Combination of time resolution and mass dispersive techniques in mass spectrometry

Claim 2

A time-resolved mass dispersive mass spectrometer comprising: a source for providing sample ions; an accelerator means for accelerating the sample ions to provide ions having a substantially constant relationship between mass and velocity; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; a mass analyzer following at least said ion accelerator including a deflection field for angularly dispersing sample ions; and a detector system responsive to ion intensity and the deflection field strength required to produced a particular angular dispersion, and coupled to said bunching device for determining ion flight time.

Claim 3

A mass spectrometer in accordance with claim 1, which further comprises an output computation device for determining ion mass based on the deflection field strength and ion flight time.

Claim 4

A mass spectrometer in accordance with claim 2, which further comprises a computer control system for controlling scanning of the deflection field strength.

Claim 5

A mass spectrometer in accordance with claim 1, wherein said mass analyzer includes a magnetic field for angularly dispersing ions.

Claim 6

A mass spectrometer in accordance with claim 4, wherein determined magnetic field strength establishes ion momentum and said output computation device establishes ion mass independent of ion kinetic energy.

Claim 7

A mass spectrometer in accordance with claim 4, operable to establish a three-dimensional data field for subsequent analysis, the three-dimensional data field including ion intensity data as a function of ion flight time and deflection magnetic field strength.

Claim 8

A mass spectrometer in accordance with claim 4, which further comprises: an entrance aperture for said detector system such that only ions of substantially a predetermined angular dispersion enter said detector system; control elements for varying in time the magnetic field strength within said magnetic mass analyzer to provide a magnetic scan; and control elements for repetitively pulsing said ion bunching device during each magnetic scan.

Claim 9

A mass spectrometer in accordance with claim 1, wherein said mass analyzer includes an electric field for angularly dispersing ions.

Claim 10

A mass spectrometer in accordance with claim 8, wherein determined electric field strength establishes ion kinetic energy and said output computation device establishes ion mass independent of ion momentum.

Claim 11

A mass spectrometer in accordance with claim 8, operable to establish a three-dimensional data field for subsequent analysis, the three-dimensional data field including ion intensity data as a function of ion flight time and deflection electric field strength.

Claim 12

A mass spectrometer in accordance with claim 8, which further comprises: an entrance aperture for said detector system such that only ions of substantially a predetermined angular dispersion enter said detector; control elements for varying in time the electric field strength within said electrostatic mass analyzer to provide an electric field scan; and control elements for repetitively pulsing said ion bunching device during each deflection electric field scan.

Claim 13

A time-resolved mass dispersive spectrometer comprising: a source for providing parent ions; a accelerator for accelerating the parent ions; a fragmentation region wherein at least some accelerated parent ions may fragment to produce daughter ions; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; a mass analyzer following said fragmentation region including a deflection field for angularly dispersing the daughter ions and any unfragmented parent ions as a function of deflection field strength; and a detector system responsive to ion intensity and the deflection field strength required to produce a particular angular dispersion and coupled to said bunching device for determining ion time-of-flight and thus velocity as an indicator of parent mass of a detected daughter ion, and as an indicator, in combination with determined deflection field strength, of parent and daughter ion mass.

Claim 14

A time-resolved mass dispersive spectrometer comprising: a source for providing parent ions; a accelerator for accelerating the parent ions; a fragmentation region wherein at least some accelerated parent ions may fragment to produce daughter ions; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; a mass analyzer following said fragmentation region including a deflection field for angularly dispersing the daughter ions and any unfragmented parent ions as a function of deflection field strength; and a detector system responsive to ion intensity and the deflection field strength required to produce a particular angular dispersion and coupled to said bunching device for determining ion time-of-flight and thus velocity as an indicator of parent mass of a detected daughter ion, and as an indicator, in combination with determined deflection field strength, of parent and daughter ion mass.

Claim 15

A mass spectrometer in accordance with claim 12, wherein said mass analyzer includes a magnetic field for angularly dispersing ions.

Claim 16

A mass spectrometer in accordance with claim 12, wherein said mass analyzer includes an electric field for angularly dispersing ions.

Claim 17

A mass spectrometer in accordance with claim 12, wherein said ion bunching device comprises an ion source for providing parent ions in pulses separated in time.

