CN101536137B - Mass spectrometer - Google Patents

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 through arranging as follows: 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, a kind of mass analyzer is provided, 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 said 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 said 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 through the axial length of ion guides device so that withdraw from the ion guides device and the 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.Can be as an alternative, 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.Can be as an alternative, 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)＞the 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)＞the 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 property.

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 the maximum of 50% corresponding axial location basically of axial distance or 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 phase 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 the maximum of 50% corresponding axial location basically of axial distance or 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 r mm 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 the 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, said 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 said 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 said 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 said 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 said 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 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.

According to the preferred embodiment, at least some electrodes in said 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 said 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 at the device of the first radial direction limit ion in the ion guides device.

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.

Be used to apply second exchange or the device of radio-frequency voltage preferably be arranged to second exchange or radio-frequency voltage put on the 3rd plate electrode and the 4th plate electrode in case preferably with the second radial direction limit ion of the first radial direction quadrature in the ion guides device.

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 said 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 said 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 electrode.

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 said 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 through at least a portion of the axial length of ion guides device through 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 said 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 potentials 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 alternate manner increase perhaps 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 alternate manner increase perhaps 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 alternate manner increase perhaps 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, 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.

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)＞the 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 or the alternating voltage of electrode 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)＞the 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 or the alternating voltage of electrode 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 at radial direction limit ion in the ion guides device.

The 7th device preferably is arranged to and is suitable in time period t ₇In will put on direct voltage or the electromotive force of at least some electrodes 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 amplitude and the device of amplitude that puts on second radio frequency or the alternating voltage of electrode of first radio frequency or the alternating voltage of electrode.

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 frequency and the device of frequency that puts on second radio frequency or the alternating voltage of electrode of first radio frequency or the alternating voltage of electrode.

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 through 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 gets into 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, a kind of mass spectrometer of mass analyzer as stated that comprises is provided.

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) 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) 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 upper reaches that are 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 upper reaches that are 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 2,5,10,20,30,40,50,60,70,80,90 or 100 electrodes with hole that ion passed in use, 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 have substantially the same hole of size or area or size or area and become hole big and/or that diminish gradually;

The (iii) heap or the row of plane, tabular or mesh electrode; The heap of its midplane, tabular or mesh electrode or row 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 are 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 at the device of the first radial direction limit ion in the ion guides device; And (b) third and fourth electrode and being used for exchanging or radio-frequency voltage puts on third and fourth electrode so that at the device of the second radial direction limit ion in the ion guides device.

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 and be suitable for exchanging or radio-frequency voltage puts 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 a plurality of electrodes of the second ion guides device or ion trap device, 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 in the second ion guides device or ion trap device, forms.

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 through the second ion guides device or ion trap device driven in 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 upper reaches drive at least some ions along at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of the axial length of the second ion guides device or ion trap device.

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 upper reaches drive at least some ions along at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of the axial length of the second ion guides device or ion trap device.

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)＞and 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 through 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 upper reaches that are 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, a kind of method that ion is carried out quality analysis is provided, 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 said 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 the one or more electrodes in said 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 through 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, a kind of mass spectrometric analysis method is provided, this method comprises the method for as stated 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, a kind of method of analyzing ion is provided, 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: can make this preferred mass analyzer compare work 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 said 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 possibly 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 phase 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 as at the first radial direction limit ion in the ion guides device.Exchange or radio-frequency voltage preferably is applied in two other plate electrodes, so as at the second radial direction limit ion in the ion guides device.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 at the arrival end of mass analyzer basically.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 through 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 through 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, come on purpose to produce axial pseudopotential ripple through suitable selection electrode gap and through 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, can be through following method scan ion so that ion withdraws from ion guides device or mass analyzer: (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 confirmed through 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 possibly 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 possibly reduce or maybe 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 phase 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 phase 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 confinement that mass-to-charge ratio is high relatively in mass analyzer, and these ions possibly tend to the electrode of knock-on ion miter guide or mass analyzer and therefore become from system, lose 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 aspect restriction, mass range and mass separation or mass resolution, optimize mass analyzer.

