a plurality of axial pseudopotential ripples with the electrode that preferably puts on ion guides device or mass analyzer so that optimally radially limit additional or second radiofrequency potential of ion in mass analyzer.Additional or second radiofrequency potential preferably is used for the ion limit that mass-to-charge ratio is high relatively and is formed in the mass analyzer, and these ions may tend to the electrode of knock-on ion miter guide or mass analyzer and therefore become lose from system originally.Additional or second radiofrequency potential be preferably such that the strong relatively radially pseudo-potential barrier of generations preferably and not appreciable impact along effective gesture distribution of the axle of ion guides device or mass analyzer.
A special advantage of the preferred embodiment is the extra degree of freedom that produces owing to the electrode that two independent radiofrequency signals are put on mass analyzer.The amplitude of these two radiofrequency signals and/or frequency and/or phase place can be different.This makes it possible to optimize mass analyzer aspect restriction, mass range and mass separation or mass resolution.
When using two radiofrequency signals, the form of two radiofrequency signals is taked four different combinations.Each electrode can identify uniquely with n and p prefix.Preferably with electrode from 1 to n number consecutively.Preferably also electrode is grouped into p electrode subset.Therefore, for example, preceding four electrodes (n=1,2,3 and 4) can constitute the first electrode subset p=1.Ensuing four electrodes (n=5,6,7 and 8) can constitute the second electrode subset p=2.Four electrodes (n=9,10,11 and 12) then can constitute third electrode subset p=3.The radiofrequency signal that puts on electrode can be provided by following formula:
Figure A200780029758D0044153935QIETU
Figure A200780029758D0044153947QIETU
Figure A200780029758D0044153958QIETU
Two radio-frequency voltages preferably have different frequencies omega respectively 1And ω 2And corresponding amplitude A and B.In addition, also existence is represented and can be introduced this true phase term of phase difference between two radiofrequency signals
Figure A200780029758D0044154018QIETU
At ω 12Simple case under, can preferably adopt ω 1With respect to ω 290 ° of phase shifts, to avoid undesirable capture effect and the P-to-P voltage difference between the electrode minimized.
As the function of radial distance R and axial location Z. п be in pseudopotential ψ in radio frequency ring heap or the ion tunnel formula ion guides device (R Z) is provided by following formula:
Ψ ( R , Z ) = z · e · Vo 2 4 · m · ω 2 · Zo 2 · I 1 ( R Zo ) 2 · cos ( Z Zo ) 2 + I 0 ( R Zo ) 2 · sin ( Z Zo ) 2 I 0 ( Ro Zo ) 2 - - - ( 1 )
Wherein m/z is the mass-to-charge ratio of ion, and e is an electron charge, V 0Be the peak value radio-frequency voltage, ω is the angular frequency of the radio-frequency voltage that applied, R 0Be the radius in the hole in the electrode, Z 0. п is the center to center interval between the adjacent ring electrode, and I0 is a first kind zeroth order modified Bessel function, and I1 is a first kind single order modified Bessel function.
By following formula as can be known, amplitude, height or the degree of depth of the axial pseudopotential ripple that preferably produces or form along the length of mass analyzer and the mass-to-charge ratio of ion are inversely proportional to.Therefore, mass-to-charge ratio for example be amplitude, height or the degree of depth of 1000 the axial pseudopotential ripple that ion experienced will be have low mass-to-charge ratio 100 the axial pseudopotential ripple that ion experienced amplitude, height or the degree of depth 10%.Therefore, if drive ion along the length of mass analyzer, then mass-to-charge ratio is that 100 ion will experience bigger axial motion resistance than the ion with higher mass-to-charge ratio 1000 on effect.This be because mass-to-charge ratio be 100 ion with experience have relatively significantly, the axial pseudopotential ripple of height or the degree of depth, and mass-to-charge ratio to be 1000 ion will experience the axial pseudopotential ripple that only has relative low amplitude, height or the degree of depth.
According to the preferred embodiment, preferably by with one or more transient state DC potential or voltage or DC potential or voltage waveform progression put on the electrode of ion guides device or mass analyzer, come to advance or drive ion or advance or drive the axial length of ion by mass analyzer along the axial length of mass analyzer.Ion along the advanced speed of the length of mass analyzer preferably depend on the amplitude of one or more transient state DC potential of putting on electrode or voltage or DC potential or voltage waveform and amplitude, height or the degree of depth of the axial pseudopotential ripple that produces along the length of mass analyzer between relation.
If ion is owing to collide the thermalization that becomes repeatedly with buffer gas, then under the situation of the fixed amplitude of the one or more transient state DC potential that put on electrode or voltage or DC potential or voltage waveform, ion will depend on amplitude, height or the degree of depth of the axial pseudopotential ripple that ion experiences along advancing of the length of mass analyzer.Yet axially amplitude, height or the degree of depth of pseudopotential ripple depend on the mass-to-charge ratio of ion.Therefore, ion will depend on the mass-to-charge ratio of ion along the advancing of length of mass analyzer, therefore will carry out quality analysis to ion.
For ion with specific mass-to-charge ratio, if the amplitude of the one or more transient state DC potential that applied or voltage or DC potential or voltage waveform is significantly less than axially amplitude, height or the degree of depth of pseudopotential ripple, then these ions will be not can not be driven along the length of mass analyzer owing to one or more transient state DC potential or voltage or DC potential or voltage waveform are applied in the electrode of mass analyzer.
For ion with specific mass-to-charge ratio, if significantly greater than amplitude, height or the degree of depth of axial pseudopotential ripple, then these ions will be driven along the length of mass analyzer the amplitude of the one or more transient state DC potential that applied or voltage or DC potential or voltage waveform.With preferably with to the electrode progression apply the substantially the same speed of the speed of one or more transient state direct voltages or electromotive force or DC potential or voltage waveform or speed or speed length drives ion along mass analyzer.
For ion with specific mass-to-charge ratio, if the amplitude of one or more transient state DC potential or voltage or DC potential or voltage waveform is similar to amplitude, height or the degree of depth of axial pseudopotential ripple, then these ions still can be driven along the length of mass analyzer, but their average speed will be slightly smaller than to the electrode progression apply the speed or the speed of one or more transient state direct voltages or electromotive force or DC potential or voltage waveform.
Amplitude, height or the degree of depth of the axial pseudopotential ripple that ion experienced that mass-to-charge ratio is high relatively be preferably lower than the low relatively ion of mass-to-charge ratio amplitude, height or the degree of depth of axial pseudopotential ripple of experience preferably.Correspondingly, be applied in electrode if having one or more transient state DC potential of specific amplitude or voltage or DC potential or voltage waveform, then will be preferably to advance the relative high ion of mass-to-charge ratio along the axle of mass analyzer with the corresponding basically speed of the speed that applies one or more transient state DC potential or voltage or DC potential or voltage waveform to electrode or speed or speed.Yet, to can not advance the low relatively ion of mass-to-charge ratio along the length of mass analyzer, because for these ions, axially amplitude, height or the degree of depth of pseudopotential ripple will be greater than the amplitudes of the one or more transient state DC potential that put on electrode or voltage or DC potential or voltage waveform.
Ion with medium mass-to-charge ratio will be along the axle of mass analyzer, still preferably to advance than speed that applies one or more transient state DC potential or voltage or DC potential or voltage waveform to electrode or little speed or the speed of speed.Therefore, be applied in electrode if having one or more transient state direct voltages of suitable amplitude or electromotive force or DC potential or voltage waveform, then mass-to-charge ratio is that 1000 ion will be 100 ion passes through mass analyzer in shorter time a length than mass-to-charge ratio.
According to the preferred embodiment, the ratio (Ro/Zo) that can be preferably that ion passes by minimizing, constitute the diameter of internal holes of electrode of mass analyzer and the interval between the adjacent electrode maximizes preferably amplitude, height or the degree of depth of the axial pseudopotential ripple that forms or produce along the length of mass analyzer, and for example the diameter in the hole by making electrode is as far as possible little and/or by the interval big as far as possible (while still guarantees radially to limit ion in mass analyzer) between the adjacent electrode is realized wherein to minimize Ro/Zo.Preferably the pseudopotential ripple that produces or form along the central shaft of mass analyzer produced relatively significantly, height or the degree of depth preferably increase resistance that ion moves along the central shaft of mass analyzer and the validity that preferably strengthens the mass-to-charge ratio separation process, the mass-to-charge ratio separation process preferably when preferably applying one or more transient state direct voltages or electromotive force or direct voltage or potential waveform to electrode in case along and through axial pseudopotential ripple also so when the length of ion guides device is driven or scan ion, take place.
According to the preferred embodiment, a crowdion can enter in the preferred mass analyzer with impulse form in time T 0.In time T 0, preferably put on the one or more transient state DC potential of electrode or the amplitude of voltage or DC potential or voltage waveform and be preferably set to minimum value or null value.Then, the amplitude of one or more transient state DC potential or voltage or DC potential or voltage waveform can be elevated to final amplitude peak by progression ground scanning, oblique ascension, increase or step in the scanning period of preferred mass analyzer.When initial, the ion that mass-to-charge ratio is high relatively will preferably occur from mass analyzer.When the amplitude of the one or more transient state direct voltages that put on electrode or electromotive force or DC potential or voltage waveform preferably increases in time, the mass-to-charge ratio ion of step-down gradually will preferably occur from mass analyzer.Therefore, will be preferably such that the backward of ion with their mass-to-charge ratio withdraws from mass analyzer over time, thereby make the high relatively ion of mass-to-charge ratio before the low relatively ion of mass-to-charge ratio, withdraw from the preferred mass analyzer.After having separated one group of ion and all ions according to the mass-to-charge ratio of ion and all having withdrawed from mass analyzer, preferably repeat this process, and preferably permit one or more other group ions and enter in the mass analyzer, in the period this one or more other group ion is carried out quality analysis in one scan down then.
Can by and the amplitude of one or more transient state direct voltage or electromotive force or DC potential or voltage waveform increase to synchronous basically mode of peaked time period from minimum value and change the time of to mass analyzer, injecting between ion set or the pulse.Therefore, can be for example at tens of milliseconds to the disengaging time or the cycle time that change or be provided with the preferred mass analyzer between the several seconds, and the separating power of not appreciable impact mass analyzer or resolution.
The preferred mass analyzer advantageously can (it can be for example in scope 10 at relative high workload pressure -3Mbar to 10 -1In the mbar) under according to the mass-to-charge ratio isolating ions of ion.Should be understood that such operating pressure is significantly higher than usually<10 -5Mbar pressure (wherein this pressure is enough low, so that the mean free path of gas molecule significantly is longer than the flight path of ion in mass analyzer) is the operating pressure of the conventional mass analyzer of work down.
Ion guides device in the working pressure range of preferred mass analyzer and the conventional mass spectrometer is suitable basically with the operating pressure of gas collision cell.It will be understood by those skilled in the art that the relative high workload pressure that can use roughing pump such as drum pump or vortex pump to realize the preferred mass analyzer.Therefore, the preferred mass analyzer need not to provide expensive high-vacuum pump such as turbomolecular pump or diffusion pump just can carry out quality analysis to ion.
The preferred mass analyzer preferably has very high transmission efficiency, because all are forwarded by the ion that the preferred mass analyzer receives basically.
The preferred mass analyzer can with the ion storage district of the upstream that can arrange or be provided in mass analyzer or the ion trap device be combined or coupling.Ion storage district or ion trap device can be arranged to accumulation and ion storage, and other ion preferably carries out quality analysis by the preferred mass analyzer.The mass spectrometer that comprises upstream ion grabber and preferred mass analyzer will preferably have relative high duty ratio.
According to an embodiment, ion storage district or ion trap device can be provided in the upstream of preferred mass analyzer, and can provide second or another mass analyzer in the downstream of preferred mass analyzer.Second or another mass analyzer can comprise quadrature boost-phase time mass analyzer or quadrupole rod collection mass analyzer.According to this embodiment, provide the mass spectrometer that preferably has high duty ratio, high transmission efficiency and improved mass resolution.
