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Mass Spectrometry - US (Electrical Patents)

Patent no: 8,598,516
Issued: December 03, 2013
Inventor: Sapargaliyev; Yerbol Aldanovich (Almaty, KZ), Sapargaliyev; Aldan Asanovich (Almaty, KZ)
Attorney: Michael Feigin

Abstract

The present invention relates to the analytical electronics used to identify compositions and structures of substances, in particular, to the analyzers comprising at least one mass-spectrometer (MS) and may be applied in such fields as medicine, biology, gas and oil industry, metallurgy, energy, geochemistry, hydrology, ecology. Technical result provides the increase in MS resolution, gain in sensitivity, precision and measurement rates of substances compositions and structures concurrently with enhancement of analyzer functional capabilities, downsizing and mass reduction. In claimed invention the ion flux generation and its guiding are performed in off-axis single-flow mode; parallel multi-stage mode; through use of three-dimensional field with mean meridian surface including without limitation three-dimensional reflecting and dual-zoned reflecting modes or by method of multi-reflection arrays. Devices to implement the claimed method are embodied. Proposed schematic ion optical diagrams allow developing different MS types notable for their minimized material intensity and geometrical dimensions.

Claims

The invention claimed is:


1. A method of mass-spectrometry, comprising:
ionizing a substance sample in an ionic source block, formation an ion flux in MS, managing motion of said ion flux including mass dispersion by at least one of the ion flux by mass/charge ratio, by means of at least one of a magnetic field and an electric field;
said magnetic field and said electric field generated by groups of ion-conducting blocks comprising ion-conducting IB-channels with boundary surfaces and IO channel systems, where IB-channels are part of a MS-channel with its own MS-channel IO system;
wherein said MS channel comprises at least one said ion-conducting IB-channel and at least one ionic source IB-channel of said ionic source block connected in series, wherein said IO channel system of each said ion-conducting IB-channel comprises at least one of:
a subsystem with a curved main axis in a cross-space dispersing mode, a subsystem with a curved main axis, in a multi-reflecting mode, and any other subsystem, hereinafter named as a management subsystem, registering ions in said ion flux using at least one detector group of a detector system;
and controlling and managing of all blocks of a mass-spectrometer as well as supporting data processing in said mass spectrometer using a controller-computer subsystem, wherein said forming and said management of said ionic source block connected in series, wherein said IO channel system of each said ion-conducting IB-channel comprises at least one of a control subsystem, a subsystem with a curved main axis in a cross-space dispersing mode, and a subsystem with a curved main axis in a multi-reflecting mode, and wherein said generating and said controlling said motion are carried out by at least one of:
(a) parallel mass-spectrometry in a said MS-channel using at least one mode selected from:
channel-multipath ion flux including a mode with multi-cell section surfaces, off-axis channel-single-path ion flux, including a mode with double-cell section surfaces;
(b) control of said ion flux using an electric IO channel system comprising at least one of an IO element enabling selection of a specified spatial orientation of said IO element relative to at least one other IO element and relative to a direction of an averaged vector of said ion flux entering said IO element, a flat unary P-multireflector, a three-dimensional P-multireflector, a cascade-multilayered multireflector, an extended P-element of refraction, a three-dimensional P-element of reflection, a P-element of non-uniform height, and a P-element of reflection with a two-dimensional reflection zone.

2. The method of claim 1 that enable single-channel and multichannel mass-spectrometry, wherein said ion flux comprises at least one single-path ion flux which passes through said MS-channel, wherein each said path ion flux is detected by an individual detector of said detector system.

3. The method of claim 2, wherein said path ion fluxes comprises at least two path ion fluxes, each received from a different source, and injected into at least one of said groups of ion conducting blocks through a different output gate of an ionic source system.

4. The method of claim 3, wherein said at least two path ion fluxes exiting from at least one said output gate of said ionic source system are supplied in at least one of:
independently of one another, and in a time correlation function relative to one another.

5. The method of claim 2, wherein values of said mass dispersion and of energy dispersion of said ion flux are regulated by energy spectrometry performed concurrently with mass-spectrometry, and mass-spectrometry at specified range intervals of an energy spectrum of said ion flux.

6. The method of claim 1, wherein one cyclicity mode used in passage of said ion flux is selected from the group consisting of single-cycle ion passage, and multi-cycle ion passage through at least some said IB-channels.

7. The method of claim 5, wherein said mass-spectrometry is performed using a mode selected from the group consisting of:
single-staged mode, MS/MS mode, and MSn-mode.

8. The method of claim 7, wherein cross-spatial space focusing of said ion flux is performed on a detector surface, at least along one of two cross-spatial space directions.

9. The method of claim 7, wherein cross-spatial space focusing of said ion flux is performed along a path of motion of said ion flux by means of pulsating voltage.

10. The method of claim 7, wherein said mass spectrometry comprises) time-of-flight mass-spectrometry, selected from the group consisting of MSn-type and MS/MS-type, and is performed by an nested time mode.

11. A nonmagnetic management subsystem for control of charged particle flux, selected from a group of functional versions consisting of:
(a) a subsystem of refraction comprising at least one IO element of refraction;
(b) a subsystem of reflection comprising n local IO elements of reflection, where:
n is an integer number and n.ltoreq.3 and including no more than two local P-elements of reflection and extended IO elements of reflection;
(c) a mixed subsystem of reflection and refraction, comprising said subsystems (a) and (b);
and (d) a multifunctional subsystem, comprising one of said subsystems (a), (b) and (c), wherein at least one IO element is multifunctional and enables selection of at least two operation modes selected from the group consisting of:
refracting, reflecting and field-free, said nonmagnetic management subsystem including at least one IO element selected from the group consisting of:
IO element enabling selection of a specified spatial orientation of said IO element relative to at least one other IO element and relative to a direction of an averaged vector of said ion flux entering said IO element, a flat unary P-multireflector, a three-dimensional P-multireflector, a cascade-multilayered multireflector, an extended P-element of refraction, a three-dimensional P-element of reflection, a P-element of non-uniform height, and a P-element of reflection with a two-dimensional reflection zone.

