Ion mobility separator with variable effective length
09552974 ยท 2017-01-24
Assignee
Inventors
- Martin Raymond Green (Bowdon, GB)
- David J. Langridge (Macclesfield, GB)
- Jason Lee WILDGOOSE (Stockport, GB)
Cpc classification
H01J49/36
ELECTRICITY
H01J49/42
ELECTRICITY
International classification
B01D59/46
PERFORMING OPERATIONS; TRANSPORTING
G01N27/62
PHYSICS
H01J49/42
ELECTRICITY
H01J49/36
ELECTRICITY
Abstract
An ion mobility separator or spectrometer is disclosed comprising an inner cylinder and an outer cylinder defining an annular volume through which ions are transmitted. Spiral electrodes a-f are arranged on a surface of the inner cylinder and/or on a surface of the outer cylinder. A first device is arranged and adapted to maintain a DC electric field and/or a pseudo-potential force which acts to urge ions from a first end of the ion mobility separator or spectrometer to a second end of the ion mobility separator or spectrometer. A second device is arranged and adapted to apply transient DC voltages to the one or more spiral electrodes in order to urge ions towards the first end of the ion mobility separator or spectrometer. The net effect is to extend the effective path length of the ion mobility separator.
Claims
1. Apparatus for separating ions according to one or more physico-chemical properties, wherein said apparatus is arranged and adapted to create an ion channel in which ions are confined in use, the apparatus comprising: a first device arranged and adapted to apply or maintain a first electrostatic potential or field, a first DC potential or field, or a first pseudo-potential or field in a first direction to cause ions to separate according to said one or more physico-chemical properties along said ion channel; and a second device arranged and adapted to move said ion channel in a second direction.
2. Apparatus as claimed in claim 1, wherein ions within said ion channel are driven in said second direction with a velocity which is substantially independent of said one or more physico-chemical properties.
3. Apparatus as claimed in claim 1, wherein said first electrostatic potential or field, said first DC potential or field, or said first pseudo-potential or field has a non-zero component orthogonal to said second direction.
4. Apparatus as claimed in claim 3, wherein said first electrostatic potential or field, said first DC potential or field, or said first pseudo-potential or field has a non-zero component parallel to said second direction.
5. Apparatus as claimed in claim 1, wherein said first direction is substantially opposite to said second direction.
6. Apparatus as claimed in claim 1, wherein said second direction is at an angle to or substantially orthogonal to said first direction or said ion channel.
7. Apparatus as claimed in claim 1, wherein said second device is arranged and adapted to increase or vary the effective path length along which ions separate according to said one or more physico-chemical properties.
8. Apparatus as claimed in claim 1, wherein said ion channel comprises a moving DC potential barrier or well, a second moving electrostatic barrier or well or a second moving pseudo-potential barrier.
9. Apparatus as claimed in claim 1, wherein said second device is arranged and adapted to drive said ions in said second direction by providing a second moving electrostatic potential barrier, a second moving DC potential barrier, or a second moving pseudo-potential barrier.
10. Apparatus as claimed in claim 9, wherein ions are separated according to said one or more physico-chemical properties: (i) in a direction substantially parallel to said second moving electrostatic potential barrier, said second moving DC potential barrier, or said second moving pseudo-potential barrier at a particular instance in time; and/or (ii) in a direction substantially orthogonal to a direction of movement of said second moving electrostatic potential barrier, said second moving DC potential barrier, or said second moving pseudo-potential barrier.
11. Apparatus as claimed in claim 1, wherein ions are separated according to their ion mobility.
12. Apparatus as claimed in claim 1, wherein ions are confined within said ion channel in a direction orthogonal to said first and second directions by RF voltages, RF potentials or pseudo-potentials.
13. Apparatus as claimed in claim 1, wherein ions separate along said ion channel towards a first end, and wherein said second device is arranged and adapted to move ions away from said first end to increase the effective length of separation.