The preferred mass analyzer can be coupled with various types of mass analyzers.The preferred mass analyzer is preferably such that with the ability that the backward of mass-to-charge ratio transmits ion the preferred mass analyzer can be coupled to the various miscellaneous equipments that can have cycle times variation or different in the time period that can fix or be provided with as required or cycle time.For example, the preferred mass analyzer can be coupled to the time of flight mass analyzer in the downstream that is arranged in the preferred mass analyzer, and in this case, the preferred mass analyzer can be arranged to have tens of milliseconds mass separation or cycle time.Alternatively, the preferred mass analyzer can be coupled to the quadrupole rod collection mass analyzer in the downstream that is arranged in the preferred mass analyzer that is arranged to be scanned.In this case, can make the preferred mass analyzer with hundreds of milliseconds mass separation or work cycle time.
The preferred mass analyzer can with axial boost-phase time mass analyzer, quadrature boost-phase time mass analyzer, 3D quadrupole ion grabber, linear quadrupole ion grabber, quadrupole rod collection mass filter or mass analyzer, the fan-shaped mass analyzer of magnetic-type, ion cyclotron resonance mass analyzer or orbital acquisition device mass analyzer is combined or coupling.This another mass analyzer can comprise that the Fourier transform that can adopt the relevant resonance frequency of quality is so that carry out the Fourier transform mass analyzer of quality analysis to ion.According to a particularly preferred embodiment, the preferred mass analyzer can with quadrature boost-phase time mass analyzer or quadrupole rod collection mass analyzer be combined or coupling.
According to an embodiment, can provide the preferred mass analyzer in the upstream of quadrature boost-phase time mass analyzer.In conventional quadrature boost-phase time mass analyzer, the ion that has approximate identical energy is arranged to by wherein periodically being applied with the quadrature accelerating region of quadrature accelerating field.Wherein be applied with the quadrature accelerating region of quadrature accelerating field length, energy of ions and quadrature accelerating field apply that frequency is used for decision to ion sampling so that the sampling duty ratio of analyzing at the time of flight mass analyzer subsequently.Have approximate identical energy but the ion that enters the quadrature accelerating region with different mass-to-charge ratioes will have different speed at them during by the quadrature accelerating region.Therefore, so that in the drift region of mass analyzer or flight time district during the quadrature speeding-up ion, some ions may surpass the quadrature accelerating region when applying the quadrature accelerating field, and other ion no show quadrature accelerating region also.This shows that in conventional quadrature boost-phase time mass analyzer, the ion that mass-to-charge ratio is different will have different sampling duty ratios.
According to the preferred embodiment, ion discharges from the preferred mass analyzer preferably as a succession of ion packet, and wherein the ion in each bag will preferably have narrow relatively mass charge ratio range and therefore also have narrow relatively VELOCITY DISTRIBUTION.According to the preferred embodiment, all ions in the ion packet of preferred mass analyzer release can preferably be arranged to arrive in the quadrature accelerating region of time of flight mass analyzer in the time substantially the same with applying the quadrature accelerating field.Thereby can realize high sampling duty ratio according to the preferred embodiment.
In order to realize high total sampler body duty ratio, preferably discharge each ion packet from the preferred mass analyzer, so that arriving the time of the quadrature accelerating region of time of flight mass analyzer, the ion in the bag enough lacks, so that ion has insufficient time to any significance degree axial dispersion.Therefore, any axial dispersion of ion will preferably be shorter than the length of the quadrature accelerating region that wherein is applied with the quadrature accelerating field subsequently.According to the preferred embodiment, in any ion packet that the preferred mass analyzer discharges when the mass charge ratio range of ion and energy of ions, the point that discharges ion from the preferred mass analyzer can be arranged to relative short with distance between the quadrature accelerating region of time of flight mass analyzer given.
The mass charge ratio range of ion preferably is arranged to narrow relatively in each ion packet that discharges from the preferred mass analyzer.Preferably the quadrature accelerating region with ion arrival time of flight mass analyzer synchronously applies the quadrature accelerating field.According to the preferred embodiment, might realize 100% sampling duty ratio basically at all ions the ion packet that discharges from the preferred mass analyzer.If the same terms is applied to then can realize total sampler body duty ratio of 100% basically according to the preferred embodiment from each follow-up ion packet of preferred mass analyzer release.
According to an embodiment, the preferred mass analyzer preferably is coupled to quadrature boost-phase time mass analyzer, thereby obtains 100% sampling duty ratio basically.Can be in the downstream of preferred mass analyzer and the upstream of quadrature boost-phase time mass analyzer provide the ion guides device so that auxiliaryly guarantee to obtain high sampling duty ratio.Ion preferably is arranged to withdraw from the preferred mass analyzer and is preferably received by the ion guides device.The ion that occurs from the preferred mass analyzer preferably be trapped in preferably along the length of ion guides device be transferred or a plurality of actual axial of translation to one of potential well.According to an embodiment, one or more transient state direct voltages or electromotive force or direct voltage or potential waveform can preferably be applied in the electrode of ion guides device, so that one or more actual axial preferably moves along the axle or the length of ion guides device to potential well or potential barrier.The preferably enough close-coupled of preferred mass analyzer and downstream ion guides device so that the ion that occurs from the outlet of preferred mass analyzer preferably a succession of bag or independent axial potential well along being transferred or translation with length through the ion guides device.Preferably to carry or the translation ion along the length of ion guides device from the substantially the same order of the outlet appearance of preferred mass analyzer with ion.Ion guides device and quadrature boost-phase time mass analyzer be also closely coupling preferably, so that each ion packet that discharges from the ion guides device is preferably preferably sampled with 100% sampling duty ratio basically by quadrature boost-phase time mass analyzer.
For instance, can be 10ms the cycle time of preferred mass analyzer.The ion packet that occurs from the outlet of preferred mass analyzer can be arranged to be collected to one of potential well and axial translation 200 actual axial, and these 200 actual axial preferably produce in the ion guides device during the cycle time at mass analyzer to potential well.Correspondingly, the axial potential well of each that produces in the ion guides device preferably receives ion in 50 μ s time periods.According to an embodiment, in the ion guides device, produce each ripple or axially the speed of potential well preferably corresponding to cycle time of quadrature boost-phase time mass analyzer.Preferably, discharge ion packet from the ion guides device and preferably reduce gradually in time in the cycle time at mass analyzer, because will preferably reduce in time from the average mass-to-charge ratio of the ion of the outlet release of ion guides device with the time of delay that pusher electrode to the time of flight mass analyzer applies between the pulse of quadrature accelerating voltage.
Preferably provide ion source in the upstream of preferred mass analyzer.Ion source can comprise desorption ionization (" DIOS ") ion source on pulsed ion source such as laser desorption ionisation (" LDI ") ion source, substance assistant laser desorpted ionized (" MALDI ") ion source or the silicon.Alternatively, ion source can comprise the continuous ionic source.If the continuous ionic source is provided, then can be preferably in ionogenic downstream and the upstream of preferred mass analyzer be provided for ion storage and ion periodically be discharged into ion trap device in the preferred mass analyzer.The continuous ionic source can comprise electron spray ionisation (" ESI ") ion source, Atmosphere Pressure Chemical Ionization (APCI) (" APCI ") ion source, electron bombardment (" EI ") ion source, atmospheric pressure photo ionization (" API ") ion source, chemi-ionization (" CI ") ion source, desorption electrospray ionization (" DESI ") ion source, atmospheric pressure MALDI (" AP-MALDI ") ion source, fast atom bombardment (" FAB ") ion source, liquid secondary ion mass spectroscopy (" LSIMS ") ion source, field ionization (FI) (" FI ") ion source or field desorption (" FD ") ion source.Can also use other continuous or pseudo-continuous ionic source.
Collision, cracking or the reaction member that can provide in the upstream of preferred mass analyzer according to an embodiment can also be provided mass spectrometer.Under a kind of mode of operation, the ion cracking or the reaction that make at least some enter collision, cracking or reaction member, thus preferably form multiple cracking, subsystem, product or adduct ion.Gained cracking then, subsystem, product or adduct ion preferably forward or are delivered to the preferred mass analyzer from collision, cracking or reaction member.Cracking, subsystem, product or adduct ion preferably carry out quality analysis by the preferred mass analyzer.
According to an embodiment, can provide mass filter in the upstream of collision, cracking or reaction member.Mass filter can be arranged to transmit ion with one or more specific mass-to-charge ratioes and all other ions of significantly decaying under mode of operation.According to an embodiment, can select specific mother or precursor ion by mass filter, all other ions are significantly decayed so that they are forwarded.Then, preferably cracking or reaction when they enter collision, cracking or reaction member of selected mother or precursor ion.Then, the cracking that is produced, subsystem, adduction or product ion preferably are passed to the preferred mass analyzer, and ion preferably separates during by the preferred mass analyzer in time at them.
Second mass filter can be provided in the downstream of preferred mass analyzer.Second mass filter can be arranged such that and only forward specific cleavage, subsystem, product or the adduct ion with one or more specific mass-to-charge ratioes.First mass filter and/or second mass filter can comprise quadrupole rod collection mass filter.Yet according to other less preferred embodiment, first mass filter and/or second mass filter can comprise the mass filter of other type.
It is particularly advantageous comparing with conventional mass analyzer such as quadrupole rod collection mass analyzer according to the mass analyzer of the preferred embodiment, because preferably detect subsequently by receive a plurality of of mass analyzer or all cracking ions basically.Therefore the preferred mass analyzer can carry out quality analysis and forward ion with very high transmission efficiency ion.By contrast, conventional sweep quadrupole rod collection mass analyzer only can transmit the ion with specific mass-to-charge ratio and therefore have low relatively transmission efficiency in any specified moment.
The preferred mass analyzer makes it possible to measure for example relative abundance of two or more specific cleavage ions with pinpoint accuracy.Though can exist inevitable duty ratio corresponding to reduce owing to measuring each specific cleavage ion to the programming of quadrupole rod collection mass analyzer so that thereby switching to the different cracking ion of transmission confirms analysis.This has caused the loss of sensitivity of each specific cleavage ion.By contrast, the preferred mass analyzer can separate different cracking ions in time, and making can not have any duty ratio or loss of sensitivity ground record then or detect every kind of ion.
Can be by before cracking, removing the selectivity that not potential interested any mother or precursor ion further improve analysis.According to an embodiment, ion can be arranged to the mass filter by the upstream that is preferably located in collision, cracking or reaction member.Mass filter can comprise quadrupole rod collection mass filter, but also can consider the mass filter of other type.Mass filter can be provided in and transmit all ions basically under the mode of operation, that is, mass filter can be arranged to work under non-resolution or ion guides mode of operation.Alternatively, under other mode of operation, mass filter can be configured to only transmit interested specific mother or precursor ion.
The preferred mass analyzer preferably forwards all ions that it receives, but it (means that mass-to-charge ratio is that 100 o'clock resolution is 100 with the resolution that can have unit mass, or mass-to-charge ratio is that 200 o'clock resolution is 200, or mass-to-charge ratio be 500 o'clock be resolution 500, or the like) conventional mass analyzer such as quadrupole rod collection mass analyzer compare and can have lower selectivity.
According to one embodiment of present invention, another mass filter or mass analyzer can be positioned the downstream of preferred mass analyzer.This another mass filter or mass analyzer preferably are arranged in the upstream of ion detector.This another mass filter or mass analyzer can comprise quadrupole rod collection mass filter or mass analyzer, but also can consider the mass filter or the mass analyzer of other type.This another mass filter or mass analyzer can forward under the non-resolution mode of operation of all ions basically.Alternatively, this another mass filter or mass analyzer can be worked only forwarding under quality filterer's operation mode of ion interested.When this another mass filter or mass analyzer were configured to transmit all ions, the preferred mass analyzer preferably was used for ion is carried out quality analysis specially.