12. The management subsystem of claim 11, comprising a local IO element having at least one of functional and design characteristics, wherein said local IO element is selected from the group of functional characteristic IO elements consisting of:
a local IO elements of refraction, a local IO lens, a local telescopic IO element, a local IO prism, a local cylindrical condenser, a local plane condenser, a local IO mirror, a single-zone local IO element of reflection, a vertical double-zone local IO element of reflection, a horizontal double-zone local IO element of reflection, a joint group of local IO elements of reflection wherein each pair of reflecting elements shares a common electrode, and a local multifunctional IO element, wherein said local IO element is selected from the group of design characteristic IO elements consisting of:
a local two-dimensional IO element, a Cartesian two-dimensional IO element on a plane, a condenser of non-uniform height on a plane, a plane condenser, a Cartesian two-dimensional IO element on a surface, a condenser of non-uniform height on a surface, a cylindrical condenser, a local three-dimensional IO element, a local doubly symmetric IO element, a sectorial transbending IO element, a sectorial transaxial IO element, a V-shaped IO element, a conic IO element, a crossed IO element, a boxlike IO element, a transbending-mixed IO element, a crossed-mixed IO element, a boxlike-mixed IO element, and a heterogenic-mixed IO element.

13. The management subsystem of claim 11, comprising at least one extended IO element selected from the group consisting of single-staged and array-staged extended IO elements, having at least one of functional and design features, where said extended IO element is selected from the group of functional feature IO elements consisting of:
an extended IO element of refraction, an extended IO lens, an extended telescopic IO element, an extended IO prisms, an extended IO element of reflection, a single-zone extended IO element of reflection, a vertical double-zone extended IO element of reflection, a horizontal double-zone extended IO element of reflection, a joint group of extended IO elements of reflection, wherein each pair of reflection elements shares a common electrode, and an extended multifunctional IO element, wherein said extended IO element is selected from the group of design characteristic IO elements consisting of:
an extended two-dimensional IO element, a Cartesian two-dimensional IO element on a plane, a condenser of non-uniform height on a plane, a plane condenser, a Cartesian two-dimensional IO element on a surface, a condenser of non-uniform height on a surface, a cylindrical condenser, an extended three-dimensional IO element, an extended doubly symmetric IO element, an alternating sectorial transbending IO element, an alternating sectorial transaxial IO element, an alternating V-shaped IO element, an alternating conic IO element, an alternating crossed IO element, an alternating boxlike IO element, an alternating transaxial bending-mixed IO element, an alternating crossed-mixed IO element, an alternating boxlike-mixed IO element, and an alternating heterogenic-mixed IO element.

14. The management subsystem of claim 11, wherein said at least one IO element comprises a doubly symmetric IO element, and electrode operating surfaces of said IO element are arranged as at least one of planar operating surfaces, concave operating surfaces, and a pair of parallel identical planar operating surfaces such that adjacent facing frontal lines of at least one electrode pair are described by sections of second-order curves.

15. The management subsystem of claim 11, wherein said at least one IO element comprises an axisymmetric IO element, and electrode operating surfaces of said IO element are selected from the group consisting of:
cylinder surfaces diaphragm-electrode surfaces;
surfaces as sectors of cones;
and revolving surfaces, generated by rotation of components thereof about a straight axis and described by segments of second-order curves, wherein at least one electrode of said IO element comprises at least one hole for ion flux passage.

16. The management subsystem of claim 15, wherein said electrode operating surfaces comprise diaphragm-electrode operating surfaces having one of planar and concave forms.

17. The management subsystem of claim 11, wherein said IO element comprises an IO element of reflection having an cover electrode, such that it is located perpendicular to an axis/plane of symmetry of an adjacent electrode of said IO element.

18. The management subsystem of claim 11, comprising a P-element configured to allow ions in said charged particle flux to move on portions of an M-surface proximate said P-element.

19. The management subsystem of claim 18, wherein said P-element comprises a first P-element comprising one of a P-element of reflection and a multifunctional P-element, and additionally comprises at least one IO element of refraction configured as a second P-element, such that output and input mean planes of said first and second P-elements are substantially parallel.

20. The management subsystem of claim 11, comprising a P-element configured to allow ions in said charged particle flux to move proximate a longitudinal-vertical plane of said P-element.

21. The management subsystem of claim 20, wherein said P-element comprises at least one P-element being one of a P-element of reflection and a multifunctional P-element, and additionally comprises at least one IO element of refraction configured as a P-element.

22. The management subsystem of claim 21, wherein longitudinal-vertical planes of said at least one P-element and said IO element of refraction are substantially parallel.

23. The management subsystem of claim 11, wherein said at least one IO element comprises a first IO element and a second IO element, defining:
an angle .beta..sub.(12)1 between vectors read counterclockwise from a unitary vector n.sub.(12), directed from said first IO element towards said second IO element and arranged on a line interconnecting effective points of reflection/refraction on a path ion flux of said first and second IO elements, towards a unitary axial vector n.sub.1 of said first IO element, wherein said angle .beta..sub.(12)1 is within the range .times..beta..times..times..pi. ##EQU00046## and an angle .beta..sub.(12)2 between vectors read counterclockwise from said unitary vector n.sub.(12) towards a unitary axial vector n.sub.2 of said second IO element, wherein said angle .beta..sub.(12)2 is within the range .pi..times..times..beta..times..times..times..pi. ##EQU00047##

24. The management subsystem of claim 23, wherein said angle .beta..sub.(12)1 is within the range .times..beta..times..times..pi. ##EQU00048## and said angle .beta..sub.(12)2 is within the range .pi..times..beta..times..times..pi. ##EQU00049##

25. The management subsystem of claim 23, comprising first, second, and third identical IO elements, configured such that:
said angle .beta..sub.(12)1 is within the range .times..pi..times..beta..times..times..times..pi. ##EQU00050## said angle .beta..sub.(12)2 is within the range .pi..times..times..beta..times..times..times..pi. ##EQU00051## an angle .beta..sub.(23)2, defined between vectors read counterclockwise from a unitary vector n.sub.(23), directed from said second IO element towards said third IO element and arranged on a line interconnecting effective points of reflection/refraction on a path ion flux of said second and said third IO elements, towards said unitary axial vector n.sub.2, is within the range .times..pi..times..times..beta..times..times..times..pi. ##EQU00052## and an angle .beta..sub.(23)3, defined between vectors, read counterclockwise from said unitary vector n.sub.(23) towards a unitary axial vector n.sub.3 of said third IO element, is within the range .pi..times..times..beta..times..times..times..pi. ##EQU00053##