14. Apparatus as claimed in claim 1, wherein said ion channel is substantially straight.
15. Apparatus as claimed in claim 1, wherein said ion channel is curved, discontinuous, spiral, or helical.
16. Apparatus for separating ions according to one or more physico-chemical properties, wherein said apparatus is arranged and adapted to create an ion channel in which ions are confined in use, the apparatus comprising: a first device arranged and adapted to apply or maintain a first electrostatic potential or field, a first DC potential or field, or a first pseudo-potential or field in a first direction to cause ions to separate according to said one or more physico-chemical properties along said ion channel; and wherein said ion channel comprises a moving DC potential barrier or well, a second moving electrostatic barrier or well or a second moving pseudo-potential barrier, and wherein said ion channel moves in a second direction.
17. Apparatus as claimed in claim 16, wherein said first electrostatic potential or field, said first DC potential or field, or said first pseudo-potential or field has a non-zero component orthogonal to said second direction.
18. Apparatus as claimed in claim 1, wherein said first direction is substantially opposite to said second direction.
19. Apparatus as claimed in claim 1, wherein said second direction is at an angle to or substantially orthogonal to said first direction or said ion channel.
20. Apparatus for separating ions according to one or more physico-chemical properties, wherein said apparatus is arranged and adapted to create an ion channel in which ions are confined in use, the apparatus comprising: a first device arranged and adapted to apply or maintain a first electrostatic potential or field, a first DC potential or field, or a first pseudo-potential or field in a first direction to cause ions to separate according to said one or more physico-chemical properties along said ion channel or an axis of said ion channel; and a second device arranged and adapted to move said ion channel in a second direction, wherein said first electrostatic potential or field, said first DC potential or field, or said first pseudo-potential or field has a non-zero component in a direction substantially orthogonal to said second direction, and wherein said first electrostatic potential or field, said first DC potential or field, or said first pseudo-potential or field has a non-zero component in a direction substantially parallel to said second direction.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Various embodiments of the present invention will now be described, by way of example only, and with reference to the accompanying drawings in which:
(2)
(3)
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(5)
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(9)
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(19) A preferred embodiment of the present invention will now be described with reference to
(20) According to an embodiment of the present invention an ion mobility separator may be provided comprising two concentric cylinders as shown in
(21) The annular volume between the two concentric cylinders 1,2 is preferably supplied with a buffer gas or drift gas such as helium or nitrogen. For example, the pressure of drift gas in the annular volume may be set to between 0.5 torr to 5 torr.
(22) According to a specific embodiment a spiral of conductive material may be attached to the outside of the inner cylinder 2 as shown in
(23)
(24) The conductive strip may be resistive and such that the total resistance of the strip may be of in the order of 50-500. This allows a potential gradient to be applied from one end of the conductive strip to the other using a second DC supply 6.
(25)
(26) In operation the second DC supply 6 may be arranged to apply a DC potential to all six conductive strips effectively producing a DC field which acts to urge ions from the entrance end 3 of the ion mobility separator to exit end 4 of the ion mobility separator.
(27) However, the first DC supply 5 is preferably only applied to one of the spiral conductive strips at any specific time.
(28) The same potentials are preferably applied to the complimentary conductive strips on the inner cylinder 2.
(29) In the preferred embodiment ions may be confined radially in the annular volume 3 by application of an AC voltage oscillating at RF frequency to the conductive strips. The RF voltage between adjacent strips is preferably 180 out of phase.
(30)
(31) Both the inner cylinder 2 and outer cylinder 1 may be made from made from a dielectric material with conductive strips on the inside and outside of each cylinder. For example a flexible PCB construction may be used.
(32) DC electrodes a,b,c,d,e,f are shown in
(33) Also shown in
(34) In operation ions are preferably pulsed into the ion mobility separator at a time T1 via the entrance 3 of the ion mobility separator. At time T1 the potential applied to strip f as shown in
(35) The potential gradient applied across each strip by the first DC voltage supply 5 preferably urges ions to progress down the ion mobility separator in a spiral path following the path DC barrier produced by the potential applied to strip f.
(36) The component of the field which results in separation of the ions is preferably orthogonal to the DC barrier.
(37) Ions passing through the buffer gas are preferably driven in a spiral path by the spiral DC gradient and will separate according to their ion mobility.
