JP2005243627A - Mass spectrometer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrospray ionization ion source and an atmospheric pressure chemical ionization ion source including a probe 1 comprising three coaxial capillary tubes 2, 3, 3'. <P>SOLUTION: A blue-flame gas torch 6 is provided downstream of the probe 1 as a combustion source. An analyte solution is sprayed from the inner capillary tube 2 of the probe 1, and combustible gas is supplied to the middle capillary tube 3 of the probe 1. Oxygen or air is supplied to the outer capillary tube 3' of the probe 1. The combustible gas supplies heat to aid desolvation of droplets emerging from the probe 1 via combustion with the surrounding oxygen-containing atmosphere when combusted by the blue-flame torch 6. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ion source and a mass spectrometer having an ion source. The preferred embodiment relates to an electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) ion source, preferably used with a mass spectrometer.

  The combination of electrospray ionization and mass spectrometry is a powerful technique for the analysis of organic compounds. Electrospray ionization involves passing an analyte volatile solvent solution through a capillary tube. The capillary tube is held at a relatively high potential relative to the chamber surrounding the capillary tube and to the ground terminal. A high velocity concentric nitrogen flow is generally provided at the tip of the capillary tube to facilitate the atomization process. The resulting relatively high electric field is transferred to the liquid volume at the tip of the capillary, resulting in partial separation of positive and negative electrolyte ions. For example, when a positive potential is applied to the capillary tube, negative ions are sent or attracted into the capillary wall while positive ions are enriched at the liquid-gas interface. When the combined force of electrostatics and electrohydrodynamics exceeds the liquid surface tension, a droplet with a net positive charge is formed and ejected from the tip of the capillary.

  Heat may be applied to charged droplets that cause further droplet radius reduction at a constant charge. A point is reached where the repulsion of the Coulomb law of charge, known as the Rayleigh limit, exceeds the surface tension. The droplet then undergoes splitting to form smaller charged droplets or microdroplets. The desolvation process continues until ions are liberated into the gas phase by ion evaporation or charge retention processes. Then, at least some of the generated ions are accommodated in a mass spectrometer for subsequent mass analysis.

  In general, electrospray ionization can be efficiently performed with a liquid flow rate of 10 to 1000 nl / min without the need to apply heat near the tip of the capillary. However, in liquid chromatography mass spectrometry (LC / MS) near or above 1 ml / min, the capillary phase is commonly used to improve ionization efficiency and overall system sensitivity due to the mobile phase flow rates commonly encountered. Often there is a need to apply significant heat to the droplets coming out of the. In particular, it is known that the capillary tube is surrounded by a further (second) flow of heated nitrogen gas. The amount of heat required to improve ionization efficiency increases with flow rate and the proportion of water in the ionized liquid.

  It would be desirable to provide an improved ion source.

  In a first main aspect, the present invention provides an ion source including two outflow devices (for example, capillary tubes).

  In an aspect, the present invention provides an ion source that includes a probe including a first effluent device and a second effluent device, and a combustion source disposed downstream of the probe.

  The ion source according to a preferred embodiment provides heat to assist desolvation while assisting droplet formation at the probe tip when combustible gas or vapor is combusted by the combustion source. It is possible to fulfill a dual function.

  It is preferred that at least a part or substantially the whole of the second effluent device surrounds, encloses or confines at least a part or substantially the whole of the first effluent device. The first outflow device and the second outflow device are preferably coaxial or substantially coaxial.

  The first and / or second effluent device preferably includes one or more capillary tubes or other forms of tubes.

  An analyte solution or liquid or flow is preferably supplied to the first effluent device and / or the second effluent device in use. Said analyte solution or liquid or flow is preferably at the time of use: (i) <1 μl / min; (ii) 1-10 μl / min; (iii) 10-50 μl / min; (iv) 50- 100 μl / min; (v) 100-200 μl / min; (vi) 200-300 μl / min; (vii) 300-400 μl / min; (viii) 400-500 μl / min; (ix) 500- 600 μl / min; (x) 600-700 μl / min; (xi) 700-800 μl / min; (xii) 800-900 μl / min; (xiii) 900-1000 μl / min; and (xiv)> The first effluent device and / or the second effluent device is supplied at a flow rate selected from the group consisting of 1000 μl / min.