26. The management subsystem of claim 25, wherein said first, second, and third identical IO elements are configured such that said angle .beta..sub.(12)1 is within the range .times..times..beta..times..times..pi. ##EQU00054## said angle .beta..sub.(12)2 is within the range .pi..beta..times..times..times..pi. ##EQU00055## said angle .beta..sub.(23)2 is within the range .times..pi..times..times..beta..times..times..times..pi. ##EQU00056## and said angle .beta..sub.(23)3 is within the range .pi..times..beta..times..times..pi. ##EQU00057##

27. The management subsystem of claim 25, wherein said first, second, and third identical IO elements are configured such that said angle .beta..sub.(12)1 is within the range .times..pi..times..beta..times..times..times..pi. ##EQU00058## said angle .beta..sub.(12)2 is within the range .pi..times..times..beta..times..times..times..pi. ##EQU00059## said angle .beta..sub.(23)2 is within the range .times..pi..times..beta..times..times..times..pi. ##EQU00060## and said angle .beta..sub.(23)3 is within the range .pi..times..beta..times..times..pi. ##EQU00061##

28. The management subsystem of claim 11, comprising a multi-element P-element arranged in a horizontal-straight-line and configured to allow arrangement of said averaged vector of said charged particle flux on an M-surface proximate said P-element.

29. The management subsystem of claim 28, wherein output and input mean planes of P-elements forming part of said management subsystem are parallel to each other.

30. The management subsystem of claim 28, comprising two P-elements having output and input mean planes intersecting at an angle .omega., and configured to allow substantial coinciding of a line of intersection of said mean planes with said averaged vector of said path ion flux at a midway point between said P-elements, wherein said angle .omega. is within the range .times..PI..times..times..pi. ##EQU00062##

31. The management subsystem of claim 30, performed as a reflection subsystem wherein the projections .theta.'.sub.1y and .theta.'.sub.2y, correspond to angles .theta.'.sub.1 and .theta.'.sub.2 on its base plane (superposed by coordinate plane yz) and projections .theta.'.sub.1x and .theta.'.sub.2x, corresponding to angles .theta.'.sub.1 and .theta.'.sub.2, on their longitudinal-incremental plane (superposed by coordinate plane xz), on the assumption that .theta.'.sub.1=.theta.'.sub.2 are determined respectively by formulas:
.times.' .times.'.times..times..times..times. .times..times..PI. .times.' .times.'.times..function..times..times. .times..times..PI. ##EQU00063## wherein:
.theta.'.sub.1--angle of input-reflection of one P-element e, .theta.'.sub.2--angle of input-reflection of the other P-element.

32. The management subsystem of claim 28, additionally comprising at least one IO element of refraction configured as a series of single IO lens elements.

33. The management subsystem of claim 32, wherein said at least one IO element of refraction is a P-element of refraction, having at least one of input and output mean planes which are substantially parallel to at least one of input and output mean planes of symmetry of at least one of two adjacent P-elements of reflection.

34. The management subsystem of claim 12, comprising a multi-element P-element arranged in a vertical straight-line and configured to allow arrangement of said averaged vector of said charged particle flux on a longitudinal-vertical plane proximate said P-element.

35. The management subsystem of claim 34, comprising two P-elements having longitudinal-vertical planes which are substantially parallel to each other.

[[snip]]

 

173. The MS of claim 162, wherein said ionic source IB-channel, mentioned in this invention, comprises at least one ion source each said ion source being adjacent to one output aperture of said ionic source, selected from the group consisting of:
holes;
screening tubes with skimmers;
screening tubes without skimmers;
and devices for preliminary forming of at least one path ion flux, wherein quantity number, configuration, and arrangement of holes of said devices conform to boundary surfaces.

174. The MS of claim 173, wherein said ionic source IB-channel additionally comprises a transient controlling source unit comprising at least one electrode with output surfaces for transferring said path ion flux.

175. The MS of claim 174, wherein the ions source of ionic source IB-channel is decided-on among the series comprising any ionic source providing forming of ion flux, e.g., electronic ionization (EI), chemical ionization (CI), electron capture (EC), electric field ionization (FI), ionization with heat spray, ionization under atmospheric pressure, electrospray, ionization under atmospheric pressure (APESI), chemical ionization under atmospheric pressure (APCI), photoionization under atmospheric pressure (APPI), inward laser desorption:
mass-spectrometry, matrix-activated laser desorption/ionization (MALDI), gas-filled MALDI, atmospheric MALDI, bombardment by fast atoms (FAB), field desorption--desorption in electric field (FD, plasma desorption (PD), ionization in inductively coupled plasma (ICP), thermal ionization, glow discharge ionization and spark ionization, plasma and glow discharge ionization, corona discharge and ionization in process of laser ablation.

176. The MS of claim 173, wherein said ionic source IB-channel is configured to allow forming of ion flow exiting said ionic source IB-channel in at least one of a pulsed flow of ions packages and a continuous ion flow.

177. The MS of claim 176, wherein said block-structured docking group comprises a block-structured docking group adjacent said ionic source block comprising at least one parallel pre-shaping IB-channel, which pre-shaping IB-channel comprises at least one structural elements configured to allow intermediate configuration, acceleration, and control of ion flux forming.

178. The MS of claim 177, wherein said pre-shaping IB-channel comprises at least one section selected from a group consisting of:
ion pre-traps;
flux drift tubes of asymmetrical cells of ion mobility, DC/field comprising input and output gates with ion gate valves;
refracting P-elements;
and diaphragms-apertures.

179. The MS of claim 178, wherein said ion pre-trap is configured to:
select certain quantities of ions generated by said ionic source IB-channel;
to store said quantities of ions;
and to output said store ions from said ion pre-trap and input said stored ions into at least one subsequent said MS block.

180. The MS of claim 179, wherein said ion pre-trap is selected from a group consisting of a controlling electrode group with an electric field, a short unit of guiding quadrupole, and a diaphragm-aperture.