(38) As the ions travel down the device at a subsequent time T2, where T2>T1, the DC voltage applied to strip f is preferably removed and a DC voltage is preferably applied only to strip e as shown in
(39) Applying the DC voltage to strips a,b,c,d,e,f in this way creates a travelling DC helix or a rotating DC helix acting to oppose the motion of ions through the device as they are urged through the drift gas by the DC potential gradient applied to each conductive strip. Ions are preferably urged back towards the entrance of the device by the DC helical travelling wave but, at the same time, the ions slip down the inclined helical wave front as they are moved towards the exit of the device by the applied DC gradient.
(40) By adjusting the speed of the travelling helical wave or the strength of the DC field the residence time of ions within the device can be extended. Ions experience a DC field acting towards the exit of the device for a longer period of time than would be expected if no helical travelling wave were present. This longer residence time is equivalent to the ions travelling through a proportionately longer ion mobility separation device and hence the ion mobility separation power is increased compared to a conventional ion mobility separation device of a comparable physical length.
(41) To aid conceptualisation of the principle of operation of the device described, a simple model may be imagined wherein the travelling helical DC barrier is stretched out to form a linear barrier existing on a flat plane.
(42) In this model ions exist in an elevated pressure of buffer gas such that ion motion is dominated by the ion mobility K.
(43) At time T1 ions are preferably urged in a direction along the inclined edge of the DC barrier by the component of the DC force E resolved in this direction. If the DC barrier at T1 is static then ions will eventually reach the exit of the device D after travelling a distance L in field E. The time for the ions to travel from the entrance to the exit (DTs) will depend on the mobility of the ion and will be given by:
(44)
(45) However, in
(46) At time T2 the DC barrier is preferably moved upwards towards the entrance of the device and now exists at the position labelled T2. The ion preferably moves on the front of this barrier in a direction normal to the barrier. Ions of all mobility values are preferably moved by substantially the same amount. As shown, the ion has been moved towards the entrance of the device and again starts to move down the barrier which is now shown in position T2 . The ion is preferably allowed to travel a distance d2, where d2=d1, under the influence of electric field E until time T3. At time T3 the barrier has again been moved and the ion has been pushed back towards the entrance. The ion is again allowed to drift a distance d3, where d1=d2=d3, until time T4 where the barrier is again moved. The ion is then allowed to travel distance d4, where d1=d2=d3=d4, before the barrier is moved again at time T5. The ion is then allowed to travel distance d5, where d1=d2=d3=d4=d5, before the barrier is moved again at time T6. Finally, the ion is allowed to move a distance d6, where d1 d2 d3 d4 d5 d6 at which point the ion exits the device. The overall distance that the ion has travelled in the field E (Lt) is:
Lt=6d1 (3)
(47) This can be compared to the distance over which the ion would have travelled in the same field if the inclined barrier had not been moved L:
L=4d1 (4)
(48) Thus the absolute length of the mobility separation device L can be extended to a longer virtual length Lt. The amount that the drift length is extended is a function of the ions mobility.
(49) To investigate the performance of this technique in terms of mobility separating power, a model similar to the theoretical model described in
(50) The parameters used in this model were length of drift region L is 100 mm, height of DC barrier is 100V, angle of DC barrier wrt exit plane =20, pressure of nitrogen (hard sphere model) P is 0.5 Torr, speed of barrier normal to wave front is 40 m/s and driving field E is 4 V/mm.
(51) The trajectories of four ions were modelled. All ions were singly charged with mass to charge ratio 500 but with differing mobility values. Ion #1 had K=0.173 M.sup.2V.sup.1s.sup.1 and cross section of 200 .sup.2; Ion #2 had K=0.139 M.sup.2V.sup.1s.sup.1 and cross section of 250 .sup.2; Ion #3 had K 0.126 M.sup.2V.sup.1s.sup.1 and cross section of 275 .sup.2; and ion #4 had K=0.115 M.sup.2V.sup.1s.sup.1 and cross section of 300 .sup.2.
(52) Groups of 1000 ions of each mobility value were modelled and the mean drift time and the standard deviation in drift time for each species was recorded.