In one embodiment, this another mass filter or mass analyzer can be arranged to transmit one or more specific mothers or cracking ion.The preselected time that this another mass filter or mass analyzer can be arranged to switch in the separation cycle time durations of preferred mass analyzer is transmitted some ions with preselected mass-to-charge ratio.Preselected mass-to-charge ratio can be corresponding to the mass-to-charge ratio of a series of interested specific mothers or cracking ion.The preselected time preferably be configured to comprise or corresponding to regioselective mother or cracking ion from time that the preferred mass analyzer withdraws from.Therefore, can be with the selectivity of this another mass filter or mass analyzer but some mothers or cracking ion are measured in essentially no any duty-cycle loss and therefore essentially no any loss of sensitivity ground.
According to an embodiment, be arranged in the another mass filter in downstream of preferred mass analyzer or mass analyzer and preferably be arranged in the cycle time of preferred mass analyzer basically synchronously to be scanned with the work of preferred mass analyzer.The mass-to-charge ratio of this another mass filter or mass analyzer transmits window gradually changing or scan mass-to-charge ratio and the time relation that rule can be arranged to as far as possible closely to mate the ion that withdraws from from the preferred mass analyzer in time.Therefore, quite the mother who withdraws from the preferred mass analyzer or the cracking ion of big figure can preferably pass this another mass filter or mass analyzer forward subsequently, are perhaps forwarded by this another mass filter or mass analyzer.This another mass filter or mass analyzer preferably are arranged to scan to low mass-to-charge ratio ground from high mass-to-charge ratio in the cycle time of preferred mass analyzer, because the preferred mass analyzer is preferably exported ion with the backward of mass-to-charge ratio.
Quadrupole rod collection mass filter or mass analyzer have the maximum scan speed that depends on quadrupole rod collection length.For 1000 daltonian scannings, maximum scan speed can typically be the 100ms level.Correspondingly, if provide quadrupole rod collection mass filter or mass analyzer in the downstream of preferred mass analyzer, then the preferred mass analyzer can be by work cycle time of hundreds of millisecond (rather than tens of millisecond) level, thereby can preferably make the work of preferred mass analyzer and quadrupole rod collection mass analyzer synchronous.
According to an embodiment, a kind of mass spectrometer can be provided, this mass spectrometer preferably includes: be used to receive the device with ion storage; Be used for device with the pulse release ion; Receive ion pulse and come the preferred mass analyzer of isolating ions according to the mass-to-charge ratio of ion; Be arranged in the quadrupole rod collection mass filter in the downstream of preferred mass analyzer; And ion detector.According to an embodiment, this mass spectrometer can comprise: first quadrupole rod collection mass filter or the analyzer; Be used to receive, cracking, storage and with the device of pulse release ion; Receive the preferred mass analyzer of ion pulse; Be arranged in the second quadrupole rod collection mass filter or the analyzer in the downstream of preferred mass analyzer; And the device that is used to detect ion.
Under mode of operation, ion can be received and cracking in the gas collisions unit by the gas collisions unit.Collision cell can be maintained at 10 -4Mbar is between the 1mbar or more preferably be maintained at 10 -3Mbar to 10 -1Pressure between the mbar.Collision cell preferably includes radio frequency ion guides device.Even ion preferably is arranged to also be restricted to the central shaft near the gas collisions unit when the collision that stands with the background gas molecule.The gas collisions unit can comprise multipole bar collection ion guides device, wherein applies to exchange or radio-frequency voltage between contiguous bar, thereby radially limits ion in collision cell.
According to another embodiment, the gas collisions unit can comprise ring heap or ion tunnel formula ion guides device, and this ring heap or ion tunnel formula ion guides device comprise a plurality of electrodes with hole, and ion passes described hole in use.The mutually anti-phase of interchange or radio-frequency voltage preferably is applied between contiguous or adjacent ring or the electrode, so that preferably radially limit ion in the gas collisions unit by generating radially pseudo-potential well.
According to a less preferred embodiment, collision cell can comprise the radio frequency ion guides device of other type.
Can be preferably such that ion enters collision cell with the energy of 10eV at least under mode of operation.Ion can stand with collision cell in gas molecule repeatedly collision and can be brought out cracking.
The gas collisions unit can be used under mode of operation ion storage and with the pulse release ion.Plate or electrode can be arranged in the outlet of collision cell, and can be maintained at and make generation prevent that basically ion from withdrawing from the electromotive force of the potential barrier of collision cell.For cation, can keep pact+10V for other electrode of collision cell electromotive force in case with ion trap in collision cell.Can provide similar plate or electrode at the inlet of collision cell, and this plate or electrode can be maintained at similar electromotive force and withdraw from collision cell to prevent ion via the inlet of collision cell.If the plate in the inlet of collision cell and/or exit or the electromotive force on the electrode are reduced to 0V to moment for other electrode that constitutes collision cell or less than 0V, then ion will preferably discharge from collision cell with pulse.Then, ion can forward the preferred mass analyzer from collision cell.
According to an embodiment, the one or more transient state DC potential that apply to the electrode of preferred mass analyzer or the amplitude of voltage or DC potential or voltage waveform preferably synchronously increase to relative high-amplitude from relative low amplitude in time gradually with the quadrupole rod collection mass filter in the downstream that is arranged in the preferred mass analyzer or the work of mass analyzer.Quadrupole rod collection mass filter preferably is arranged to synchronously scan with the cycle time of preferred mass analyzer or step reduces quality or mass-to-charge ratio.
Description of drawings
Now only by example and describe various embodiment of the present invention with reference to the accompanying drawings, in the accompanying drawings:
Fig. 1 shows mass analyzer in accordance with a preferred embodiment of the present invention;
Fig. 2 shows the amplitude or the degree of depth along the axial pseudopotential ripple of the length of preferred mass analyzer for the ion that is 100 for mass-to-charge ratio;
Fig. 3 shows the amplitude or the degree of depth along the axial pseudopotential ripple of the length of preferred mass analyzer for the ion that is 1000 for mass-to-charge ratio;
Fig. 4 shows one embodiment of the present of invention, and wherein the preferred mass analyzer is coupled to quadrature boost-phase time mass analyzer via transfer optics;
Fig. 5 shows the mass chromatogram that when mass analyzer was worked with the cycle time of 100ms mass-to-charge ratio is 311 and 556 ion;
Fig. 6 shows the mass chromatogram that when mass analyzer was worked with 1 second cycle time mass-to-charge ratio is 311 and 556 ion;
Fig. 7 shows another embodiment, and wherein the preferred mass analyzer is coupled to scanning quadrupole rod collection mass filter or mass analyzer; And
Fig. 8 shows another embodiment, and wherein the preferred mass analyzer is coupled to quadrature boost-phase time mass analyzer via ion tunnel formula ion guides device.
Embodiment
Referring now to Fig. 1 mass analyzer is according to an embodiment of the invention described.Mass analyzer preferably includes ion guides device 2, and ion guides device 2 comprises a plurality of ring electrodes with hole, and ion passes described hole in use.Though not shown in Figure 1, electrode is arranged preferably that in groups wherein each group comprises a plurality of electrodes.All electrodes in the group preferably are connected to the phase homophase of first interchange or radio-frequency voltage.Contiguous or adjacent set preferably is connected to the mutually anti-phase of first interchange or radio-frequency voltage.In addition, adjacent electrode preferably is connected to the mutually anti-phase of second interchange or radio-frequency voltage source.Preferably at the inlet of ion guides device 2 electrode 3 that provides access, and preferably provide exit electrodes 4 in the outlet of ion guides device 2.Can provide gate electrode 1 in the upstream of inlet electrode 3 alternatively.According to an embodiment, inlet electrode 3 and gate electrode 1 can comprise same parts.
Preferably the electromotive force that for example reduces gate electrode 1 by moment ground makes ion enter ion guides device 2 with the recurrent pulses form.The ion that enters ion guides device 2 preferably experiences such radio frequency non homogen field: its be used for since radially pseudo-potential well generation and radially limit ion in ion guides device 2.Advantageously, the preferred mass analyzer preferably is maintained at middle pressure.
According to the preferred embodiment, one or more transient state direct voltages or electromotive force or direct voltage or potential waveform preferably are applied in the electrode that comprises ion guides device 2.Fig. 1 shows in specified moment and applies the transient state direct voltage simultaneously to two electrodes of ion guides device 2.One or more transient state direct voltages or electromotive force or direct voltage or potential waveform preferably along the length of ion guides device 2 by progression put on electrode.One or more transient state direct voltages or electromotive force or direct voltage or potential waveform preferably put on the mode that any special electrodes only continues the relatively short time period with transient state direct voltage or electromotive force and put on the electrode that constitutes ion guides device 2.Then, one or more transient state direct voltages or electromotive force or direct voltage or potential waveform preferably are switched to or put on one or more adjacent electrodes.
To the electrode progression apply one or more transient state direct voltages or electromotive force or direct voltage or potential waveform and be preferably such that the one or more transient state direct current of length translation gesture mound or true gesture mound along ion guides device 2.This be preferably such that with one or more transient state direct voltages or electromotive force or direct voltage or potential waveform progression put on the identical direction of electrode and drive or advance at least some ions along the length of ion guides device 2.
Preferably applying second consistently to electrode exchanges or radio-frequency voltage.Preferably being maintained at second along the adjacent electrode of the axle of ion guides device exchanges or radio-frequency voltage supply mutually anti-phase.This be preferably such that since radially pseudo-potential well generation and radially limit ion in mass analyzer 2.In addition, applying first along the length of ion guides device 2 to a plurality of electrodes exchanges or the radio-frequency voltage supply is preferably such that along the axial length of ion guides device 2 and forms or produce a plurality of time averaging axial pseudopotential ripples or gesture mound, potential barrier or potential trough.
Fig. 2 shows in comprising the mass analyzer that encircles heap or ion tunnel formula ion guides device 2 as shown in fig. 1 has the axial pseudopotential ripple that ion experienced of low relatively mass-to-charge ratio 100 or the amplitude or the degree of depth of gesture mound or pseudo-potential barrier.The electrode of ion guides device 2 is modeled as to be connected to frequency be that 2.7MHz and P-to-P voltage are the single radio frequency voltage supply of 400V.The center to center of ring electrode is modeled as 1.5mm at interval and the interior diameter of ring electrode is modeled as 3mm.
Fig. 3 shows the amplitude or the degree of depth that have reduced of the axial pseudopotential ripple that ion experienced that has high relatively mass-to-charge ratio 1000 in the mass analyzer that comprises as shown in fig. 1 ring heap or ion tunnel formula ion guides device 2 or gesture mound or pseudo-potential barrier.The electrode of ion guides device 2 is modeled as to be connected to frequency be that 2.7MHz and P-to-P voltage are the single radio frequency voltage supply of 400V.The center to center of ring electrode is modeled as 1.5mm at interval and the interior diameter of ring electrode is modeled as 3mm.
The minimum value of time average shown in Fig. 2 and Fig. 3 or axial pseudopotential ripple or pseudo-potential barrier is corresponding to the axial location or the displacement of ring electrode.From Fig. 2 and Fig. 3 as seen, axially the pseudopotential ripple or the amplitude of pseudo-potential barrier or the mass-to-charge ratio of the degree of depth and ion are inversely proportional to.For example, the amplitude with axial pseudopotential ripple that ion experienced of low relatively mass-to-charge ratio 100 is about 5V (as shown in Figure 2), and the amplitude with axial pseudopotential ripple that ion experienced of high relatively mass-to-charge ratio 1000 is about 0.5V (as shown in Figure 3).
Axially effective depth, height or the amplitude dependence of pseudopotential ripple or pseudo-potential barrier are in the mass-to-charge ratio of ion.Therefore, when along the length drives of ion guides device 2, pushing or when advancing ion, ion with high relatively mass-to-charge ratio 1000 will preferably experience less axial resistance (because for the high relatively ion of mass-to-charge ratio, axially amplitude, height or the degree of depth of pseudopotential ripple are low relatively), by contrast, ion with low relatively mass-to-charge ratio 100 will experience bigger axial resistance (because for the low relatively ion of mass-to-charge ratio, axially amplitude, height or the degree of depth of pseudopotential ripple are high relatively).