When using two radiofrequency signals, the form of two radiofrequency signals is taked four different combinations.Each electrode can come to 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:

n _odd，p _odd

n _even，p _odd

n _odd，p _even

n _even，p _even

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.At ω ₁=ω ₂Simple 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 radial distance R and axial location Z _{. ∏}Function be in pseudopotential ψ in radio frequency ring heap or the ion tunnel formula ion guides device (R Z) is provided by following formula:

$\mathrm{\&Psi;}(R,Z):=\frac{z\&CenterDot;e\&CenterDot;{\mathrm{<figure-callout\; id="2"\; label="Vo"\; filenames="H2007800297586E00011.png,H2007800297586E00061.png"\; state="\{\{state\}\}">Vo</figure-callout>}}^2}{4\&CenterDot;m\&CenterDot;{\mathrm{\&omega;}}^2\&CenterDot;{\mathrm{<figure-callout\; id="2"\; label="Zo"\; filenames="H2007800297586E00011.png,H2007800297586E00061.png"\; state="\{\{state\}\}">Zo</figure-callout>}}^2}\&CenterDot;\frac{I1{\left(\frac{R}{\mathrm{Zo}}\right)}^2\&CenterDot;\cos {\left(\frac{Z}{\mathrm{Zo}}\right)}^2+I0{\left(\frac{R}{\mathrm{Zo}}\right)}^2\&CenterDot;\sin {\left(\frac{Z}{\mathrm{Zo}}\right)}^2}{I0{\left(\frac{\mathrm{Ro}}{\mathrm{Zo}}\right)}^2}---\left(1\right)$

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. _∏Be the center to center interval between the adjacent ring electrode, I0 is a first kind zeroth order modified Bessel function, and I1 is a first kind single order modified Bessel function.

Can know that by following formula 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 amplitude, height or the degree of depth.

According to the preferred embodiment; Preferably through with one or more transient state DC potentials 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 through 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 potentials 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 with buffer gas repeatedly; Then under the situation of the fixed amplitude of the one or more transient state DC potentials 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 potentials 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 driven along the length of mass analyzer owing to one or more transient state DC potentials 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 potentials that applied or voltage or DC potential or voltage waveform.With preferably with to the electrode progression apply the substantially the same speed of speed or the speed of one or more transient state direct voltages or electromotive force or DC potential or voltage waveform 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 potentials 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 potentials or voltage or DC potential or the voltage waveform of specific amplitude, then will be preferably to advance the high relatively 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 potentials or voltage or DC potential or voltage waveform to electrode or speed or speed.Yet; With not advancing 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 potentials 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 potentials 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 or electromotive force or DC potential or the voltage waveform of suitable amplitude, 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) at diameter and the interval between the adjacent electrode of internal holes that can be preferably that ion passes through minimizing, constitute the electrode of mass analyzer 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 through making electrode is as far as possible little and/or through 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.The pseudopotential ripple that preferably 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 get 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 potentials of electrode or the amplitude of voltage or DC potential or voltage waveform and preferably be set to minimum value or null value.Then, the amplitude of one or more transient state DC potentials 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, with being 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 in the period this one or more other group ion being carried out quality analysis in following one scan then in one or more other group ion entering mass analyzers.

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 at the upper reaches 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 high relatively duty ratio.

According to an embodiment, ion storage district or ion trap device can be provided at the upper reaches 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, the mass spectrometer that preferably has high duty ratio, high transmission efficiency and improved mass resolution is provided.