Claim 18

A mass spectrometer in accordance with claim 13, which further comprises: an entrance aperture for said detector system such that only ions of substantially a predetermined angular dispersion enter said detector system; control elements for varying in time the magnetic field strength within said magnetic mass analyzer to provide a magnetic scan; and control elements for repetitively pulsing said ion bunching device during each magnetic scan.

Claim 19

A mass spectrometer in accordance with claim 16, wherein said detector system includes a transient recorder for recording ions arriving at a plurality of individual times for each of a plurality of individual values of magnetic field strength.

Claim 20

A mass spectrometer in accordance with claim 13, wherein said detector system includes a microchannel array ion detector for recording ions arriving with a plurality of angular dispersions for a particular value of magnetic field strength.

Claim 21

A mass spectrometer in accordance with claim 18, wherein said detector system comprises microchannel transient recorders for recording ions arriving at a plurality of individual times for each of a plurality of individual values of angular dispersion for each pulse of said ion bunching device.

Claim 22

A mass spectrometer in accordance with claim 13, operable to establish a three-dimensional data field for subsequent analysis, the three-dimensional data field including ion intensity data as a function of ion flight time and deflection magnetic field strength.

Claim 23

A mass spectrometer in accordance with claim 14, which further comprises: an entrance aperture for said detector system such that only ions of substantially a predetermined angular dispersion enter said detector system: control elements for varying in time the electric field strength within said electrostatic mass analyzer to provide an electric field scan; and control elements for repetitively pulsing said ion bunching device during each deflection electric field scan.

Claim 24

A mass spectrometer in accordance with claim 21, wherein said detector system includes a transient recorder for recording ions arriving at a plurality of individual times for each of a plurality of individual values of electric field strength.

Claim 25

A mass spectrometer in accordance with claim 14, wherein said detector system includes a microchannel array ion detector for simultaneously recording ions arriving with a plurality of angular dispersions for a particular value of deflection electric field strength.

Claim 26

A mass spectrometer in accordance with claim 23, wherein said microchannel array comprises microchannel transient recorders for recording ions arriving at a plurality of individual times for each of a plurality of individual values of angular dispersion for each pulse of said ion bunching device.

Claim 27

A mass spectrometer in accordance with claim 14, operable to establish a three-dimensional data field for subsequent analysis, the three-dimensional data field including ion intensity data as a function of ion flight time and deflection electric field strength.

Claim 28

A mass spectrometer in accordance with claim 12, wherein said fragmentation region comprises a drift region space facilitating metastable decomposition.

Claim 29

A mass spectrometer in accordance with claim 12, wherein said fragmentation region comprises a collision chamber.

Claim 30

A mass spectrometer in accordance with claim 13, wherein said fragmentation region comprises a drift region space facilitating metastable decomposition.

Claim 31

A mass spectrometer in accordance with claim 13, wherein said fragmentation region comprises a collision chamber.

Claim 32

A mass spectrometer in accordance with claim 14, wherein said fragmentation region comprises a drift region space facilitating metastable decomposition.

Claim 33

A mass spectrometer in accordance with claim 14, wherein said fragmentation region comprises a collision chamber.

Claim 34

A combined chromatography and time-resolved mass dispersive mass spectrometry system comprising: a chromatographic column for providing components of a sample as a function of time; a source coupled to the output of said chromatographic column for ionizing the sample components to provide parent ions; an accelerator for accelerating the parent ions; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; a mass analyzer following at least said ion accelerator including a deflection field for angularly dispersing sample ions; and a detector system responsive to ion intensity and the deflection field strength required to produce a particular angular dispersion, and coupled to said bunching device for determining ion flight time.

Claim 35

A combined chromatography and time-resolved mass dispersive mass spectrometry system comprising: a chromatographic column for providing components of a sample as a function of time; a source coupled to the output of said chromatographic column for ionizing the sample components to provide parent ions; an accelerator for accelerating the parent ions; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; a mass analyzer following at least said ion accelerator including a deflection field for angularly dispersing sample ions; and a detector system responsive to ion intensity and the deflection field strength required to produce a particular angular dispersion, and coupled to said bunching device for determining ion flight time.