181. The MS of claim 180, wherein said block-structured docking group additionally comprises a distributing-accelerating block arranged behind a performing block which comprises at least one distributing-accelerating IB-channel, wherein one of said distributing-accelerating block and said distributing-accelerating IB-channel comprises at least one pre-analyzing-guiding accelerator configured to allow guiding of said ion flux towards an analyzing-dispersing IB-channel which comprises at least two accelerating electrodes with at least, one output gate.

182. The MS of claim 181, wherein said at least one output gate of said pre-analyzing-guiding accelerator is covered with a fine mesh.

183. The MS of claim 181, configured to confine an angle .beta..sub.(12)1 defined between output directions of said ion flux from the said ionic source IB-channel and from said pre-analyzing-guiding accelerator within the range of .ltoreq..beta..times..ltoreq..pi. ##EQU00070## and wherein said pre-analyzing-guiding accelerator is arranged radially with radial ion output when .beta..sub.(12)1.apprxeq.0 and is arranged orthogonally when .beta..times..apprxeq..pi. ##EQU00071##

184. The MS of claim 183, wherein said distributing-accelerating IB-channel is configured to form a pulse ion flux as said ion flux passes through said pre-analyzing-guiding accelerator.

185. The MS of claim 183, wherein said distributing-accelerating IB-channel comprises two segments, wherein one of said two segments is configured to use an alternating voltage while another of said two segments is configured to use a static voltage.

186. The MS of claim 183, wherein said distributing-accelerating IB-channel is configured to form thin ions packages appropriate for time-of-flight mass-analysis of said ion flux as said ion flux passes through said pre-analyzing-guiding accelerator.

187. The MS of claim 186, wherein its distributing-accelerating IB-channel is performed with option feature allowing an orthogonal ions output .times..times..beta..times..apprxeq..pi. ##EQU00072## its accumulation area is performed as a monofield generating a quadratic electrostatic field, while the edge of earthed electrode of the said monofield is coupled to the earthed fluxgate electrode (mesh) within the area of ions acceleration (palser) with uniform field.

188. The MS of claim 181, wherein said distributing-accelerating IB-channels are configured as static and are configured to allow forming of a continuous ion flux as said ion flux is output from said pre-analyzing-guiding accelerator.

189. The MS of claim 181, wherein said distributing-accelerating IB-channel additionally comprises a pre-analyzing ions accumulator, arranged ahead of said pre-analyzing guiding accelerator and serially connected to said pre-analyzing guiding accelerator, where said pre-analyzing ion accumulator is configured to allow receipt, accumulation, and intermittent emission of said ions in at least one of radial, axial, and orthogonal directions through said apertures.

190. The MS of claim 189, wherein said pre-analyzing ion accumulator is selected from a group consisting of a linear RF-only IC and a curved quadrupole.

191. The MS of claim 173, wherein its detector group comprises one or more ions detector with entrance gate arranged on the entry d-surface, where each path ion flux corresponds, to an individual ion detector of detector element decided-on among the terms series comprising:
Faraday cylinder;
secondary electron multiplier with at least one dynode;
scintillator and photomultiplier;
microchannel;
microsphere board;
at least two slots of detection;
at least two anodes.

192. The MS of claim 191, wherein, at least, one ions detector of detecting group is provided with ions separator of certain transmission band and comprises, at least, one of series terms comprising control grids, logical Bradbury-Nielsen terms, plane-parallel deflector (condenser).

193. The MS of claim 191, wherein each ions detector is connected to the system of data acquisition and data-storage provided with analog-to-digital converter (adaptive data compression protocol).

194. The MS of claim 191, wherein at least one ion detector is configured within said MS.

195. The MS of claim 194, wherein said ion detector is configured to allow extension of a dynamic range of said MS through alternative scanning associated with varied intensity of voltage of at least one of a pulsating ionic source and said distributing-accelerating IB-channel.

196. The MS of claim 194, wherein said ion detector is configured to extend a dynamic range of said MS through alternative scanning in varying durations of ion injections into an output gate of said ion source.

197. The MS of claim 194, wherein said ion detector is configured to allow automatic gain control.

198. The MS of claim 181, wherein its analyzing-dispersing block comprises at least, one analyzing-dispersing IB-channel, decided-on among the series comprising the following:
toroidal and cylindrical sectoral electrical analyzers;
sectoral magnetic analyzers;
orbitrap analyzer;
Fourier analyzer ICR;
static analyzer, e.g., the IO channel system of IB-channel is performed with curved main axis in cross-space dispersing mode, mentioned in this invention;
the time-of-flight (TOF IB-channel) analyzer and its IO channel system are performed in one of said modes, mentioned in this invention.

199. The MS of claim 181, further comprising a detecting group arranged on at least side adjacent said analyzing-dispersing IB-channel, wherein said detecting group comprising multiple ion detectors of different types, mentioned in this invention.

200. The MS of claim 198, wherein its block-structured docking group additionally includes an block of fragmentation cell comprising at least, one IB-channel of fragmentation cell-set filled with gas and provided with differential pumping cascades wherein each fragmentation cell is provided at least, with two apertures to access the path ion flux into the fragmentation cell and to exit from it.

201. The MS of claim 200, wherein each its path ion flux corresponds to one individual fragmentation cell (section of fragmentation cells).

202. The MS of claim 201, wherein at least one fragmentation cell is performed with option feature to using it in two modes:
passage of ions through fragmentation cell without substantial atomization or with ions atomization (fragmentation) within fragmentation cell (inside of fragmentation cell).

203. The MS of claim 199, wherein said block-structured docking group additionally includes one ion selecting block comprising at least one IB-channel of ion selection, configured to allow sequential reduction of the range of ion mass selection through at least one ion selecting step.

204. The MS of claim 203, wherein said IB-channel of ion selection is selected from a group consisting of:
a quadrupole IB-channel;
an ion trap;
a static IB-channel;
and a TOF IB-channel analyzer.

205. The MS of claim 203, comprising a detecting group arranged at least on one side of said IB-channel of ion selection.

206. The MS of claim 203, wherein at least one of said analyzing-dispersing IB-channels and said IB-channel of ion selection comprises means of adjusting a path length and a voltage of ion acceleration.