Preferably, by preferably to the electrode progression of ion guides device 2 one or more transient state direct voltages of applying or electromotive force or direct voltage or potential waveform drive ion along the length of ion guides device 2.According to the preferred embodiment, putting on the one or more transient state direct voltages of electrode or the amplitude of electromotive force or direct voltage or potential waveform preferably increases in the work period of mass analyzer gradually, so that the more and more lower ion of mass-to-charge ratio begins to overcome axial pseudopotential ripple and is therefore driven or drive along the length of ion guides device 2, and final outlet ejection from ion guides device 2.
Fig. 4 shows one embodiment of the present of invention, and wherein preferred mass analyzer 2 is coupled to quadrature boost-phase time mass analyzer 7 via transfer optics 6.Ion from the ion source (not shown) preferably accumulates in the ion trap device 5 of the upstream that is arranged in preferred mass analyzer 2.Preferably applying pulse by the gate electrode 1 to the outlet that is arranged in ion trap device 5 then comes periodically to discharge ion from ion trap device 5.In the moment that discharges ions from ion trap device 5, preferably the amplitude of the one or more transient state DC potential that apply to the electrode of ion guides device 2 or voltage or DC potential or voltage waveform preferably is arranged at minimum value, more preferably is arranged at 0V.Then, the amplitude of the one or more transient state DC potential that apply to the electrode of mass analyzer 2 or voltage or DC potential or voltage waveform preferably increases or ramps up to final maximum or voltage from 0V or minimum value are linear in the cycle time of preferred mass analyzer 2.The cycle time of preferred mass analyzer 2 can be for example in the scope of 10ms-1s.In the cycle time of preferred mass analyzer 2, ion preferably occurs from preferred mass analyzer 2 with their backward of mass-to-charge ratio.The ion that withdraws from mass analyzer 2 preferably forwards the vacuum chamber that holds quadrature boost-phase time mass analyzer 7 then preferably by transfer optics 6.Quadrature boost-phase time mass analyzer 7 preferably carries out quality analysis to ion.
The amplitude that Fig. 4 also shows one or more transient state direct voltages that the electrode to preferred mass analyzer 2 applies or electromotive force or DC potential or voltage waveform is how preferably in three continuous operation intraperiod lines increase of mass analyzer.The corresponding voltage pulse that also shows for ion is entered in the preferred mass analyzer 2 with impulse form and apply to gate electrode 1.
Carried out testing the validity that proves mass analyzer 2.LEK (LeucineEnkephalin) (M+=556) and sulfadimethoxine (Sulfadimethoxine) mixture (M+=311) be injected into basically in the mass spectrometer of arranging as shown in Figure 4.Ion is arranged to enter the ion guides device 2 of preferred mass analyzer 2 from ion trap device 5 with impulse form during 800 μ s gate pulses.Period between the gate pulse and therefore be set at 100ms the cycle time of preferred mass analyzer 2.The one or more transient state DC potential that apply to the electrode of ion guides device 2 or the 100ms of amplitude between gate pulse of voltage or DC potential or voltage waveform in cycle time from the linear oblique ascension of 0V or increase to 2V.
Fig. 5 shows the gained reconstruction quality chromatogram that mass-to-charge ratio is 311 and 556 ion.This mass chromatogram is to come reconstruct according to the flight time data of gathering in cycle time at the 100ms of mass analyzer 2.It is 311 ion with mass-to-charge ratio is that 556 ion is compared the length that need the longer time pass through preferred mass analyzer 2 that this reconstruction quality chromatogram shows mass-to-charge ratio.
Repeat this experiment then, but the width of gate pulse increases to 8ms from 800 μ s.Time between the gate pulse and therefore also increase to 1s the cycle time of preferred mass analyzer 2 from 100ms.Fig. 6 shows the gained reconstruction quality chromatogram that mass-to-charge ratio is 311 and 556 ion.This mass chromatogram is to come reconstruct according to the flight time data of gathering in cycle time at the 1s of mass analyzer 2.It is 311 ion with mass-to-charge ratio is that 556 ion is compared the length that need the longer time pass through preferred mass analyzer 2 that this reconstruction quality chromatogram shows mass-to-charge ratio equally.
According to some embodiment, preferred mass analyzer 2 can have medium mass-to-charge ratio resolution.Yet preferred mass analyzer 2 can be coupled to high-resolution relatively scanning/stepping mass analyzer, such as the quadrupole rod collection mass analyzer 8 in the downstream that preferably is arranged in preferred mass analyzer 2.Fig. 7 shows an embodiment, wherein provides preferred mass analyzer 2 in the upstream of quadrupole rod collection mass analyzer 8.Preferably provide ion detector 9 in the downstream of quadrupole rod collection mass analyzer 8.Preferably synchronously scan the mass-to-charge ratio transmission window of quadrupole rod collection mass analyzer 8 in use with the expection mass-to-charge ratio of the ion that occurs from preferred mass analyzer 2.Preferred mass analyzer 2 is coupled to the four-electrode quality analyzer 8 that is arranged in the downstream has preferably improved mass spectrometric overall instrument duty ratio and sensitivity.
The output of preferred mass analyzer 2 is ion mass-to-charge ratio function in time preferably.At any given time, the mass charge ratio range that withdraws from the ion of preferred mass analyzer 2 will be preferably narrow relatively.Correspondingly, the ion with specific mass-to-charge ratio will preferably withdraw from mass analyzer 2 in the short relatively time period.Therefore, the mass-to-charge ratio of scanning quadrupole rod set analysis device 8 transmits window, and can to put and withdraw from the expection mass charge ratio range of ion of preferred mass analyzer 2 at any time synchronous, thereby the duty ratio of scanning quadrupole rod collection mass analyzer 8 is preferably increased.
The amplitude that Fig. 7 also shows one or more transient state direct voltages that the electrode to preferred mass analyzer 2 applies or electromotive force or DC potential or voltage waveform is how preferably in three continuous operation intraperiod lines increase of mass analyzer.The corresponding voltage pulse that also shows for ion is entered in the preferred mass analyzer 2 with impulse form and apply to gate electrode 1.
But, can rather than press the mass-to-charge ratio transmission window that linear mode increases quadrupole rod collection mass analyzer 8 by the step mode according to an alternative embodiment.Can be by making the mass-to-charge ratio of quadrupole rod collection mass analyzer 8 transmit the window step or step to a limited number of predetermined value with the synchronous basically mode of the release of the ion that withdraws from preferred mass analyzer 2.This makes it possible to increase the transmission efficiency and the duty ratio of quadrupole rod collection mass filter 8 under the mode of operation of only being concerned about and wishing measurement, detect or analyze some specific ion with some mass-to-charge ratio.
An alternative embodiment of the invention has been shown among Fig. 8, and wherein preferred mass analyzer 2 is coupled to quadrature boost-phase time mass analyzer 7 via ion guides device 10.According to this embodiment, preferably provide the mass spectrometer that has improved overall duty ratio and sensitivity.Ion guides device 10 preferably includes each a plurality of electrode that all have the hole.One or more transient state DC potential or voltage or DC potential voltage waveform preferably are applied in the electrode of ion guides device 10, so that drive or the translation ion along the length of ion guides device 10.Ion guides device 10 preferably is arranged to effectively the ion that occurs from preferred mass analyzer 2 be sampled.Therefore, the ion that occurs from preferred mass analyzer 2 as bag in any moment with narrow relatively mass charge ratio range preferably be arranged to be trapped in preferably ion guides device 10 in, form or a plurality of actual axial of generation to one of potential well.The actual axial that preferably forms in ion guides device 10 or produce preferably continues translation along the length of ion guides device 10 to potential well.Ion packet preferably is trapped in the discrete potential well in the ion guides device 10, so that the ion in potential well preferably is not delivered to adjacent potential well.
Preferably the length along ion guides device 10 continues the axial potential well that translation forms or produces in ion guides device 10.After axially potential well arrived the downstream of ion guides device 10, contained ion packet preferably was released in this axial potential well, and ion packet is preferably forwarded quadrature boost-phase time mass analyzer 7.Quadrature quickens to extract the extraction electrode 11 that pulse preferably is applied in quadrature boost-phase time mass analyzer 7.It is preferably synchronous from the release of ion guides device 10 with ion packet that quadrature quicken to extract pulse, so that maximization enters the drift of quadrature boost-phase time mass analyzer 7 or the sampling efficiency of the ion packet in the flight time district.
The amplitude that Fig. 8 also shows one or more transient state direct voltages that the electrode to preferred mass analyzer 2 applies or electromotive force or DC potential or voltage waveform is how preferably in three continuous operation intraperiod lines increase of mass analyzer.The corresponding voltage pulse that also shows for ion is entered in the preferred mass analyzer 2 with impulse form and apply to gate electrode 1.
Can consider various additional embodiments.According to an embodiment, mass analyzer 2 can comprise the ring electrode with rectangle, square or slotted eye.According to another embodiment, mass analyzer 2 can comprise the multipole bar collection of segmentation ion guides device.
According to an embodiment, ion can directly enter the preferred mass analyzer 2 from ion source with impulse form.For example, can provide MALDI ion source or other pulsed ion source, and when the ionogenic target plate of laser beam hits, ion can enter in the preferred mass analyzer 2 with impulse form.
According to an embodiment, can provide collision, cracking or reaction member in the upstream and/or the downstream of preferred mass analyzer 2.According to an embodiment, the electrical potential difference between preferred mass analyzer 2 and collision, cracking or the reaction member can be in the cycle time of preferred mass analyzer 2 and preferably oblique ascension or increase and the oblique deascension or reduce gradually gradually of the amplitude of one or more transient state DC potential of applying along with the electrode to the ion guides device 2 of preferred mass analyzer or voltage or direct voltage or potential waveform.According to this embodiment, preferably optimize the energy of ions that withdraws from mass analyzer 2 at the follow-up cracking that in collision, cracking or the reaction member in the downstream that is provided in preferred mass analyzer 2, takes place.
Though the present invention has been described with reference to preferred embodiment, it will be understood by those skilled in the art that the various changes of making under the situation of the scope of the invention that can in not breaking away from, illustrate on form and the details as claims.

Claims (128)

1. mass analyzer comprises:
The ion guides device that comprises a plurality of electrodes;
Be used for to have that first of the first frequency and first amplitude exchanges or radio-frequency voltage puts at least some electrodes of described a plurality of electrodes so that produce one or more axially devices of time averaging or pseudo-potential barrier, gesture ripple or potential well along at least a portion of the axial length of described ion guides device in use;
Be used for to have that second of the second frequency and second amplitude exchanges or radio-frequency voltage puts on one or more electrodes so that radially limit the device of ion in described ion guides device in use; And
Be used for driving or driving ion and/or driving or drive ion at least a portion by the axial length of described ion guides device so that withdraw from described ion guides device and device in the described ion guides device is axially caught or be limited to the ion of mass-to-charge ratio in second different range by described a plurality of axially time averaging or pseudo-potential barrier, gesture ripple or potential wells at the ion of mass-to-charge ratio in first scope under the mode of operation along at least a portion of the axial length of described ion guides device.
2. mass analyzer as claimed in claim 1, wherein said first frequency is significantly different with described second frequency.
3. mass analyzer as claimed in claim 1, wherein said first frequency is substantially the same with described second frequency.
4. as the described mass analyzer of any claim in the claim 1,2 or 3, wherein said first frequency is selected from: (i)<and 100kHz; (ii) 100-200kHz; (iii) 200-300kHz; (iv) 300-400kHz; (v) 400-500kHz; (vi) 0.5-1.0MHz; (vii) 1.0-1.5MHz; (viii) 1.5-2.0MHz; (ix) 2.0-2.5MHz; (x) 2.5-3.0MHz; (xi) 3.0-3.5MHz; (xii) 3.5-4.0MHz; (xiii) 4.0-4.5MHz; (xiv) 4.5-5.0MHz; (xv) 5.0-5.5MHz; (xvi) 5.5-6.0MHz; (xvii) 6.0-6.5MHz; (xviii) 6.5-7.0MHz; (xix) 7.0-7.5MHz; (xx) 7.5-8.0MHz; (xxi) 8.0-8.5MHz; (xxii) 8.5-9.0MHz; (xxiii) 9.0-9.5MHz; (xxiv) 9.5-10.0MHz; And (xxv)〉10.0MHz.