Claim 36

A combined chromatography and time-resolved mass dispersive mass spectrometry system comprising: a chromatographic column for providing components of a sample as a function of time; a source coupled to the output of said chromatographic column for ionizing the sample components to provide parent ions; an accelerator for accelerating the parent ions; a fragmentation region wherein at least some accelerated parent ions may fragment to produce daughter ions; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; a mass analyzer following said fragmentation region including a deflection field for angularly dispersing the daughter ions and any unfragmented parent ions as a function of ion mass and velocity and of deflection field strength; and a detector system responsive to ion intensity and the deflection field strength required to produce a particular angular dispersion, and coupled to said bunching device for determining ion time-of-flight and thus velocity as an indicator of parent mass of a detected daughter ion, and as an indicator, in combination with determined deflection field strength, of parent and daughter ion mass.

Claim 37

A combined chromatography and time-resolved mass dispersive mass spectrometry system comprising: a chromatographic column for providing components of a sample as a function of time; a source coupled to the output of said chromatographic column for ionizing the sample components to provide parent ions; an accelerator for accelerating the parent ions; a fragmentation region wherein at least some accelerated parent ions may fragment to produce daughter ions; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; a mass analyzer following said fragmentation region including a deflection field for angularly dispersing the daughter ions and any unfragmented parent ions as a function of ion mass and velocity and of deflection field strength; and a detector system responsive to ion intensity and the deflection field strength required to produce a particular angular dispersion, and coupled to said bunching device for determining ion time-of-flight and thus velocity as an indicator of parent mass of a detected daughter ion, and as an indicator, in combination with determined deflection field strength, of parent and daughter ion mass.

Claim 38

A combined chromatography and mass spectrometry system in accordance with claim 33, wherein said chromatographic column comprises a gas chromatographic column.

Claim 39

A combined chromatography and mass spectrometry system in accordance with claim 33, wherein said chromatographic column comprises a liquid chromatographic column.

Claim 40

A combined chromatography and mass spectrometry system in accordance with claim 33, wherein said mass analyzer includes a magnetic field for angularly dispersing ions.

Claim 41

A combined chromatography and mass spectrometry system in accordance with claim 33, wherein said mass analyzer includes a deflection electric field for angularly dispersing ions.

Claim 42

A retrofit kit for converting a magnetic sector mass spectrometer of the general type including an ion source for providing sample ions, and ion accelerator for accelerating the sample ions, a magnetic mass analyzer including a magnetic deflection field for angularly dispersing sample ions as a function of momentum and as a function of magnetic deflection field strength, an ion detector responsive to the ion intensity output of the magnetic sector, and an aperture such that only ions of predetermined angular dispersion enter the detector to a time-resolved mass dispersive mass spectrometer, said retrofit kit comprising: an ion bunching device for bunching ions prior to their entering a drift region in the spectrometer extending downstream of the ion bunching device; and a detector system responsive to ion intensity and the deflection magnetic field strength required to produce a particular angular dispersion and coupled to said bunching device for determining ion flight time.

Claim 43

A retrofit kit for converting a magnetic sector mass spectrometer of the general type including an ion source for providing sample ions, and ion accelerator for accelerating the sample ions, a magnetic mass analyzer including a magnetic deflection field for angularly dispersing sample ions as a function of momentum and as a function of magnetic deflection field strength, an ion detector responsive to the ion intensity output of the magnetic sector, and an aperture such that only ions of predetermined angular dispersion enter the detector to a time-resolved mass dispersive mass spectrometer, said retrofit kit comprising: an ion bunching device for bunching ions prior to their entering a drift region in the spectrometer extending downstream of the ion bunching device; and a detector system responsive to ion intensity and the deflection magnetic field strength required to produce a particular angular dispersion and coupled to said bunching device for determining ion flight time.

Claim 44

A time-resolved multi-sector mass dispersive mass spectrometer comprising: a source for providing sample ions an accelerator for accelerating the sample ions; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; first and second mass analyzers in tandem following at least said ion accelerator, each of said mass analyzers including a deflection field for angularly dispersing ions; an aperture between said mass analyzers such that only ions exiting said first mass analyzer with substantially a predetermined angular dispersion enter said second mass analyzer; and a detector system responsive to ion intensity and the deflection field strength required to produce a particular angular dispersion, and coupled to said bunching device for determining flight time.

Claim 45

A time-resolved multi-sector mass dispersive mass spectrometer comprising: a source for providing sample ions an accelerator for accelerating the sample ions; a drift region for time separation included in said mass spectrometer, and an ion bunching device upstream of at least the drift region; first and second mass analyzers in tandem following at least said ion accelerator, each of said mass analyzers including a deflection field for angularly dispersing ions; an aperture between said mass analyzers such that only ions exiting said first mass analyzer with substantially a predetermined angular dispersion enter said second mass analyzer; and a detector system responsive to ion intensity and the deflection field strength required to produce a particular angular dispersion, and coupled to said bunching device for determining flight time.