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 are 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.Can be as an alternative, the preferred mass analyzer can be coupled to the quadrupole rod collection mass analyzer in the downstream that are arranged in the preferred mass analyzer that is arranged to be scanned.Under this situation, 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 the Fourier transform that can adopt the relevant resonance frequency of quality so that ion carried out the Fourier transform mass analyzer of quality analysis.According to a special 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 the preferred mass analyzer be provided at the upper reaches 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 through wherein periodically being applied with the quadrature accelerating region of quadrature accelerating field.The frequency that applies that wherein is applied with length, energy of ions and the quadrature accelerating field of the quadrature accelerating region of quadrature accelerating field is used for to the ion sampling decision so that the sampling duty ratio of analyzing at the time of flight mass analyzer subsequently.But the ion that has approximate identical energy have the entering quadrature accelerating region of different mass-to-charge ratioes will have different speed at them during through 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 possibly 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 during mass charge ratio range and the energy of ions of ion, can be arranged to short relatively given from the distance between the quadrature accelerating region of the point of preferred mass analyzer release of ionic and time of flight mass analyzer.

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 to 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 upper reaches of quadrature boost-phase time mass analyzer the ion guides device is provided 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 one of potential well, be collected 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 in the ion guides device, produces 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; The average mass-to-charge ratio of the ion that discharges from the outlet of ion guides device preferably reduces gradually in time in the cycle time at mass analyzer from ion guides device release of ionic bag and to the time of delay that the pusher electrode of time of flight mass analyzer applies between the pulse of quadrature accelerating voltage, because will preferably reduce in time.

Preferably ion source is provided at the upper reaches 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.Can be as an alternative, ion source can comprise the continuous ionic source.If the continuous ionic source is provided, then can be preferably in ionogenic downstream and the upper reaches of preferred mass analyzer be provided for ion storage and ion periodically be discharged into the ion trap device in the preferred mass analyzer.The continuous ionic source can comprise electron spray ionisation (" ESI ") ion source; 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; FI (" FI ") ion source or field desorption (" FD ") ion source.Can also use other continuous or pseudo-continuous ionic source.

Mass spectrometer can also comprise collision, cracking or the reaction member that can provide at the upper reaches of preferred mass analyzer according to an embodiment.Under a kind of mode of operation, the ion cracking or the reaction that make at least some get into 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 mass filter be provided at the upper reaches 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 by significantly decay so that they are forwarded.Then, preferably cracking or reaction when they get into 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 through the preferred mass analyzer at them in time.

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 for example measure with pinpoint accuracy the relative abundance of two kinds or more kinds of specific cleavage ions.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 come further to improve the selectivity of analyzing through before cracking, removing not potential interested any mother or precursor ion.According to an embodiment, ion can be arranged to the mass filter through the upper reaches that preferably are positioned at 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 under non-resolution or ion guides mode of operation, work.Can be as an alternative, 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 upper reaches 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.Can be as an alternative, this another mass filter or mass analyzer can only forward work 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 have basically no any duty-cycle loss and therefore have basically no any loss of sensitivity ground and measure some mothers or cracking ion.

According to an embodiment, another mass filter or the mass analyzer that is arranged in the downstream of preferred mass analyzer preferably is 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 in the cycle time of preferred mass analyzer, scan to low mass-to-charge ratio ground from high mass-to-charge ratio, 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 quadrupole rod collection mass filter or mass analyzer are provided 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 when the collision that stands with the background gas molecule, also be restricted to the central shaft near the gas collisions unit.The gas collisions unit can comprise multipole bar collection ion guides device, wherein between contiguous bar, applies to exchange or radio-frequency voltage, 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 said hole in use.The phase anti-phase of interchange or radio-frequency voltage preferably is applied between contiguous or adjacent ring or the electrode, so that preferably come radially to limit ion in the gas collisions unit through 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 energy with 10eV at least under mode of operation gets into collision cell.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.Similar plate or electrode can be provided 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 for other electrode that constitutes collision cell, are reduced to 0V to moment 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 potentials 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 amplitude with the quadrupole rod collection mass filter in the downstream that are arranged in the preferred mass analyzer or the work of mass analyzer in time gradually.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 through example and illustrate and describe various embodiment of the present invention, 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 said hole in use.Though not shown in Fig. 1, electrode is arranged in groups that preferably 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 phase anti-phase of first interchange or radio-frequency voltage.In addition, adjacent electrode preferably is connected to the phase anti-phase of second interchange or rf voltage source.Preferably at the inlet of ion guides device 2 electrode 3 that provides access, and preferably exit electrodes 4 is provided in the outlet of ion guides device 2.Can at the upper reaches of inlet electrode 3 gate electrode 1 be provided alternatively.According to an embodiment, inlet electrode 3 can comprise same parts with gate electrode 1.