5. as the described mass analyzer of arbitrary aforementioned claim, wherein said second frequency is selected from: (i)<and 100kHz; (ii) 100-200kHz; (iii) 200-300kHz; (iv) 300-400kHz; (v) 400-500kHz; (vi) 0.5-1.0MHz; (vii) 1.0-1.5MHz; (viii) 1.5-2.0MHz; (ix) 2.0-2.5MHz; (x) 2.5-3.0MHz; (xi) 3.0-3.5MHz; (xii) 3.5-4.0MHz; (xiii) 4.0-4.5MHz; (xiv) 4.5-5.0MHz; (xv) 5.0-5.5MHz; (xvi) 5.5-6.0MHz; (xvii) 6.0-6.5MHz; (xviii) 6.5-7.0MHz; (xix) 7.0-7.5MHz; (xx) 7.5-8.0MHz; (xxi) 8.0-8.5MHz; (xxii) 8.5-9.0MHz; (xxiii) 9.0-9.5MHz; (xxiv) 9.5-10.0MHz; And (xxv)〉10.0MHz.
6. as the described mass analyzer of arbitrary aforementioned claim, wherein said first amplitude is significantly different with described second amplitude.
7. as the described mass analyzer of any claim among the claim 1-5, wherein said first amplitude is substantially the same with described second amplitude.
8. as the described mass analyzer of arbitrary aforementioned claim, wherein said first amplitude is selected from: (i)<and the 50V peak-to-peak value; (ii) 50-100V peak-to-peak value; (iii) 100-150V peak-to-peak value; (iv) 150-200V peak-to-peak value; (v) 200-250V peak-to-peak value; (vi) 250-300V peak-to-peak value; (vii) 300-350V peak-to-peak value; (viii) 350-400V peak-to-peak value; (ix) 400-450V peak-to-peak value; (x) 450-500V peak-to-peak value; And (xi)〉500V peak-to-peak value.
9. as the described mass analyzer of arbitrary aforementioned claim, wherein said second amplitude is selected from: (i)<and the 50V peak-to-peak value; (ii) 50-100V peak-to-peak value; (iii) 100-150V peak-to-peak value; (iv) 150-200V peak-to-peak value; (v) 200-250V peak-to-peak value; (vi) 250-300V peak-to-peak value; (vii) 300-350V peak-to-peak value; (viii) 350-400V peak-to-peak value; (ix) 400-450V peak-to-peak value; (x) 450-500V peak-to-peak value; And (xi)〉500V peak-to-peak value.
10. as the described mass analyzer of arbitrary aforementioned claim, wherein said first interchange or radio-frequency voltage exchange with described second or radio-frequency voltage between phase difference be selected from: (i) 0-10 °; (ii) 10-20 °; (iii) 20-30 °; (iv) 30-40 °; (v) 40-50 °; (vi) 50-60 °; (vii) 60-70 °; (viii) 70-80 °; (ix) 80-90 °; (x) 90-100 °; (xi) 100-110 °; (xii) 110-120 °; (xiii) 120-130 °; (xiv) 130-140 °; (xv) 140-150 °; (xvi) 150-160 °; (xvii) 160-170 °; (xviii) 170-180 °; (xix) 180-190 °; (xx) 190-200 °; (xxi) 200-210 °; (xxii) 210-220 °; (xxiii) 220-230 °; (xxiv) 230-240 °; (xxv) 240-250 °; (xxvi) 250-260 °; (xxvii) 260-270 °; (xxviii) 270-280 °; (xxix) 280-290 °; (xxx) 290-300 °; (xxxi) 300-310 °; (xxxii) 310-320 °; (xxxiii) 320-330 °; (xxxiv) 330-340 °; (xxxv) 340-350 °; And (xxxvi) 350-360 °.
11. as the described mass analyzer of arbitrary aforementioned claim, wherein said first interchange or radio-frequency voltage exchange with described second or radio-frequency voltage between phase difference be selected from: (i) 0 °; (ii) 90 °; (iii) 180 °; And (iv) 270 °.
12. as the described mass analyzer of arbitrary aforementioned claim, wherein said ion guides device comprises a plurality of first electrode groups, and wherein each first electrode group comprises at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 electrode or a plurality of electrode.
13. mass analyzer as claimed in claim 12, wherein said ion guides device comprise m the first electrode group, wherein m is selected from: (i) 1-10; (ii) 11-20; (iii) 21-30; (iv) 31-40; (v) 41-50; (vi) 51-60; (vii) 61-70; (viii) 71-80; (ix) 81-90; (x) 91-100; And (xi)〉100.
14. as claim 12 and 13 described mass analyzers, at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 electrode in wherein one or more or each first electrode group or a plurality of electrode are supplied described first and exchange or the phase homophase of radio-frequency voltage.
15. as the described mass analyzer of any claim in the claim 12,13 or 14, the axial length of at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said first electrode group is selected from: (i)<1mm; (ii) 1-2mm; (iii) 2-3mm; (iv) 3-4mm; (v) 4-5mm; (vi) 5-6mm; (vii) 6-7mm; (viii) 7-8mm; (ix) 8-9mm; (x) 9-10mm; (xi) 10-11mm; (xii) 11-12mm; (xiii) 12-13mm; (xiv) 13-14mm; (xv) 14-15mm; (xvi) 15-16mm; (xvii) 16-17mm; (xviii) 17-18mm; (xix) 18-19mm; (xx) 19-20mm; And (xxi)〉20mm.
16. as the described mass analyzer of any claim among the claim 12-15, the axially spaced-apart between at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said first electrode group is selected from: (i)<1mm; (ii) 1-2mm; (iii) 2-3mm; (iv) 3-4mm; (v) 4-5mm; (vi) 5-6mm; (vii) 6-7mm; (viii) 7-8mm; (ix) 8-9mm; (x) 9-10mm; (xi) 10-11mm; (xii) 11-12mm; (xiii) 12-13mm; (xiv) 13-14mm; (xv) 14-15mm; (xvi) 15-16mm; (xvii) 16-17mm; (xviii) 17-18mm; (xix) 18-19mm; (xx) 19-20mm; And (xxi)〉20mm.
17. as the described mass analyzer of any claim among the claim 12-16, wherein said one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells have along the axial length of described ion guides device, with the corresponding minimum value in centre or center of the described first electrode group.
18. as the described mass analyzer of any claim among the claim 12-17, wherein said one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells have along the axial length of described ion guides device, with the first electrode group between axial distance or the maximum of 50% corresponding axial location basically of spacing.
19. as the described mass analyzer of any claim among the claim 12-18, wherein said one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential well has for the ion with specific mass-to-charge ratio minimum value and/or the maximum for substantially the same height, the degree of depth or amplitude, and wherein said minimum value and/or maximum has and the axial arranged of the described first electrode group or periodically substantially the same periodicity.
20. as the described mass analyzer of arbitrary aforementioned claim, wherein said ion guides device comprises a plurality of second electrode groups, and wherein each second electrode group comprises at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 electrode or a plurality of electrode.
21. mass analyzer as claimed in claim 20, wherein said ion guides device comprise n the second electrode group, wherein n is selected from: (i) 1-10; (ii) 11-20; (iii) 21-30; (iv) 31-40; (v) 41-50; (vi) 51-60; (vii) 61-70; (viii) 71-80; (ix) 81-90; (x) 91-100; And (xi)〉100.
22. as claim 20 and 21 described mass analyzers, at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 electrode in wherein one or more or each second electrode group or a plurality of electrode are supplied described second and exchange or the phase homophase of radio-frequency voltage.
23. as the described mass analyzer of any claim in the claim 20,21 or 22, the axial length of at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said second electrode group is selected from: (i)<1mm; (ii) 1-2mm; (iii) 2-3mm; (iv) 3-4mm; (v) 4-5mm; (vi) 5-6mm; (vii) 6-7mm; (viii) 7-8mm; (ix) 8-9mm; (x) 9-10mm; (xi) 10-11mm; (xii) 11-12mm; (xiii) 12-13mm; (xiv) 13-14mm; (xv) 14-15mm; (xvi) 15-16mm; (xvii) 16-17mm; (xviii) 17-18mm; (xix) 18-19mm; (xx) 19-20mm; And (xxi)〉20mm.
24. as the described mass analyzer of any claim among the claim 20-23, the axially spaced-apart between at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said second electrode group is selected from: (i)<1mm; (ii) 1-2mm; (iii) 2-3mm; (iv) 3-4mm; (v) 4-5mm; (vi) 5-6mm; (vii) 6-7mm; (viii) 7-8mm; (ix) 8-9mm; (x) 9-10mm; (xi) 10-11mm; (xii) 11-12mm; (xiii) 12-13mm; (xiv) 13-14mm; (xv) 14-15mm; (xvi) 15-16mm; (xvii) 16-17mm; (xviii) 17-18mm; (xix) 18-19mm; (xx) 19-20mm; And (xxi)〉20mm.
25. as the described mass analyzer of arbitrary aforementioned claim, wherein axially adjacent electrode is supplied the mutually anti-phase of described second interchange or radio-frequency voltage.
26. as the described mass analyzer of any claim among the claim 20-25, wherein said one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells have along the axial length of described ion guides device, with the corresponding minimum value in centre or center of the described second electrode group.
27. as the described mass analyzer of any claim among the claim 20-26, wherein said one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells have along the axial length of described ion guides device, with the second electrode group between axial distance or the maximum of 50% corresponding axial location basically of spacing.
28. as the described mass analyzer of any claim among the claim 20-27, wherein said one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential well has for the ion with specific mass-to-charge ratio minimum value and/or the maximum for substantially the same height, the degree of depth or amplitude, and wherein said minimum value and/or maximum has and the axial arranged of the described second electrode group or periodically substantially the same periodicity.
29. as the described mass analyzer of arbitrary aforementioned claim, wherein said first scope is selected from: (i)<100; (ii) 100-200; (iii) 200-300; (iv) 300-400; (v) 400-500; (vi) 500-600; (vii) 600-700; (viii) 700-800; (ix) 800-900; (x) 900-1000; And (xi)〉1000.
30. as the described mass analyzer of arbitrary aforementioned claim, wherein said second scope is selected from: (i)<100; (ii) 100-200; (iii) 200-300; (iv) 300-400; (v) 400-500; (vi) 500-600; (vii) 600-700; (viii) 700-800; (ix) 800-900; (x) 900-1000; And (xi)〉1000.
31. as the described mass analyzer of arbitrary aforementioned claim, wherein said being used for exchanges or device that radio-frequency voltage puts at least some electrodes of described a plurality of electrodes is arranged to and is adapted such that along at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of the axial length of described ion guides device produce one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells described first.
32. as the described mass analyzer of arbitrary aforementioned claim, wherein produce or provide described one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential well along at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of the center longitudinal axis of described ion guides device.
33. as the described mass analyzer of arbitrary aforementioned claim, wherein said one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential well extended rmm at least away from the center longitudinal axis of described ion guides device in the radial direction, and wherein r is selected from: (i)<1; (ii) 1-2; (iii) 2-3; (iv) 3-4; (v) 4-5; (vi) 5-6; (vii) 6-7; (viii) 7-8; (ix) 8-9; (x) 9-10; And (xi)〉10.