207. The MS of claim 206, wherein said analyzing-dispersing IB-channel is configured to allow at least one of said ion path length and said voltage to be less than a value for said IB-channel of ion selection.

208. The MS of claim 207, wherein said MS-channel is configured to allow ion time-of-flight through said IB-channel of ion selection to be at least three times as large as ion time-of-flight through said analyzing-dispersing IB-channel.

209. The MS of claim 208, wherein at least one of said IB-channel of ion selection and said analyzing-dispersing IB-channel is nonmagnetic.

210. The MS of claim 208, wherein said IB-channel of ion selection is configured as a time-of-flight IB-channel and said IO channel system is configured in multireflecting mode and selected from the group consisting of:
single, single-train-multilayer and multi-row-multilayer modes.

211. The MS of claim 210, wherein said analyzing-dispersing IB-channel mentioned in this invention is configured as a time-of-flight IB-channel with straight axes.

212. The MS of claim 205, wherein said block-structured docking group additionally comprises blocks of additional ion accumulation, comprising at least one IB-channel of additional ions accumulation, configured to allow selection of the ion subsets or at least some of their derivatives.

213. The MS of claim 212, wherein said IB-channel of additional ion accumulation is selected from the group consisting of linear RF-only IC and curved quadrupole.

214. The MS of claim 212, wherein at least one said MS-channel is configured to allow implementation of a series of steps towards for ion flux:
(ab) inject said path ion flux via an IB-channel of said ionic source into a pre-shaping IB-channel;
(bc) eject said path ion flux from said pre-shaping IB-channel and inject said path ion flux into a distributing-accelerating IB-channel;
(cd) eject said path ion flux from said distributing-accelerating IB-channel, inject said path ion flux into said ion selecting IB-channel, and register said path ion flux in at least one detector group at said ion selecting IB-channel;
(de) eject said path ion flux from said ion selecting IB-channel and inject it into a fragmentation cell;
select from the series comprising {(ec) and (ef)}:
eject the path ion flux from the cell of fragmentation and inject it depending on the path ion flux composition after the effect of the cell of fragmentation on the ion flux at appropriate option into one of channels: distributing-accelerating IB-channel;
IB-channel of additional ion accumulation and storage of taken-off ions masses;
(Q11) at least, one cycle comprising series steps such as (cd), (de) and {(ec) or (ef)} to accumulate ions of specified masses in the IB-channel of additional ion accumulation;
select from the series comprising (fc) and {(fe) and further (ec)}:
(fc)-eject the path ion flux from the IB-channel of additional ion accumulation and inject it into the distributing-accelerating IB-channel;
{(fe)}:
eject the path ion flux from the IB-channel of additional ion accumulation and inject it into cell of fragmentation;
and further {(ec)}:
eject the path ion flux from the cell of fragmentation and inject it into distributing-accelerating IB-channel;
(Q12) at least, one cycle comprising (Q11) with subsequent selection from (fc) and {(fe) and further (ec)};
(cg) eject the path ion flux from the distributing-accelerating IB-channel and inject it into the analyzing-dispersing IB-channel, as well register the path ion flux at least in one detector group of analyzing-dispersing IB-channel;
at the option, depending on results of step (cg) realization, implement the steps of channel ion flux transfer by means of two of groups of steps: (Q13), at least, one cycle comprising single-stepping implementation of all steps of path ion flux advance as it is specified in (ab)-(cg) mentioned in this claim;
select from the series comprising (ge), {(gc) and further (ce)}:
eject the path ion flux from the analyzing-dispersing IB-channel and inject it, conforming to appropriate option, into one of channels:
into the fragmentation cells;
{(eject the path ion flux from the analyzing-dispersing IB-channel inject it into the distributing-accelerating IB-channel) and further (eject the path ion flux from the distributing-accelerating IB-channel and inject it into fragmentation cells)};
(Q14) at least, one cycle comprising implementation of all steps:
beginning by the step selected from the group consisting of {(ec), (ef)} and finishing by (cg) step as it is specified in this claim.

215. The MS of claim 212, wherein at least one MS-channel is performed with option feature allowing sequential steps to transferring channel ion flux (second version of extended-multiblock mode):
(ab);
(bc);
(cd);
(de);
decided-on among the group of {(ec), (ef)};
(Q11);
decided-on among the group of (fc) and {(fe) and further (ec)};
(cg);
at the option, depending on results of step (cg) realization implement the steps of channel ion flux transfer by means of one of two groups of steps: (Q23) at least, one cycle comprising sequential implementation of all steps (ab)-(cg) as said in this claim;
selection from the series comprising (ge) and {(gc) and further (ce)};
(Q24) at least, one cycles comprising sequential implementation of all steps:
beginning from decided-on among the group of {(ec) or (ef)} to (cg) as said in this claim.

216. The MS of claim 211, wherein at least one MS-channel is performed with option feature allowing sequential steps in transferring channel ion flux by skipping the IB-channel of additional ion accumulation (multiblock mode of operation): (ab);
(bc);
(cd);
(de);
(ec);
(Q31) at least, one cycle comprising increments as steps follows:
(cd), (de) and (ec);
step (cg);
at the option, depending on results of step (cg) realization implement the steps of channel ion flux transfer by means of one of two groups of steps:
(Q33) at least, one cycle comprising sequential implementation of all steps (ab)-(cg) as said in this claim;
select from the series comprising (ge) and {(gc) and further (ce)};
(Q34) at least, one cycle comprising sequential implementation of all steps beginning from (ec) to (cg) as it is specified in this claim.

217. The MS of claim 200, wherein at least, one MS-channel is performed with option features allowing to implement series steps of path ion flux advance by-passing the IB-channel of additional ion accumulation and IB-channel of ions selecting, failing all last mentioned IB-channel inclusive (mean modularity level of operation without ions selecting):
(ab);
(bc);
(cg);
(ge) or {(gc) and further (ce)};
(ec);
(cg);
at the option, perform the series steps of path ion flux advance depending on results of (cg) step implementation:
at the option, depending on results of step (cg) completion implement the steps of channel ion flux transfer by means of one of two (Q43), (Q44) groups of steps:
(Q43) at least, one cycle comprising implementation of all steps beginning from (ab) to the last (cg) step mentioned in this claim;
(Q44) at least, one cycle comprising implementation of all steps (ec);
(cg) decided-on among the group of (ge) and {(gc) and further (ce)} mentioned in this claim.