The electromotive force that preferably for example reduces gate electrode 1 through moment ground makes ion get into ion guides device 2 with the recurrent pulses form.The ion that gets into ion guides device 2 preferably experiences such radio frequency non homogen field: it is used for because the radially generation of pseudo-potential well 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 specific electrode 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 the phase anti-phase of radio-frequency voltage supply.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 the mass analyzer that comprises ring heap as shown in fig. 1 or ion tunnel formula ion guides device 2 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 in the mass analyzer that comprises ring as shown in fig. 1 heap or ion tunnel formula ion guides device 2, has high relatively mass-to-charge ratio 1000 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.Visible from Fig. 2 and Fig. 3, 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, the 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 at the upper reaches that are arranged in preferred mass analyzer 2.Preferably applying pulse through the gate electrode 1 to the outlet that is arranged in ion trap device 5 then comes from ion trap device 5 release of ionic periodically.In the moment from ion trap device 5 release of ionic, the one or more transient state DC potentials that preferably apply to the electrode of ion guides device 2 or the amplitude of voltage or DC potential or voltage waveform preferably are arranged at minimum value, more preferably are arranged at 0V.Then, the one or more transient state DC potentials that apply to the electrode of mass analyzer 2 or the amplitude of voltage or DC potential or voltage waveform preferably increase or ramp 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 through 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 line property increase of mass analyzer.Also show the corresponding voltage pulse that applies to gate electrode 1 for ion is got in the preferred mass analyzer 2 with impulse form.

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 during 800 μ s gate pulses, get into the ion guides device 2 of preferred mass analyzer 2 from ion trap device 5 with impulse form.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 potentials 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 are arranged in preferred mass analyzer 2.Fig. 7 shows an embodiment, wherein at the upper reaches of quadrupole rod collection mass analyzer 8 preferred mass analyzer 2 is provided.Preferably ion detector 9 is provided 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 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 that has 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 able to preferably increase.

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 line property increase of mass analyzer.Also show the corresponding voltage pulse that applies to gate electrode 1 for ion is got in the preferred mass analyzer 2 with impulse form.

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 for selecting embodiment according to one.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 under the mode of operation of only being concerned about and hoping measurement, detect or analyze some specific ion with some mass-to-charge ratio, increase the transmission efficiency and the duty ratio of quadrupole rod collection mass filter 8.

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, the mass spectrometer that has improved overall duty ratio and sensitivity is provided preferably.Ion guides device 10 preferably includes each a plurality of electrode that all have the hole.One or more transient state DC potentials 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 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 in ion guides device 10, forms 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 gets into 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 line property increase of mass analyzer.Also show the corresponding voltage pulse that applies to gate electrode 1 for ion is got in the preferred mass analyzer 2 with impulse form.

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 get into the preferred mass analyzer 2 from ion source with impulse form.For example, MALDI ion source or other pulsed ion source can be provided, and when the ionogenic target plate of laser beam hits, ion can get in the preferred mass analyzer 2 with impulse form.

According to an embodiment, can collision, cracking or reaction member be provided in the upper reaches 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 potentials 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 to the follow-up cracking that in collision, cracking or the reaction member in the downstream that are 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 and under not breaking away from the situation of liking the scope of the invention of illustrating in the claim enclosed, to make the various changes on form and the details.