(53)
(54)
(55) There is clearly a marked improvement in IMS separation power using the technique according to the preferred embodiment. This is accompanied as expected by an increase in the drift time for all the species.
(56) It can also be seen, by comparison of
(57) Because the drift time is not linearly dependent on the mobility of the ions, the mobility resolution R can no longer be calculated directly from the expression:
(58)
(59) To produce an expression for the resolution of the device an analytical expression is required describing the motion of the ions within the travelling helical wave.
(60)
V=K.Math.E (6)
(61) A detector 9 is placed initially at the end of the drift tube 8 and moves away from the exit of the drift tube 8 with a constant velocity Vd effectively increasing the total length of the tube L.sub.tot as the ions drift. The field E is assumed to be constant throughout the ions journey to the detector 9.
(62) The time t.sub.tot at which an ion reaches the receding detector 9 is given by:
(63)
(64) The extent to which a packet of ions introduced into the drift cell spreads with time is governed by diffusion within the buffer gas.
(65) The standard deviation in the width if the ion packet with time oL is given by:
(66)
wherein k is Boltzmann constant, T is the temperature in Kelvin, t is the drift time and q is the charge on the ion.
(67) The standard deviation in terms of time at for the system may found by division of Eqn. 8 by the relative velocity of the ion given by Eqn. 7:
(68)
(69) The FWHM of the mobility peak in time t is:
t=2{square root over (2ln2)}.Math.t (10)
(70) To compare the results from the SIMION (RTM) model described an additional factor must be applied to represent the ion arriving at the detector 9 at a non normal angle . This has the effect of reducing the observed FWHM peak width by a factor F, wherein F =sin().
(71)
(72) In this model the drift region L was modelled as 100 mm, the velocity V.sub.d of the detector was 29 m/s and the driving field E was 4 V/mm.
(73) There is very good agreement with the results from the SIMION () simulation shown in
(74) To derive an expression for mobility resolution using this model, Eqn. 2 may be re-written as:
(75)
(76) Substituting Eqns. 7 and 8 into Eqn. 9 and evaluating yields an expression for the mobility resolution R of the device for a given detector velocity. The detector velocity is analogous to the speed of rotation of the helical DC barrier in the preferred embodiment:
(77)
(78)
(79) The dashed line 11 shows the resolution obtained from a standard DC drift tube of the same length L operating at the same pressure and field E. A mobility resolution of 13 was calculated for the standard drift tube. Increases in resolution of between 3 and 5 are achieved over this range of mobility according to the preferred embodiment. To achieve these resolutions at the same pressure and field using a standard drift tube a drift tube length of between 0.9-2.5 m would be required which is impractical.
(80) The mobility resolution is dependent of the mobility of the ion as the total effective distance the ions travel in the applied field depends on the ions mobility.
(81) In the embodiment described, ions are driven towards the exit of the device by the DC field acting along the helical DC barrier and are moved back towards the exit of the device by sweeping or rotating the DC barrier. Ions eventually exit in the direction in which they are urged by the DC field and may be detected. However, improved IMS separation may also be achieved by driving ions such that they exit in the opposite direction i.e. in the direction in which they are urged by the travelling or rotating helical DC barrier.
(82)
(83) The order in which the four species modelled elute from the device is reversed with ions having relatively low ion mobility exiting the device before ions with higher mobility.
(84)
(85) It should be noted that that during IMS separation the amplitude of the DC field may be ramped or stepped over a range of values and/or the velocity of the travelling spiral DC barrier may be ramped or stepped over a range of values. In this mode of operation the resolving power of the device may be maximised for specific mobility ranges.
(86) In another mode of operation an additional DC or RF barrier may be arranged at one end of the device (or at some point along the length of the device) such that once ions have entered the device they cannot exit or travel past this point. By adjusting the magnitude of the DC field and the speed of the opposing travelling DC helix, all ions may be driven to the end of the device and can effectively be trapped at a specific location within the device. Ions may be trapped by a combination of the exit barrier and the DC travelling spiral or by the exit barrier and the DC field acting along the length of the DC spiral.