34. as the described mass analyzer of arbitrary aforementioned claim, wherein drop on ion in scope 1-100,100-200,200-300,300-400,400-500,500-600,600-700,700-800,800-900 or the 900-1000 for mass-to-charge ratio, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% described axially amplitude, height or the degree of depth of time averaging or pseudo-potential barrier, gesture ripple or potential well are selected from: (i)<and 0.1V; (ii) 0.1-0.2V; (iii) 0.2-0.3V; (iv) 0.3-0.4V; (v) 0.4-0.5V; (vi) 0.5-0.6V; (vii) 0.6-0.7V; (viii) 0.7-0.8V; (ix) 0.8-0.9V; (x) 0.9-1.0V; (xi) 1.0-1.5V; (xii) 1.5-2.0V; (xiii) 2.0-2.5V; (xiv) 2.5-3.0V; (xv) 3.0-3.5V; (xvi) 3.5-4.0V; (xvii) 4.0-4.5V; (xviii) 4.5-5.0V; (xix) 5.0-5.5V; (xx) 5.5-6.0V; (xxi) 6.0-6.5V; (xxii) 6.5-7.0V; (xxiii) 7.0-7.5V; (xxiv) 7.5-8.0V; (xxv) 8.0-8.5V; (xxvi) 8.5-9.0V; (xxvii) 9.0-9.5V; (xxviii) 9.5-10.0V; And (xxix)〉10.0V.
35. as the described mass analyzer of arbitrary aforementioned claim, wherein provide or produce at least 1,2,3,4,5,6,7,8,9 or 10 axial time averaging or pseudo-potential barrier, gesture ripple or potential well for every centimetre along the axial length of described ion guides device in use.
36. as the described mass analyzer of arbitrary aforementioned claim, wherein said a plurality of electrodes comprise a plurality of electrodes with hole, wherein ion passes described hole in use.
37. as the described mass analyzer of arbitrary aforementioned claim, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said electrode has circle, rectangle, square or oval-shaped hole basically.
38. as the described mass analyzer of arbitrary aforementioned claim, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said electrode has the hole that size is substantially the same or area is substantially the same.
39. as the described mass analyzer of any claim among the claim 1-37, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said electrode has at size or area on the direction of the axle of described ion guides device and becomes hole big and/or that diminish gradually.
40. as the described mass analyzer of arbitrary aforementioned claim, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said electrode has the hole that its interior diameter or yardstick are selected from following interior diameter or yardstick: (i)≤1.0mm; (ii)≤2.0mm; (iii)≤3.0mm; (iv)≤4.0mm; (v)≤5.0mm; (vi)≤6.0mm; (vii)≤7.0mm; (viii)≤8.0mm; (ix)≤9.0mm; (x)≤10.0mm; And (xi)〉10.0mm.
41. as the described mass analyzer of arbitrary aforementioned claim, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said electrode is spaced from each other and is selected from the axial distance of following axial distance: (i) be less than or equal to 5mm; (ii) be less than or equal to 4.5mm; (iii) be less than or equal to 4mm; (iv) be less than or equal to 3.5mm; (v) be less than or equal to 3mm; (vi) be less than or equal to 2.5mm; (vii) be less than or equal to 2mm; (viii) be less than or equal to 1.5mm; (ix) be less than or equal to 1mm; (x) be less than or equal to 0.8mm; (xi) be less than or equal to 0.6mm; (xii) be less than or equal to 0.4mm; (xiii) be less than or equal to 0.2mm; (xiv) be less than or equal to 0.1mm; And (xv) be less than or equal to 0.25mm.
42. as the described mass analyzer of arbitrary aforementioned claim, at least some electrodes in wherein said a plurality of electrode comprise the hole, and the ratio of the center to center axially spaced-apart between the interior diameter in wherein said hole or yardstick and the adjacent electrode is selected from: (i)<1.0; (ii) 1.0-1.2; (iii) 1.2-1.4; (iv) 1.4-1.6; (v) 1.6-1.8; (vi) 1.8-2.0; (vii) 2.0-2.2; (viii) 2.2-2.4; (ix) 2.4-2.6; (x) 2.6-2.8; (xi) 2.8-3.0; (xii) 3.0-3.2; (xiii) 3.2-3.4; (xiv) 3.4-3.6; (xv) 3.6-3.8; (xvi) 3.8-4.0; (xvii) 4.0-4.2; (xviii) 4.2-4.4; (xix) 4.4-4.6; (xx) 4.6-4.8; (xxi) 4.8-5.0; And (xxii)〉5.0.
43. as the described mass analyzer of arbitrary aforementioned claim, at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode in the wherein said electrode has thickness or the axial length that is selected from following thickness or axial length: (i) be less than or equal to 5mm; (ii) be less than or equal to 4.5mm; (iii) be less than or equal to 4mm; (iv) be less than or equal to 3.5mm; (v) be less than or equal to 3mm; (vi) be less than or equal to 2.5mm; (vii) be less than or equal to 2mm; (viii) be less than or equal to 1.5mm; (ix) be less than or equal to 1mm; (x) be less than or equal to 0.8mm; (xi) be less than or equal to 0.6mm; (xii) be less than or equal to 0.4mm; (xiii) be less than or equal to 0.2mm; (xiv) be less than or equal to 0.1mm; And (xv) be less than or equal to 0.25mm.
44. as the described mass analyzer of any claim among the claim 1-35, wherein said ion guides device comprises segmented poles collection ion guides device.
45. mass analyzer as claimed in claim 44, wherein said ion guides device comprise segmentation four utmost points, sextupole or ends of the earth ion guides device or contain the ion guides device of eight above segmented poles collection.
46. as claim 44 or 45 described mass analyzers, wherein said ion guides device comprises a plurality of electrodes with the cross section that is selected from following cross section: (i) approximate or circular basically cross section; The (ii) approximate or face of hyperbolical basically; The cross section of (iii) arc or part circular; The cross section of (iv) approximate or substantial rectangular; And (v) approximate or foursquare basically cross section.
47. as the described mass analyzer of any claim among the claim 1-35, wherein said ion guides device comprises a plurality of electrode groups, wherein said electrode group is axially spaced apart along the axial length of described ion guides device, and wherein each electrode group comprises a plurality of plate electrodes.
48. mass analyzer as claimed in claim 47, wherein each electrode group comprises first plate electrode and second plate electrode, and wherein said first plate electrode and second plate electrode are arranged on the same plane basically and are arranged in the either side of the center longitudinal axis of described ion guides device.
49. mass analyzer as claimed in claim 48 also comprises being used for direct voltage or electromotive force are put on described first plate electrode and second plate electrode so that limit the device of ion in described ion guides device in the radial direction first.
50. as claim 48 or 49 described mass analyzers, wherein each electrode group also comprises the 3rd plate electrode and the 4th plate electrode, wherein said the 3rd plate electrode be arranged on the same plane basically with the 4th plate electrode and described first plate electrode and second plate electrode and with the arranged in orientation different with second plate electrode with described first plate electrode in the either side of the center longitudinal axis of described ion guides device.
51. mass analyzer as claimed in claim 50 wherein saidly is used to apply second and exchanges or the device of radio-frequency voltage is arranged to exchange or radio-frequency voltage puts on described the 3rd plate electrode and the 4th plate electrode so that limit ion in the radial direction in described ion guides device second described second.
52. as the described mass analyzer of arbitrary aforementioned claim, wherein saidly be used for applying described first and exchange or the device of radio-frequency voltage is arranged to exchange or radio-frequency voltage puts at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode of described a plurality of electrodes described first.
53. as the described mass analyzer of arbitrary aforementioned claim, wherein saidly be used for applying described second and exchange or the device of radio-frequency voltage is arranged to exchange or radio-frequency voltage puts at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode of described a plurality of electrodes described second.
54. as the described mass analyzer of arbitrary aforementioned claim, wherein said ion guides utensil has the length that is selected from following length: (i)<20mm; (ii) 20-40mm; (iii) 40-60mm; (iv) 60-80mm; (v) 80-100mm; (vi) 100-120mm; (vii) 120-140mm; (viii) 140-160mm; (ix) 160-180mm; (x) 180-200mm; And (xi)〉200mm.
55. as the described mass analyzer of arbitrary aforementioned claim, wherein said ion guides device comprises at least: (i) 10-20 electrode; (ii) 20-30 electrode; (iii) 30-40 electrode; (iv) 40-50 electrode; (v) 50-60 electrode; (vi) 60-70 electrode; (vii) 70-80 electrode; (viii) 80-90 electrode; (ix) 90-100 electrode; (x) 100-110 electrode; (xi) 110-120 electrode; (xii) 120-130 electrode; (xiii) 130-140 electrode; (xiv) 140-150 electrode; Or (xv)〉150 electrodes.
56. as the described mass analyzer of arbitrary aforementioned claim, the wherein said device that is used to drive or drive ion comprises the device that is used for generating along at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of described ion guides device the linear axial DC electric field.
57. as the described mass analyzer of arbitrary aforementioned claim, the wherein said device that is used to drive or drive ion comprises the device that is used for generating along at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of described ion guides device non-linear or step axial DC electric field.
58. as claim 56 or 57 described mass analyzers, also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce the device of described axial DC electric field.
59. as the described mass analyzer of arbitrary aforementioned claim, the wherein said device that is used for driving or drive ion comprises the device that is used for polyphase ac or radio-frequency voltage are put at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode of described electrode.
60. as the described mass analyzer of arbitrary aforementioned claim, the wherein said device that is used to drive or drive ion comprises and is arranged in use to drive or to drive ion and/or driving or drive the airflow apparatus of ion by at least a portion of the axial length of described ion guides device by air-flow or differential pressure effect at least a portion along the axial length of described ion guides device.
61. as the described mass analyzer of arbitrary aforementioned claim, the wherein said device that is used for driving or drive ion comprises the device that is used for one or more transient state direct voltages or electromotive force or one or more direct voltage or potential waveform are put at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% electrode of described electrode.
62. mass analyzer as claimed in claim 61, wherein said one or more transient state direct voltages or electromotive force or one or more direct voltage or potential waveform produce one or more gesture mound, potential barrier or potential well.
63. as claim 61 or 62 described mass analyzers, wherein said one or more transient state direct voltages or potential waveform comprise repetitive pattern or square wave.
64. as claim 61,62 or 63 described mass analyzers, wherein a plurality of in use axial DC gesture mound, potential barrier or potential well be along the length translation of described ion guides device, perhaps a plurality of transient state DC potential or voltage along the axial length of described ion guides device by progression put on electrode.
65. as the described mass analyzer of any claim among the claim 61-64, also comprise first device, described first device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or the alternate manner increase or with step, gradually or alternate manner reduce amplitude, height or the degree of depth of described one or more transient state direct voltage or electromotive force or described one or more direct voltage or potential waveform.
66. as the described mass analyzer of claim 65, wherein said first device is arranged to and is suitable in time period t 1In will described one or more transient state direct voltages or electromotive force or described one or more direct voltage or potential waveform amplitude, height or the degree of depth increase gradually, reduce gradually, gradually change, scan, linear increase, linearity reduce, with step, gradually or the alternate manner increase or with step, gradually or alternate manner reduce x 1V.
67. as the described mass analyzer of claim 66, wherein x 1Be selected from: (i)<0.1V; (ii) 0.1-0.2V; (iii) 0.2-0.3V; (iv) 0.3-0.4V; (v) 0.4-0.5V; (vi) 0.5-0.6V; (vii) 0.6-0.7V; (viii) 0.7-0.8V; (ix) 0.8-0.9V; (x) 0.9-1.0V; (xi) 1.0-1.5V; (xii) 1.5-2.0V; (xiii) 2.0-2.5V; (xiv) 2.5-3.0V; (xv) 3.0-3.5V; (xvi) 3.5-4.0V; (xvii) 4.0-4.5V; (xviii) 4.5-5.0V; (xix) 5.0-5.5V; (xx) 5.5-6.0V; (xxi) 6.0-6.5V; (xxii) 6.5-7.0V; (xxiii) 7.0-7.5V; (xxiv) 7.5-8.0V; (xxv) 8.0-8.5V; (xxvi) 8.5-9.0V; (xxvii) 9.0-9.5V; (xxviii) 9.5-10.0V; And (xxix)〉10.0V.
68. as claim 66 or 67 described mass analyzer, wherein t 1Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
69. as the described mass analyzer of any claim among the claim 61-68, also comprise second device, described second device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or the alternate manner increase or with step, gradually or alternate manner reduce to apply the speed or the speed of described one or more transient state direct voltage or electromotive force or described one or more DC potential or voltage waveform to described electrode.