218. The MS of claim 199, wherein at least one MS-channel is performed with option feature allowing a sequential implementation of all steps to transferring the channel ion flux by-passing the IB-channels of additional ion accumulation and the IB-channel of fragmentation cell, failing all last mentioned IB-channels inclusive (mean modularity level of operation without ions fragmentation):
(ab);
(bc);
(cd);
(dc) output the channel ion flux from the ions selecting IB-channel and input it into distributing-accelerating IB-channel;
(Q51) at least, one cycle comprising implementation of all steps (cd) and (dc);
step (cg).

219. The MS of claim 199, wherein at least one MS-channel is performed with option feature allowing sequential implementation of all steps to transferring the channel ion flux by-passing the IB-channel of additional ion accumulation, IB-channel of ions selecting and IB-channel of fragmentation cell, failing all last mentioned IB-channels inclusive (small modularity regime of operation):
(ab);
(bc);
(cg).

220. The MS of claim 162, wherein when it is performed as a time-of-flight analyzing-dispersing IB-channel it comprises a data transmitting and data processing system providing parallel reception of child fragments spectra without intermixing the ions spectra representing the primary materials.

Description

FIELD OF THE DISCLOSED TECHNOLOGY

This invention may be applied in fields such as medicine, biology, gas and oil industry, metallurgy, energy, geochemistry, hydrology, ecology, food industry, narcotics control, and drug testing.

BACKGROUND OF THE DISCLOSED TECHNOLOGY

Terms used in this disclosure are explained in definitions included in the invention description. Several such terms, related mainly to novel objects proposed herein, require supplemental explanations for their single-valued interpretation which are offered herein. A P-element is defined as an IO (ion-optical) element that is configured to create a two-dimensional mean geometric surface (M-surface, hereinafter) of the IO element. The M-surface is formed by perpendicular displacement of a generated straight line. In a general case, the P-element may be created from a nonplanar two-dimensional mean surface. Particular embodiments of the P-elements are modes in which they combine geometric mean planes and a plane of electric field symmetry and/or of magnetic field antisymmetry.

The P-elements are divided into cartesian-two-dimensional P-elements and three-dimensional P-elements. All P-elements are considered to be three-dimensional P-elements with the exception of Cartesian-two-dimensional type P-elements having uniform or nonuniform heights, depending only on two coordinate axes in Cartesian coordinates. Cartesian-two-dimensional P-elements are divided into planar-two-dimensional P-elements with geometric mean planes and surface-two-dimensional P-elements, such as a M-surface, which is formed by parallel displacement of the straight-line along the bent line, zigzag line or bent-zigzag line.

Several examples of the P-elements are: cylindrical condensers, P-elements having asymmetrically nonuniform heights in a parallel front-edge arrangement of Cartesian-two-dimensional electrodes, plane condensers, P-elements with axially asymmetric horizontal orientation of electrodes and with symmetrically nonuniform height or uniform height of electrodes arrangement, sectoral magnetic P-elements, and conic P-elements (V-shaped, conic).

Extensions of the M-surface off the field of the P-element at its input and output are referred to respectively as the input and output mean planes of the P-element.

The P-elements extended in either direction are referred to as extended P-elements. Extended P-elements are designed for simultaneous or successive actions on a single path or multipath ion flux at different segments along the length of the extended P-element.

Any IO system or sub-system interacting three or more times with an ion flux, such as single multi-reflectors, and any IO system or sub-system comprising three or more P-elements, may be described using projections on two or three mutually perpendicular characteristic planes, e.g., a base plane, an incremental plane or longitudinal-incremental plane, and a transverse-incremental plane.

The base plane of an incremental IO system or sub-system is a plane that is perpendicular to the linear axes of extended P-elements parallel to each other.

At least three quarters of the components of planar IO systems or sub-systems, also referred to as the supporting portion of planar IO systems or sub-systems, may be located on a single plane, e.g., their supporting plane. The base plane of a planar IO system is a plane parallel to the ion flux between three or more conjoined sections of supporting P-elements of the IO system, such that the ion flux passes from one section to the other, and this base plane has the smallest angle relative to the supporting plane of the IO system.

The incremental plane of the IO system or subsystem is a plane perpendicular to the base plane of the IO system or subsystem.

The IO systems are divided into two-dimensional systems and three-dimensional systems. IO systems configured to provide ion motion, mainly close upon one or around one plane, are typically two-dimensional systems (for example, IO planar systems and R-multi-reflectors of rectilinear reflecting type), while other IO systems are typically three-dimensional systems.

A planar IO system or sub-system (e.g., planar R-multi-reflector or planar control subsystem) is considered to be open (non-closed type), if it is configured to provide an out-of-base-plane arrangement of descending and outgoing branches of ion paths in the IO system or sub-system. IO systems or subsystems of a non-closed type are considered to be single-plane systems or sub-systems provided that the descending and outgoing branches of ion paths are arranged in one plane. Any other IO systems or sub-systems of non-closed type, which do not meet these conditions are considered to be non-coplanar.

An open IO system or sub-system is defined as a system or sub-system with parallel-projective symmetrically non-coplanar input/output, if it is configured to provide arrangement of descending and outgoing branches of ion paths in one or more planes, the arrangement being one of a typical line components of this IO system or sub-system and perpendicular to the IO system or sub-system base plane.

In a multinodal reflecting IO system, e.g., in a control subsystem (reflection or reflection/refraction subsystem) or in a R-multi-reflector, any constituent IO reflection units designed to receive the ion flux entering from the outside of the IO system and to remove the ion flux from the IO system are referred to as the first (or receiving) IO reflection unit and the last (or output) IO reflection unit, respectively. Other IO reflection units of the multimodal reflecting IO system are referred to as mean IO reflection units, or, each IO reflection unit is referred to by its number along the streamline of ion flux. For example, in a two-loop reflecting R-multi-reflector with four IO reflection units, the IO reflection unit located on one diagonal segment of a typical line with the receiving IO reflection unit is referred to as the second reflection unit, and the IO reflection unit located on one diagonal segment of a typical line with the output IO reflection unit is referred to as the third reflection unit.