(87) Once ions are trapped they can be scanned out by ramping or stepping the amplitude of the DC field or by ramping or stepping the velocity of the travelling helical DC barrier or by a combination of both. In this mode of operation the resolving power of the device may be maximised for a wide range of mobilities.
(88) By varying the driving forces within the device it is possible to arrange ions with different mobility ranges to exit via different ends of the device simultaneously if desired.
(89) In the preferred embodiment ions enter the device at one end of the annular volume, however, ions may be arranged to enter the annular volume at any point along the length of the device via a separate ion entrance through the outer cylinder.
(90) The device may also be operated as an ion guide without any IMS separation according to another mode of operation. In this mode of operation the DC field acting to urge ions along the DC spiral barrier may be effectively set to zero and the travelling DC spiral may be used to drive ions through the device. The travelling or rotating DC spiral may be used to transmit a continuous, discontinuous or pulsed ion beam.
(91) The device will operate as an RF ion guide over a wide range of buffer gas pressure. The transit time of ions through the device may be precisely controlled by adjusting the speed of the travelling DC spiral as described.
(92) At an elevated buffer gas pressure the travelling spiral DC barrier can transport a continuous beam of ions or a discontinuous beam of ions with no effective mobility separation. This is not possible using a static axial DC driving force.
(93) At an elevated buffer gas pressure the travelling spiral DC barrier can transport a continuous beam of ions or a discontinuous beam of ions with no effective mobility separation and no partitioning of the ion beam. This is not generally possible using a conventional DC travelling wave gas cell.
(94) When used with a continuous ion beam the device may be used as a high or low mobility cut off filter. For example. the speed of the travelling DC helical barrier opposing the DC field may be adjusted so that only ions having an ion mobility above a certain mobility value will exit the device. Ions of lower mobility will not be driven towards the exit of the device or will be driven back towards the exit.
(95) Although the preferred embodiment has a cylindrical geometry other embodiments with planar and other geometries are also intended to fall within the scope of the present invention.
(96)
(97) Although this is not as compact a design as the preferred embodiment, the mobility resolution which can be achieved for a given length L is significantly higher than can be achieved with a standard drift tube of length L with a field E.
(98) Another planar embodiment is shown in
(99)
(100) Various different methods of containing ions in the z and x directions for the embodiments shown in
(101)
(102) Ions eventually exit the device at the central point 17. In this embodiment ions may be injected at the centre of the spiral and driven towards the outside of the spiral by increasing the speed of rotation of the spiral DC barrier or by decreasing the field E sufficiently.
(103) It should be noted that the direction of both the radial field and the direction of rotation of the spiral may be reversed without changing the principle of operation.
(104) As for the embodiments in
(105) In the embodiments described in
(106)
(107) Various modifications to the embodiments shown and described above are contemplated.
(108) For example, modifications may be made to the way in which the time and position varying DC barrier is applied. For example, rather than applying the potential in a series of discreet steps with potentials suddenly appearing and disappearing on different elements of the device, the amplitude of the DC potential may be applied and then removed using a smooth continuous function. This allows for a smoother transition between the travelling waves experienced by the ions.
(109) In the preferred embodiment described above the potential forming the travelling DC barrier is shown and described as being applied to only one conductive strip at a time. However, it may also be advantageous to apply the potential to groups of adjacent conductive strips. Other embodiments are contemplated which affect the magnitude and the shape of the travelling wave.
(110) The confining RF voltage may be applied in other ways than described in the preferred embodiment. For example, the RF confining potential may be applied between the complimentary spirals on the inner and outer cylinder such that the conductive strips on the inner cylinder are supplied with RF potential 180 degrees out of phase with the strips on the outer cylinder. All strips on the inner cylinder may be arranged to be at the same phase and all strips on the outer cylinder may be arranged to be at the same phase.
(111) Alternatively, the RF confining potential may be applied such that spirals on the inner cylinder have opposite phases to the complimentary spirals on the outer cylinder.
(112) However, adjacent spirals on the inner and the outer may have opposite phases of RF.
(113) Other schemes may be envisaged resulting in RF confinement.