Claim 46

A mass spectrometer in accordance with claim 39, wherein said first mass analyzer comprises an electric sector and said second mass analyzer comprises a magnetic sector.

Claim 47

A mass spectrometer in accordance with claim 39, wherein said first mass analyzer comprises a magnetic sector and said second mass analyzer comprises an electric sector.

Claim 48

A mass spectrometer in accordance with claim 39, which comprises a fragmentation region prior to said first mass analyzer.

Claim 49

A mass spectrometer in accordance with claim 39, which comprises a fragmentation region between said first and second mass analyzers.

Claim 50

A mass spectrometer in accordance with claim 39, which comprises a first fragmentation region prior to said first mass analyzer and a second fragmentation region between said first and second mass analyzers.

Claim 51

A mass spectrometry method for determining relationships between selected parent ions and daughter ions produced by fragmentation, said method comprising the steps of: ionizing a quantity of sample to produce parent ions; accelerating the parent ions; facilitating fragmentation of at least some accelerated parent ions to produce daughter ions without substantial change in velocity; directing the daughter ions and any unfragmented parent ions through a deflection field for angularly dispersing ions; bunching the ions and allowing ions, at any point subsequent to bunching, to separate along a path of travel, through a drift region in the spectrometer extending downstream of the ion bunching, and effectively separate in time; and detecting ions subsequent to passage through the deflection field and subsequent to separation in time, for determining deflection field strength required to produce a particular angular dispersion, and determining ion time-of-flight through said drift region, and thus velocity as an indicator of parent mass of a detected daughter ion, and as an indicator, in combination with determined deflection field strength, of parent and daughter ion mass.

Claim 52

A mass spectrometry method for determining relationships between selected parent ions and daughter ions produced by fragmentation, said method comprising the steps of: ionizing a quantity of sample to produce parent ions; accelerating the parent ions; facilitating fragmentation of at least some accelerated parent ions to produce daughter ions without substantial change in velocity; directing the daughter ions and any unfragmented parent ions through a deflection field for angularly dispersing ions; bunching the ions and allowing ions, at any point subsequent to bunching, to separate along a path of travel, through a drift region in the spectrometer extending downstream of the ion bunching, and effectively separate in time; and detecting ions subsequent to passage through the deflection field and subsequent to separation in time, for determining deflection field strength required to produce a particular angular dispersion, and determining ion time-of-flight through said drift region, and thus velocity as an indicator of parent mass of a detected daughter ion, and as an indicator, in combination with determined deflection field strength, of parent and daughter ion mass.

Claim 53

A mass spectrometry method in accordance with claim 45, wherein said step of directing ions through a deflection field comprises directing the daughter ions and any unfragmented parent ions through a magnetic field.

Claim 54

A mass spectrometry method in accordance with claim 45, wherein said step of directing ions through a deflection field comprises directing the daughter ions and any unfragmented parent ions through an electric field.

Claim 55

A mass spectrometry method in accordance with claim 45, wherein said step of bunching the ions comprises pulsing an ion source wherein the parent ions are produced.

Claim 56

A mass spectrometry method in accordance with claim 46, which further comprises: allowing only ions of substantially a predetermined angular dispersion to be detected; varying the magnetic field strength in time to provide a magnetic scan; and repetitively pulsing said ion bunching device during each magnetic scan, each pulse corresponding to a particular value of magnetic field strength, such that any ions reaching said detector following a particular pulse have a particular momentum.

Claim 57

A mass spectrometry method in accordance with claim 47, which further comprises: allowing only ions of predetermined angular dispersion to be detected; varying the deflection electric field strength as a function of time to provide a deflection electric scan; and repetitively pulsing said ion bunching device during each deflection electric field scan, each pulse corresponding to a particular value of deflection electric field strength, such that any ions reaching said detector following a particular pulse have a particular kinetic energy.

Claim 58

A mass spectrometer in accordance with claim 1, wherein such accelerator means provides sample ions having substantially equal kinetic energy.

Claim 59

A mass spectrometer in accordance with claim 1, wherein said accelerator means provides sample ions having substantially equal momentum.