In general, various mass-spectrometric methods and mass-spectrometers (MS) are known. In general, a mass-spectrometric method provides the following: a) Ionize the substance sample in an ionic source unit and remove the ion flux (ions) out it and form the ion flux and control its motion, including its mass dispersion by ion masses (mass dispersion by values of ion mass/charge ratios, m/z), with the aid of static or variable components of magnetic and/or electric fields. The fields are typically generated by groups of ion-conducting blocks composed of ion-conducting IB-channels with boundary surfaces and channel IO subsystems (P-elements), each of which is a part of a MS-channel within an IO system (series-connected ion-conducting IB-channels and ionic source IB-channel of ionic source unit). At that, the channel IO subsystem of each ion-conducting IB-channel comprises one or more control subsystems, or comprises a curve main axis in a cross-space dispersing mode or in a multi-reflecting mode; b) Register ions by means of one or more sensors of a detector system; c) Control and manage the operations of all blocks of the mass-spectrometer as well as support the data processing by means of a controller-computer system. A mass-spectrometer (MS) to perform mass-spectrometry processes consists in general of the following:

a) MS-blocks: ionic source unit formed of a group of ion-conducting blocks, composed of a coupling module element and an analyzer-disperser block. The ionic source units include IB-channels with boundary surfaces and channel IO subsystems (P-elements), and each IB-channel of a block is a part of the MS-channel with the IO system, resulting in an ion-conducting IB-channels of ion-conducting blocks together with the ionic source IB-channel of the ionic source unit. The channel IO subsystems (P-elements) comprises one or more IO control subsystems, or comprises a curve main axis in a cross-space dispersing mode or in a multi-reflecting mode;

b) Detector circuit;

c) Controller-computer system. Each IB-channel serves to form and control motions of channel ion flux and includes a channel IO subsystem with one or more IO elements, each of which contains two or more electrodes and one or more boundary surfaces, the surfaces being surfaces of output or surfaces of input and output for channel ion flux. An ionic source type of an IB-channel, also referred to as an IB-channel of an ionic source unit or an ionic source IB-channel, includes surfaces of output, mainly, in coincidence with a boundary electrode of the ionic source IB-channel. An ion-conducting type of IB-channel, also referred to as an IB-channel of an ion-conducting module or an ion-conducting IB-channel, contains boundary surfaces and channel IO subsystems (IO elements), comprising a single control subsystem or more such subsystems; or comprising a curve main axis in a cross-space dispersing mode or in a multi-reflecting mode.

There are multiple alternatives of MS block-structured docking groups depending on specified tasks to be solved by proposed MS means. According to a quantitative module composition of block-structured docking groups, the MS may include different types of MS modularity levels: extended-multimodule and multimodule MS; MS of mean modularity level, medium modular MS and small-section modular MS.

Small-section modular MS are designed to be operated in a single-stage mass-spectrometry process. As such, a MS block-structured docking group is composed of minimum structural elements: a pre-shaping module and a distributing accelerator module. The block-structured docking group of a MS of mean modularity level is composed of a pre-shaping module, a distributing accelerator module and a module of a refinement cell or an ion trapping module.

The block-structured docking group of multimodule MS is composed of a pre-shaping module, a distributing accelerator module, a module of a refinement cell and an ion trapping module. The block-structured docking group of an extended-multimodule MS is composed of a pre-shaping module, a distributing accelerator module, a module of a refinement cell, an ion trapping module, and a module of further ion accumulation trapping.

The MS of mean modularity level including the module of the refinement cell, the multimodule MS, and the extended-multimodule MS allow to carry out molecule structure analyses based on multi-stage, e.g., tandem, mass-spectrometry (MS/MS) or to carry out the spectrometry with multiple-cycle ion accumulation of a certain mass range (MSn).

All known MS, with the exception of parallel multi-channel quadrupole type MS, are single channel, channel-single-path, MS, ensuring simultaneous analysis of only single-path axial ion flux.

Known parallel multi-channel MS, containing, in one vacuum volume, at least several channels, and referred to as parallel MS, comprise a single-stage quadrupole MS. U.S. Pat. No. 7,381,947, Publ. Jun. 3, 2008 describes a single-stage quadrupole MS, including N channels, where N is a integer number greater than one, composed of the following: an ionic source module including N ionic source IB-channels, each of which has a single source of ions; a block-structured docking group provided with a pre-shaping module and a distributing accelerator module, each of which contains N IB-channels; a dispersing analyzer module which contains N dispersing analyzer IB-channels; a detector system, including N ion detectors; and a controller computer system. The dispersing analyzer module comprises N coupled quadrupole IB-channels having common interchannel electrodes, each of which is a single-path (single-flow) channel.

This MS type, just as all known single-stage MS with a quadrupole ion trap, is notable for its poor weighing accuracy, i.e., up to <20 ppm and shows a relatively low resolution power up to several tens of thousands.

The main disadvantage of this MS type is in the low value of resolution power/costs ratio. Moreover, this MS type is related to low-modular MS and does not allow to carry out structure analyses.

Known methods of spectrometry and mass-spectrometer (MS) described in the invention of A. Makarov (Pub. No.: US 2009/0166528 A1, Publ. Jul. 2, 2009) is the closest prototype to the claimed invention. The block-structured docking group of this MS prototype comprises a pre-shaping module, a distributing accelerator module, a refinement cell, and a module of ion trapping. Some MS versions optionally comprise a module of further ion accumulation. Each MS module comprises one IB-channel. Depending on the type of dispersing analyzer IB-channel, different MS versions comprise a different number of detector modules and outputs to them. The Makarov reference (trapping distribution module) is mainly used as a dispersing analyzer IB-channel. Additionally, this prior invention teaches other versions of dispersing analyzer IB-channel embodiment, e.g. in a multi-reflecting mode.

The Makarov prototype is notable for its high weighing precision in multi-reflecting mode up to <2 ppm (at internal calibrations). It has resolution power over 100000. Such a device costs several millions of US$.