70. as the described mass analyzer of claim 69, wherein said second device is arranged to and is suitable in time period t 2In will increase gradually to speed or the speed that described electrode applies described one or more transient state direct voltage or electromotive force or described one or more direct voltage or potential waveform, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 2M/s.
71. as the described mass analyzer of claim 70, wherein x 2Be selected from: (i)<1; (ii) 1-2; (iii) 2-3; (iv) 3-4; (v) 4-5; (vi) 5-6; (vii) 6-7; (viii) 7-8; (ix) 8-9; (x) 9-10; (xi) 10-11; (xii) 11-12; (xiii) 12-13; (xiv) 13-14; (xv) 14-15; (xvi) 15-16; (xvii) 16-17; (xviii) 17-18; (xix) 18-19; (xx) 19-20; (xxi) 20-30; (xxii) 30-40; (xxiii) 40-50; (xxiv) 50-60; (xxv) 60-70; (xxvi) 70-80; (xxvii) 80-90; (xxviii) 90-100; (xxix) 100-150; (xxx) 150-200; (xxxi) 200-250; (xxxii) 250-300; (xxxiii) 300-350; (xxxiv) 350-400; (xxxv) 400-450; (xxxvi) 450-500; And (xxxvii)〉500.
72. as claim 70 or 71 described mass analyzer, wherein t 2Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
73. as the described mass analyzer of arbitrary aforementioned claim, also comprise the 3rd device, described the 3rd device be arranged to be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on that described first of described electrode exchanges or the amplitude of radio-frequency voltage.
74. as the described mass analyzer of claim 73, wherein said the 3rd device is arranged to and is suitable in time period t 3In will be described first exchange or the amplitude of radio-frequency voltage increases gradually, reduces gradually, gradually changes, scans, linearly increases, linearity reduces, with step, gradually or the alternate manner increase or with step, gradually or alternate manner reduce x 3V.
75. as the described mass analyzer of claim 74, wherein x 3Be selected from: (i)<the 50V peak-to-peak value; (ii) 50-100V peak-to-peak value; (iii) 100-150V peak-to-peak value; (iv) 150-200V peak-to-peak value; (v) 200-250V peak-to-peak value; (vi) 250-300V peak-to-peak value; (vii) 300-350V peak-to-peak value; (viii) 350-400V peak-to-peak value; (ix) 400-450V peak-to-peak value; (x) 450-500V peak-to-peak value; And (xi)〉500V peak-to-peak value.
76. as claim 74 or 75 described mass analyzer, wherein t 3Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
77. as the described mass analyzer of arbitrary aforementioned claim, also comprise the 4th device, described the 4th device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on described first radio frequency of described electrode or the frequency of alternating voltage.
78. as the described mass analyzer of claim 77, wherein said the 4th device is arranged to and is suitable in time period t 4In will put on described first radio frequency of described electrode or alternating voltage frequency increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 4MHz.
79. as the described mass analyzer of claim 78, wherein x 4Be selected from: (i)<100kHz; (ii) 100-200kHz; (iii) 200-300kHz; (iv) 300-400kHz; (v) 400-500kHz; (vi) 0.5-1.0MHz; (vii) 1.0-1.5MHz; (viii) 1.5-2.0MHz; (ix) 2.0-2.5MHz; (x) 2.5-3.0MHz; (xi) 3.0-3.5MHz; (xii) 3.5-4.0MHz; (xiii) 4.0-4.5MHz; (xiv) 4.5-5.0MHz; (xv) 5.0-5.5MHz; (xvi) 5.5-6.0MHz; (xvii) 6.0-6.5MHz; (xviii) 6.5-7.0MHz; (xix) 7.0-7.5MHz; (xx) 7.5-8.0MHz; (xxi) 8.0-8.5MHz; (xxii) 8.5-9.0MHz; (xxiii) 9.0-9.5MHz; (xxiv) 9.5-10.0MHz; And (xxv)〉10.0MHz.
80. as claim 78 or 79 described mass analyzer, wherein t 4Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
81. as the described mass analyzer of arbitrary aforementioned claim, also comprise the 5th device, described the 5th device be arranged to be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on that described second of described electrode exchanges or the amplitude of radio-frequency voltage.
82. as the described mass analyzer of claim 81, wherein said the 5th device is arranged to and is suitable in time period t 5In will be described second exchange or the amplitude of radio-frequency voltage increases gradually, reduces gradually, gradually changes, scans, linearly increases, linearity reduces, with step, gradually or the alternate manner increase or with step, gradually or alternate manner reduce x 5V.
83. as the described mass analyzer of claim 82, wherein x 5Be selected from: (i)<the 50V peak-to-peak value; (ii) 50-100V peak-to-peak value; (iii) 100-150V peak-to-peak value; (iv) 150-200V peak-to-peak value; (v) 200-250V peak-to-peak value; (vi) 250-300V peak-to-peak value; (vii) 300-350V peak-to-peak value; (viii) 350-400V peak-to-peak value; (ix) 400-450V peak-to-peak value; (x) 450-500V peak-to-peak value; And (xi)〉500V peak-to-peak value.
84. as claim 82 or 83 described mass analyzer, wherein t 5Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
85. as the described mass analyzer of arbitrary aforementioned claim, also comprise the 6th device, described the 6th device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on described second radio frequency of described electrode or the frequency of alternating voltage.
86. as the described mass analyzer of claim 85, wherein said the 6th device is arranged to and is suitable in time period t 6In will put on described second radio frequency of described electrode or alternating voltage frequency increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 6MHz.
87. as the described mass analyzer of claim 86, wherein x 6Be selected from: (i)<100kHz; (ii) 100-200kHz; (iii) 200-300kHz; (iv) 300-400kHz; (v) 400-500kHz; (vi) 0.5-1.0MIIz; (vii) 1.0-1.5MIIz; (viii) 1.5-2.0MHz; (ix) 2.0-2.5MHz; (x) 2.5-3.0MHz; (xi) 3.0-3.5MHz; (xii) 3.5-4.0MHz; (xiii) 4.0-4.5MHz; (xiv) 4.5-5.0MHz; (xv) 5.0-5.5MHz; (xvi) 5.5-6.0MHz; (xvii) 6.0-6.5MHz; (xviii) 6.5-7.0MHz; (xix) 7.0-7.5MHz; (xx) 7.5-8.0MHz; (xxi) 8.0-8.5MHz; (xxii) 8.5-9.0MHz; (xxiii) 9.0-9.5MHz; (xxiv) 9.5-10.0MHz; And (xxv)〉10.0MHz.
88. as claim 86 or 87 described mass analyzer, wherein t 6Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
89. as the described mass analyzer of arbitrary aforementioned claim, also comprise the 7th device, described the 7th device be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on the direct voltage of at least some electrodes in the described electrode of described ion guides device or the amplitude of electromotive force, and be used for limiting ion in the radial direction in described ion guides device.
90. as the described mass analyzer of claim 89, wherein said the 7th device is arranged to and is suitable in time period t 7In will put on the described direct voltage of described at least some electrodes or electromotive force amplitude increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce x 7V.
91. as the described mass analyzer of claim 90, wherein x 7Be selected from: (i)<0.1V; (ii) 0.1-0.2V; (iii) 0.2-0.3V; (iv) 0.3-0.4V; (v) 0.4-0.5V; (vi) 0.5-0.6V; (vii) 0.6-0.7V; (viii) 0.7-0.8V; (ix) 0.8-0.9V; (x) 0.9-1.0V; (xi) 1.0-1.5V; (xii) 1.5-2.0V; (xiii) 2.0-2.5V; (xiv) 2.5-3.0V; (xv) 3.0-3.5V; (xvi) 3.5-4.0V; (xvii) 4.0-4.5V; (xviii) 4.5-5.0V; (xix) 5.0-5.5V; (xx) 5.5-6.0V; (xxi) 6.0-6.5V; (xxii) 6.5-7.0V; (xxiii) 7.0-7.5V; (xxiv) 7.5-8.0V; (xxv) 8.0-8.5V; (xxvi) 8.5-9.0V; (xxvii) 9.0-9.5V; (xxviii) 9.5-10.0V; And (xxix)〉10.0V.
92. as claim 90 or 91 described mass analyzer, wherein t 7Be selected from: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
93. as the described mass analyzer of arbitrary aforementioned claim, also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on the amplitude of described first radio frequency of described electrode or alternating voltage and put on described second radio frequency of described electrode or the device of the amplitude of alternating voltage.
94. as the described mass analyzer of arbitrary aforementioned claim, also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on the frequency of described first radio frequency of described electrode or alternating voltage and put on described second radio frequency of described electrode or the device of the frequency of alternating voltage.
95. as the described mass analyzer of arbitrary aforementioned claim, also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce to put on described first radio frequency or the alternating voltage of described electrode and put on described second radio frequency of described electrode or the device of the phase difference between the alternating voltage.
96., also comprise being used under mode of operation, described ion guides device being maintained at the device that is selected from the pressure of downforce: (i)<1.0 * 10 as the described mass analyzer of arbitrary aforementioned claim -1Mbar; (ii)<1.0 * 10 -2Mbar; (iii)<1.0 * 10 -3Mbar; And (iv)<1.0 * 10 -4Mbar.
97., also comprise being used under mode of operation, described ion guides device being maintained at the device that is selected from the pressure of downforce: (i) as the described mass analyzer of arbitrary aforementioned claim〉1.0 * 10 -3Mbar; (ii)〉1.0 * 10 -2Mbar; (iii)〉1.0 * 10 -1Mbar; (iv)〉1mbar; (v)〉10mbar; (vi)〉100mbar; (vii)〉5.0 * 10 -3Mbar; (viii)〉5.0 * 10 -2Mbar; (ix) 10 -4-10 -3Mbar; (x) 10 -3-10 -2Mbar; And (xi) 10 -2-10 -1Mbar.
98. as the described mass analyzer of arbitrary aforementioned claim, also comprise be arranged to and be suitable for increasing gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce device by the air-flow of described ion guides device.
99. as the described mass analyzer of arbitrary aforementioned claim, wherein under mode of operation, ion is arranged to basically to withdraw from described mass analyzer with the backward of mass-to-charge ratio, so that the high relatively ion of mass-to-charge ratio withdrawed from described mass analyzer before the low relatively ion of mass-to-charge ratio.
100. as the described mass analyzer of arbitrary aforementioned claim, wherein under mode of operation, ion is arranged to be trapped in still not cracking basically in described ion guides device in the described ion guides device.
101. as the described mass analyzer of arbitrary aforementioned claim, also comprise being used in described ion guides device the collision cooling or the device of thermalized ions basically.
102. as the described mass analyzer of arbitrary aforementioned claim, also comprise being used under mode of operation in described ion guides device the device of cracking ion basically.
103. as the described mass analyzer of arbitrary aforementioned claim, also comprise the inlet that is arranged in described ion guides device and/or one or more electrodes in exit, wherein ion enters and/or withdraws from described ion guides device with impulse form under mode of operation.
104. as the described mass analyzer of arbitrary aforementioned claim, wherein said mass analyzer has the cycle time that is selected from following cycle time: (i)<1ms; (ii) 1-10ms; (iii) 10-20ms; (iv) 20-30ms; (v) 30-40ms; (vi) 40-50ms; (vii) 50-60ms; (viii) 60-70ms; (ix) 70-80ms; (x) 80-90ms; (xi) 90-100ms; (xii) 100-200ms; (xiii) 200-300ms; (xiv) 300-400ms; (xv) 400-500ms; (xvi) 500-600ms; (xvii) 600-700ms; (xviii) 700-800ms; (xix) 800-900ms; (xx) 900-1000ms; (xxi) 1-2s; (xxii) 2-3s; (xxiii) 3-4s; (xxiv) 4-5s; And (xxv)〉5s.
105. a mass spectrometer comprises as the described mass analyzer of arbitrary aforementioned claim.