Claims (16)

1. mass analyzer comprises:

Comprise a plurality of ion guides devices with the electrode in hole, ion passes said hole in use;

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 said 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 said 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 said ion guides device in use;

Wherein said first frequency is different with said second frequency, and/or said first amplitude is different with said second amplitude, and/or said first interchange or radio-frequency voltage exchanges with said second or radio-frequency voltage between have phase difference; And

Be used for driving or driving ion and/or driving or drive ion at least a portion through the axial length of said ion guides device so that withdraw from said ion guides device and the device in the said ion guides device is axially caught or be limited to the ion of mass-to-charge ratio in second different range by said 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 said ion guides device.

2. mass analyzer as claimed in claim 1, wherein axial adjacent electrode is supplied the phase anti-phase of said second interchange or radio-frequency voltage.

3. mass analyzer as claimed in claim 1, 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 said ion guides device linear, non-linear or step axial dc electric field.

4. mass analyzer as claimed in claim 1, the wherein said device that is used for driving or drive ion comprise 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 said electrode.

5. mass analyzer as claimed in claim 1, the wherein said device that is used for driving or drive ion comprise 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 said electrode.

6. mass analyzer as claimed in claim 5; Wherein a plurality of in use axial dc gesture mound, potential barrier or potential well be along the length translation of said ion guides device, perhaps a plurality of transient state DC potentials or voltage along the axial length of said ion guides device by progression put on electrode.

7. like claim 5 or 6 described mass analyzers; Also comprise first device, said first 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 increase perhaps with step, gradually or alternate manner reduce amplitude, height or the degree of depth of said one or more transient state direct voltage or electromotive force or said one or more direct voltage or potential waveform.

8. mass analyzer as claimed in claim 5; Also comprise second device, said second 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 increase perhaps with step, gradually or alternate manner reduce to apply the speed or the speed of said one or more transient state direct voltage or electromotive force or said one or more DC potential or voltage waveform to said electrode.

9. mass analyzer as claimed in claim 1; Also comprise the 3rd device, said 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 said first of said electrode exchanges or the amplitude of radio-frequency voltage.

10. mass analyzer as claimed in claim 1; Also comprise the 4th device, said 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 said first radio frequency of said electrode or the frequency of alternating voltage.

11. mass analyzer as claimed in claim 1; Also comprise the 5th device, said 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 said second of said electrode exchanges or the amplitude of radio-frequency voltage.

12. mass analyzer as claimed in claim 1; Also comprise the 6th device, said 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 said second radio frequency of said electrode or the frequency of alternating voltage.

13. mass analyzer as claimed in claim 1; Wherein under mode of operation; Ion is arranged to withdraw from said mass analyzer with the backward of mass-to-charge ratio, so that the high relatively ion of mass-to-charge ratio withdrawed from said mass analyzer before the low relatively ion of mass-to-charge ratio.

14. mass analyzer as claimed in claim 1, wherein under mode of operation, ion is arranged to be trapped in still not cracking in said ion guides device in the said ion guides device.

15. a mass spectrometer comprises mass analyzer as claimed in claim 1.

16. the method that ion is carried out quality analysis comprises:

Provide to comprise a plurality of ion guides devices with the electrode in hole, ion passes said hole in use;

To have that first of the first frequency and first amplitude exchanges or radio-frequency voltage puts at least some electrodes in said 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 said ion guides device;

To have that second of the second frequency and second amplitude exchanges or radio-frequency voltage puts on the one or more electrodes in said a plurality of electrode, so that radially limit ion in said ion guides device;

Wherein said first frequency is different with said second frequency, and/or said first amplitude is different with said second amplitude, and/or said first interchange or radio-frequency voltage exchanges with said second or radio-frequency voltage between have phase difference; And

At least a portion along the axial length of said ion guides device drives or drives ion and/or driving or drive ion at least a portion through the axial length of said ion guides device, so that the ion of mass-to-charge ratio in first scope withdraws from said ion guides device and the ion of mass-to-charge ratio in second different range axially caught or be limited in the said ion guides device by said a plurality of axial time averaging or pseudo-potential barrier, gesture ripple or potential wells under mode of operation.

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