The main disadvantage of this prototype is in low value of resolution power/costs ratio (marginal costs). It provides no MS versions assuring flexible configuration modification for specific tasks through varied levels of block-structured docking group modularity. Moreover, this prototype does not consider species of electric (nonmagnetic) time-of-flight (TOF) IB-channels and their characteristics promising to enhance values of resolution power/costs ratios.

Values of the resolution power/costs ratio and the MS power potentials are determined mainly by the MS modularity level as well as by the functional characteristics and by the cost of IB-channels (especially by the resolution power of dispersing analyzer IB-channel and the IB-channel of ion trapping, if any) suitable for assembly of such modules.

The MS with different modularity levels are commonly based on use of electric IB-channels of multi-resolution modes, such as nonmagnetic static electric fields or electric fields with variable components, by virtue of the resolution power/costs ratio in their operations as IB-channels of ions trapping and mass dispersing analyzer IB-channel. A nonmagnetic/electric IB-channel differs from other types of IB-channels (e.g., with double focusing, ion cyclotron resonance, sectoral-magnetic, Fourier analyzers etc.) by smaller geometrical dimensions, masses and power capacity, and by a simple and reliable design. Moreover they are relatively cheap. E.g., nonmagnetic time-of-flight MS (TOF MS) based on the electric time-of-flight IB-channel surpasses other MS types by its unlimited mass ranges (up to tens of millions of atomic mass) and higher analysis rates. These TOF MS functional capabilities allow to carry out analyses unreachable by means of other types of mass-spectrometers, e.g., analyze time-varying processes or organic matters which are mixtures of different individual compounds (e.g., oil).

Currently there are known electric TOF IB-channels used in MS, which may be classified by four main resolution levels, i.e.: first resolution level specifies the radio frequency TOF IB-channels of linear type (variable fields) and of electrostatic type with a straight main optical axis (static fields); second resolution level specifies the reflectron TOF IB-channels (with straight main optical axis and single-reflecting channels); third resolution level specifies the reflectron TOF IB-channels with a curved main axis (including single-, double-, and triple-reflection subsystems with a curve axis or reflection-refraction subsystem) and having vectors of input and output path ion flux spaced from each other; fourth resolution level specifies the multi-reflecting TOF IB-channels (over five reflections).

There are known linear radio frequency (variable fields) and electrostatic with straight main optical axis (static fields) TOF IB-channels used in different linear TOF MS (s-TOF MS)--such as AXIMA-LNR [www.analyt.ru], MSX-4 [www.niivt.ru] and those described in patent RU 2367053. In linear radio frequency IB-channels (e.g., RU 2367053) plate electrodes generating periodic two-dimensional linear high frequency (HF) fields are provided along the axis between ions source and ions detector. HF fields step up the path and time of ion movement in the TOF MS, enhancing ions dispersion by masses (i.e., enhancing MS resolution capacity) as compared to electrostatic IB-channels with a straight main optical axis (static fields).

Linear TOF IB-channels in the TOF MS provide only a low resolution level (resolution reaches some hundreds), but they are small-sized, simple in operations, and power and cost saving.

There are known reflectron TOF IB-channels (e.g.: RF patent No. 2 103 763 C, Publ. 27 Jan. 1998; U.S. Pat. No. 4,694,168, Publ. 15 Sep. 1987) used in the reflectron TOF MS (sR-TOF MS) where the area of all operating processes of ion flux covers the TOF MS straight main axis. The reflectron IB-channel in each such sR-TOF MS comprises a special area of a single reflection of ion packages within an electric field. Reflection of an ion package is used to enhance resolution power through time-of-flight focusing of the ion package by ionic energy. As with all known patents and manufactured devices related to the sR-TOF MS, in order to reflect ion packages there are applied uniform electric fields enclosed by one or several fine-meshed metal screens.

A method of single-reflecting spectrometry with straight main optical axis based on the reflectron IB-channel consists of directing ion packages towards one or several electric fields, enclosed by screens, at a right angle to the mesh planes, reflection of the ion packages throughout the electric fields and further ion package logging. As such, along the path from the source to the detector, ion packages pass twice through each screen required to generate electric fields commonly considered as uniform.

Reflectron IB-channels in a sR-TOF MS provide a mean resolution level (resolution reaches up to several thousand), while they are small-sized, simple in operations, and power- and cost saving.

The main sR-TOF MS disadvantage is in the relatively low resolution power due to the fact that the fine-mesh screens located in the area of ion movement give rise to several phenomena adversely affecting the performance characteristics of reflectron IB-channels, in particular, to ions scattering at the screens and uncontrolled extra ionic energy spread, and consequently, to lowering of IB-channel resolution power.

There are known reflectron TOF MSs (cR-TOF MS) comprising IB-channels with ion flux axes spaced from each other (for spaced source and detector) and with a curved main axis (e.g.: U.S. Pat. No. 6,621,073, B1, Publ. 16 Sep. 2003; US, 2008/0272287 A1, Publ. 6 Nov. 2008).

Methods described in the above mentioned patents consist of operation of an IB-channel with one to three reflecting electric fields and direction of ion packages emitted by a source into these reflecting electric fields at acute angles relatively to vectors of the fields; of ion packages reflecting in the electric fields; and further of ion packages logging.

In U.S. Pat. No. 6,621,073, B1 and US patent 2008/0272287 A1 the IB-channels comprise uniform electrostatic or reflector fields enclosed by one or several close-mesh screens extended at slit diaphragms. In US patent 2008/0272287 A1, the diaphragms and detector slits are sized considering that the width of a reflected ion package is greater than its width when incoming due to different ionic energy in the package.

There is known a single-reflecting and triply-reflecting embodiment of an IB-channel used in cR-TOF MSs (U.S. Pat. No. 6,717,132 B2, Publ. Apr. 6, 2004), specifying gridless reflector fields generated by slit diaphragms for single-triple reflections. Herein it is assumed that the field of slit diaphragms within an area of ion flux passage is a Cartesian-two-dimensional field, in which no forces act on the ions in a horizontal direction.

The main disadvantage of the IB-channel with a Cartesian-two-dimensional field consists in the default of focusing ions... [[snip]]

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