106., also comprise being selected from following ionogenic ion source: (i) electron spray ionisation (" ESI ") ion source as the described mass spectrometer of claim 105; (ii) atmospheric pressure photo ionization (" APPI ") ion source; (iii) Atmosphere Pressure Chemical Ionization (APCI) (" APCI ") ion source; (iv) substance assistant laser desorpted ionized (" MALDI ") ion source; (v) laser desorption ionisation (" LDI ") ion source; (vi) atmospheric pressure ionization (" API ") ion source; (vii) desorption ionization (" DIOS ") ion source on the silicon; (viii) electron bombardment (" EI ") ion source; (ix) chemi-ionization (" CI ") ion source; (x) field ionization (FI) (" FI ") ion source; (xi) field desorption (" FD ") ion source; (xii) inductively coupled plasma (" ICP ") ion source; (xiii) fast atom bombardment (" FAB ") ion source; (xiv) liquid secondary ion mass spectroscopy (" LSIMS ") ion source; (xv) desorption electrospray ionization (" DESI ") ion source; (xvi) nickel-63 isotopic ion source; And (xvii) thermal spray ion source.
107., also comprise continuously or the pulsed ion source as claim 105 or 106 described mass spectrometers.
108., also comprise the upstream that is arranged in described mass analyzer and/or one or more mass filters in downstream as the described mass spectrometer of any claim in the claim 105,106 or 107.
109. as the described mass spectrometer of claim 108, wherein said one or more mass filters are selected from: (i) quadrupole rod collection mass filter; (ii) time of flight mass filter or mass analyzer; (iii) Wein filter; And (iv) fan-shaped mass filter of magnetic-type or mass analyzer.
110., also comprise the upstream that is arranged in described mass analyzer and/or the one or more second ion guides devices or the ion trap device in downstream as the described mass spectrometer of any claim among the claim 105-109.
111. as the described mass spectrometer of claim 110, wherein said one or more second ion guides devices or ion trap device are selected from:
(i) multipole bar collection or the multipole bar collection of segmentation ion guides device or ion trap device comprise quadrupole rod collection, sextupole bar collection, ends of the earth bar collection or contain eight bar collection with upper boom;
(ii) ion tunnel or ion funnel formula ion guides device or ion trap device, comprise a plurality of electrodes or at least 2 with hole that ion passed in use, 5,10,20,30,40,50,60,70,80,90 or 100 electrodes, at least 1% in the wherein said electrode, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% electrode has substantially the same hole of size or area or size or area and becomes hole big and/or that diminish gradually;
(iii) plane, the heap or the row of tabular or mesh electrode, its midplane, described heap or row tabular or mesh electrode comprise a plurality of or at least 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 planes, tabular or mesh electrode, or at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% described plane, tabular or mesh electrode roughly is arranged on the plane that ion is advanced in use; And
(iv) ion trap device or ion guides device, comprise that wherein each electrode group comprises along the axial arranged a plurality of electrode groups of the length of described ion trap device or ion guides device: (a) first and second electrodes and be used for direct voltage or electromotive force are put on described first and second electrodes so that limit the device of ion in described ion guides device in the radial direction first; And (b) third and fourth electrode and be used for and exchange or radio-frequency voltage puts on described third and fourth electrode so that limit the device of ion in described ion guides device in the radial direction second.
112. as claim 110 or 111 described mass spectrometers, wherein said second ion guides device or ion trap device comprise ion tunnel or ion funnel formula ion guides device or ion trap device, and at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% electrode in the wherein said electrode has interior diameter or the yardstick that is selected from following interior diameter or yardstick: (i)≤and 1.0mm; (ii)≤2.0mm; (iii)≤3.0mm; (iv)≤4.0mm; (v)≤5.0mm; (vi)≤6.0mm; (vii)≤7.0mm; (viii)≤8.0mm; (ix)≤9.0mm; (x)≤10.0mm; And (xi)〉10.0mm.
113. as claim 110,111 or 112 described mass spectrometers, wherein said second ion guides device or ion trap device comprise that also the second ion guides device exchanges or the radio-frequency voltage device, the described second ion guides device exchanges or the radio-frequency voltage device is arranged to will exchange or radio-frequency voltage puts at least 1% in described a plurality of electrodes of described second ion guides device or ion trap device with being suitable for, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% electrode is so that radially limit ion in described second ion guides device or ion trap device.
114. as the described mass spectrometer of any claim among the claim 110-113, wherein said second ion guides device or ion trap device are arranged to and are suitable for receiving ion beam or group and conversion or dividing described ion beam or group from described mass analyzer, so that at any special time at least 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 independent ion packet are limited and/or are isolated from described second ion guides device or the ion trap device, and wherein each ion packet is limited individually and/or is isolated from the independent axial potential well that forms in described second ion guides device or ion trap device.
115., also comprise being arranged to and being suitable under mode of operation upstream and/or at least 1% of the axial length of at least some ions by described second ion guides device or ion trap device driven in the downstream as the described mass spectrometer of any claim among the claim 110-114,5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%, perhaps along at least 1% of described axial length, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% drives the device of at least some ions.
116. as the described mass spectrometer of any claim among the claim 110-115, also comprise the transient state dc voltage device, described transient state dc voltage device is arranged to and is suitable for one or more transient state direct voltages or electromotive force or one or more transient state direct voltage or potential waveform are put on the described electrode that constitutes described second ion guides device or ion trap device, so as downstream and/or the upstream along at least 1% of the axial length of described second ion guides device or ion trap device, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% drives at least some ions.
117. as the described mass spectrometer of any claim among the claim 110-116, also comprise and exchanging or the radio-frequency voltage device, described interchange or radio-frequency voltage device are arranged to and are suitable for two or more phase shift direct currents or radio-frequency voltage are put on the electrode that constitutes described second ion guides device or ion trap device, so as downstream and/or the upstream along at least 1% of the axial length of described second ion guides device or ion trap device, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% drives at least some ions.
118., also comprise being arranged to and being suitable at least a portion of described second ion guides device or ion trap device is maintained at the device that is selected from the pressure of downforce: (i) as the described mass spectrometer of any claim among the claim 110-117〉0.0001mbar; (ii)〉0.001mbar; (iii)〉0.01mbar; (iv)〉0.1mbar; (v)〉1mbar; (vi)〉10mbar; (vii)〉1mbar; (viii) 0.0001-100mbar; And (ix) 0.001-10mbar.
119., also comprise being arranged to and being suitable for bringing out collision, cracking or the consersion unit that dissociate (" CID ") comes the cracking ion by collision as the described mass spectrometer of any claim among the claim 105-118.
120. as the described mass spectrometer of any claim among the claim 105-119, also comprise the collision, cracking or the consersion unit that are selected from following equipment: (i) (" the SID ") cracking apparatus that dissociates is brought out on the surface; (ii) electron transfer dissociation cracking apparatus; (iii) electron capture dissociation cracking apparatus; (iv) electron collision or the impact cracking apparatus that dissociates; (v) photo-induced dissociating (" PID ") cracking apparatus; (the vi) laser induced cracking apparatus that dissociates; (vii) infrared radiation brings out dissociation apparatus; (viii) ultra-violet radiation brings out dissociation apparatus; (ix) nozzle-knockout interface cracking apparatus; (x) endogenous cracking apparatus; (xi) cracking apparatus that dissociates is brought out in the ion source collision; (xii) heat or temperature source cracking apparatus; (xiii) electric field brings out cracking apparatus; (xiv) cracking apparatus is brought out in magnetic field; (xv) enzymic digestion or enzyme degraded cracking apparatus; (xvi) ion-ionic reaction cracking apparatus; (xvii) ion-molecule reaction cracking apparatus; (xviii) ion-atomic reaction cracking apparatus; (xix) ion-metastable ion reaction cracking apparatus; (xx) ion-metastable molecule reaction cracking apparatus; (xxi) ion-metastable atom reaction cracking apparatus; (xxii) be used to make ionic reaction to form the ion-ionic reaction equipment of adduction or product ion; (xxiii) be used to make ionic reaction to form the ion-molecule reaction equipment of adduction or product ion; (xxiv) be used to make ionic reaction to form the ion-atomic reaction equipment of adduction or product ion; (xxv) be used to make ionic reaction to form the ion-metastable ion consersion unit of adduction or product ion; (xxvi) be used to make ionic reaction to form the ion-metastable molecule consersion unit of adduction or product ion; And (xxvii) be used to make ionic reaction to form the ion-metastable atom consersion unit of adduction or product ion.
121. as claim 119 or 120 described mass spectrometers, also comprise be arranged to and be suitable in the cycle time of described mass analyzer or during increase gradually, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or alternate manner reduce the device of the electrical potential difference between described mass analyzer and described collision, cracking or the reaction member.
122., also comprise the upstream that is arranged in described mass analyzer and/or the another mass analyzer in downstream as the described mass spectrometer of any claim among the claim 105-121.
123. as the described mass spectrometer of claim 122, wherein said another mass analyzer is selected from: (i) Fourier transform (" FT ") mass analyzer; (ii) Fourier Transform Ion cyclotron Resonance (" FTICR ") mass analyzer; (iii) flight time (" TOF ") mass analyzer; (iv) quadrature boost-phase time (" oaTOF ") mass analyzer; (v) axially boost-phase time mass analyzer; (the vi) fan-shaped mass spectrometer of magnetic-type; (vii) Borrow (Paul) or 3D four-electrode quality analyzer; (viii) 2D or linear four-electrode quality analyzer; (ix) Peng Ning (Penning) grabber mass analyzer; (x) ion trap device mass analyzer; (xi) Fourier transform orbital acquisition device; (xii) electrostatic ionic synchrometer; (xiii) static Fourier transform mass spectrometer; And (xiv) quadrupole rod collection mass filter or mass analyzer.
124. as claim 122 or 123 described mass spectrometers, also comprise be arranged to and be suitable in the cycle time of described mass analyzer or during synchronously increase gradually with the work of described mass analyzer, reduce gradually, gradually change, scan, linearly increase, linearity reduces, with step, gradually or alternate manner increases or with step, gradually or the alternate manner mass-to-charge ratio that reduces described another analyzer transmit the device of window.
125. the method that ion is carried out quality analysis comprises:
The ion guides that comprises a plurality of electrodes device is provided;
To have that first of the first frequency and first amplitude exchanges or radio-frequency voltage puts at least some electrodes in described a plurality of electrode, so that produce one or more axially time averaging or pseudo-potential barrier, gesture ripple or potential wells along at least a portion of the axial length of described ion guides device;
To have that second of the second frequency and second amplitude exchanges or radio-frequency voltage puts on one or more electrodes in described a plurality of electrode, so that radially limit ion in described ion guides device; And
At least a portion along the axial length of described ion guides device drives or drives ion and/or driving or drive ion at least a portion by the axial length of described ion guides device, so that the ion of mass-to-charge ratio in first scope withdraws from described ion guides device and the ion of mass-to-charge ratio in second different range axially caught or be limited in the described ion guides device by described a plurality of axial time averaging or pseudo-potential barrier, gesture ripple or potential wells under mode of operation.
126. a mass spectrometric analysis method comprises as the described method of ion being carried out quality analysis of claim 125.
127. mass analyzer that comprises the ion guides device, wherein have different amplitudes and/or frequency and/or phase place two in use and exchange or radio-frequency voltage is applied in described ion guides device, and wherein produce a plurality of axially time averaging or pseudo-potential barrier, gesture ripple or potential wells along at least a portion of the axial length of described ion guides device.
128. a method of analyzing ion comprises:
The ion guides device is provided; And
To have different amplitudes and/or frequency and/or phase place two and exchange or radio-frequency voltage puts on described ion guides device, wherein at least a portion along the axial length of described ion guides device produces a plurality of axially time averaging or pseudo-potential barrier, gesture ripple or potential wells.
CN2007800297586A 2006-07-10 2007-07-09 Mass spectrometer Expired - Fee Related CN101536137B (en)

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US11/483,961 US7405401B2 (en) 2004-01-09 2006-07-10 Ion extraction devices, mass spectrometer devices, and methods of selectively extracting ions and performing mass spectrometry
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PCT/GB2006/002728 WO2007010272A2 (en) 2005-07-21 2006-07-21 Mass spectrometer
GB0704923.2 2007-03-14
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US91389707P 2007-04-25 2007-04-25
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