(114) The geometry of the device need not have a circular cross section. Elliptical, rectangular or irregular cross sections can be envisaged.
(115) The inner component shown in
(116) The pitch of the travelling helical barrier described by the angle in
(117) The driving force opposing the travelling DC helix may be a mass dependent force such as a pseudo potential force rather than a DC field. A pseudo potential driving force may be created by applying progressively higher amplitude of RF voltage with distance along the length of the device or by reducing the gap between the inner and the outer cylinder from the entrance end to the exit end.
(118) In this case separation will be related to both the mobility and the mass to charge ratio of the ions.
(119) It is possible to construct the device to produce the required fields in different ways than described in relation to the preferred embodiment. For example, the inner and outer cylinders may be concentric RF ring stacks with opposite phases of RF on adjacent rings. If these rings are themselves radially segmented then appropriate static and time varying DC potentials may be applied to the segments to produce the required fields.
(120) Using this type of construction it is possible to apply a more traditional DC travelling wave to the device. The combination of a travelling DC helix opposed by a DC travelling wave may be used for enhanced mobility separation or mass separation as described in Additionally using a multiply segmented ring stack a travelling pseudo potential helical barrier may be produced by altering the amplitude of RF applied to each segment in a time varying manner.
(121) More than one travelling helical DC barrier may be simultaneously imposed over the length of the device creating more than one unique pathway for ions to travel down the device.
(122) In another embodiment, this device may be used as a cylindrical differential ion mobility device (DIMS) device. In this embodiment the RF confining potential may be asymmetric or an additional asymmetric waveform may be applied to the RF confining electrodes between the inner and outer cylinder. In this embodiment the RF confining potential is applied between the complimentary spirals on the inner and outer cylinder such that the conductive strips on the inner cylinder are supplied with RF potential 180 degrees out of phase with the strips on the outer cylinder. All strips on the inner cylinder are the same phase and all strips on the outer cylinder are the same phase.
(123) This results in dispersion of the ions in the radial direction between the inner and outer cylinders with respect to their differential ion mobility.
(124) Only ions within a specific band of differential ion mobilities will be contained within the device. Other ions will be lost to the electrodes of the inner or outer cylinder. By applying an additional DC voltage between the outer and the inner cylinders (compensation voltage) ions with different differential mobility can be arranged to be transferred though the device.
(125) If, during differential ion mobility separation, ions are driven through the device by the helical travelling wave with no DC field, ions will only be separated in the radial direction. Ions may be introduced into this device as a continuous beam or as a pulse or packet of ions.
(126) If DC field or a combination of DC and opposing helical travelling wave is used to drive ions through the device ions will separate radially with respect to their differential mobility and along the length of the spiral with respect to ion mobility.
(127) The device can also be used in conjunction with another separation device (for example ion mobility or mass separator) or filter upstream or downstream of the device.
(128) If a second IMS separation device is placed upstream of the device disclosed, the output of the first device can be synchronised to the changes in the speed of the helical DC travelling wave or the DC field strength to allow the IMS resolution to be optimised over a wide range of mobilities.
(129) The embodiments disclosed may used in conjunction with each other or as multiple devices is series with ions passing from one device to another. For example, multiple devices constructs a shown for the planar spiral geometry in
(130) The devices disclosed may be used to analyse both positive and negative ions simultaneously. If positive ions are introduced at one end of the device and negative ions are introduced at the opposite end of the device these ions will travel in opposite directions and exit the device at opposite ends. Positive ions will take will take a unique path through the device compared to negative ions because of the nature of the travelling DC barriers. It is possible to use this characteristic to populate the device with both positive and negative ions and control their interaction time by removing or reducing the DC barrier. In this way ion-ion interactions such as electron transfer dissociation ETD, Hydrogen deuterium exchange HDX, or charge reduction may be performed.
(131) It is possible to trap both positive and negative ions using the embodiments of the travelling DC barrier described by arranging ions to be urged towards the centre of the device by barriers rotating or moving in opposite directions at either end of the device.
(132) Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the scope of the invention as set forth in the accompanying claims.