  The first gas or vapor is preferably supplied to the first effluent device and / or the second effluent device in use. The first gas or vapor preferably assists in the atomization of the analyte solution or liquid or flow. The first gas or vapor is preferably flammable and (i) acetone; (ii) acetylene; (iii) benzene; (iv) butane; (v) butyl alcohol (butanol); (vi ) Diethyl ether; (vii) ethane; (viii) ethyl alcohol (ethanol); (ix) ethylene; (x) ethylene oxide; (xi) hexane; (xii) hydrogen; (xiii) isopropyl alcohol (isopropanol); (xiv) (Xv) methyl alcohol (methanol); (xvi) methyl ethyl ketone; (xvii) n-pentane; (xviii) propane; (xix) propylene; (xx) styrene; (xxi) toluene; (xxii) xylene; (xxiii) ) Carbon monoxide; (xxiv) Saturated hydrocarbon; (xxv) Unsaturated hydrocarbon; (xxvi) Alcohol; (xxvii) Ester; (xxviii) Ether; (xxix) Hydrocarbon; (xxx) Volatile oil; (xxxi) Jet fuel; (xxxii) Naphtha; (xxxiii) Turpentine oil; (xxxiv) Cyclic compound; (xxxv) Ketone; (x xxvi) inorganic gas; (xxxvii) organic gas; (xxxviii) hydrogen sulfide; (xxxix) ammonia; (xxxx) propanol; (xxxxi) ethyl acetate; (xxxxii) heptane; and (xxxxiii) exlene Preferably it is selected from the group.

  However, according to at least another preferred embodiment, the first gas may simply support combustion and thus include air or oxygen.

  The first gas or vapor is preferably, in use, (i) <1 bar; (ii) 1-2 bar; (iii) 2-3 bar; (iv) 3-4 bar; (v) 4 -5 bar; (vi) 5-6 bar; (vii) 6-7 bar; (viii) 7-8 bar; (ix) 8-9 bar; (x) 9-10 bar; and (xi)> 10 bar is supplied to the first and / or second outflow device at a pressure selected from the group consisting of bar.

  Preferably, the first gas or steam promotes or increases the combustion of the second gas or steam. The combustion of the second gas or steam is preferably performed by the combustion source. The first gas or vapor preferably provides heat as it burns to aid in the desolvation of the droplets.

  The combustion source preferably includes a blue flame ignition rod, a gas ignition rod, or a blow lamp.

  The combustion source is preferably arranged for burning the second gas or steam. The second gas or steam is preferably supplied directly to the combustion source. Said second gas or vapor is preferably (i) acetone; (ii) acetylene; (iii) benzene; (iv) butane; (v) butyl alcohol (butanol); (vi) diethyl ether; (vii) Ethane; (viii) Ethyl alcohol (ethanol); (ix) Ethylene; (x) Ethylene oxide; (xi) Hexane; (xii) Hydrogen; (xiii) Isopropyl alcohol (isopropanol); (xiv) Methane; (xv) Methyl alcohol (Methanol); (xvi) methyl ethyl ketone; (xvii) n-pentane; (xviii) propane; (xix) propylene; (xx) styrene; (xxi) toluene; (xxii) xylene; (xxiii) carbon monoxide; (xxiv (Xxv) Unsaturated hydrocarbon; (xxvi) Alcohol; (xxvii) Ester; (xxviii) Ether; (xxix) Hydrocarbon; (xxx) Volatile oil; (xxxi) Jet fuel; (xxxii) Naphtha (xxxiii) Turpentine oil; (xxxiv) Cyclic compound; (xxxv) Ketone; (xxxvi) Inorganic gas; (xxxvii (Xxxviii) hydrogen sulfide; (xxxix) ammonia; (xxxx) propanol; (xxxxi) ethyl acetate; (xxxxii) heptane; and (xxxxiii) exlene. Contains gas or steam.

  Preferably, the probe has a first longitudinal axis, and the combustion source has a second longitudinal axis. The angle between the first anteroposterior axis and the second anteroposterior axis is preferably (i) 0-10 °; (ii) 10-20 °; (iii) 20-30 °; (iv) 30-40 °; (v) 40-50 °; (vi) 50-60 °; (vii) 60-70 °; (viii) 70-80 °; (ix) 80-90 °; (x) 85- 95 °; (xi) 90-100 °; (xii) 100-110 °; (xiii) 110 ° -120 °; (xiv) 120-130 °; (xv) 130-140 °; (xvi) 140-150 (Xvii) 150-160 °; (xviii) 160-170 °; and (xix) 170-180 °.

  Preferably, the ion source further includes an enclosure for enclosing the probe and / or the combustion source. The enclosure preferably includes a gas inlet and a gas outlet. The background gas is preferably introduced into the enclosure through the gas inlet when in use. The background gas preferably supports combustion and therefore preferably contains air or oxygen. The enclosure is preferably, in use, (i) <100 mbar; (ii) 100-500 mbar; (iii) 500-600 mbar; (iv) 600-700 mbar; (v) 700-800 mbar; vi) 800-900 mbar; (vii) 900-1000 mbar; (viii) 1000-1100 mbar; (ix) 1100-1200 mbar; (x) 1200-1300 mbar; (xi) 1300-1400 mbar; (xii) Held at a pressure selected from the group consisting of 1400-1500 mbar; (xiii) 1500-2000 mbar; and (xiv)> 2000 mbar.

  According to a preferred embodiment, the ion source comprises an electrospray ion source. The ion source preferably includes a spray device for spraying the sample and causing droplet formation of the sample. The first effluent device and / or the second effluent device are preferably (i) <± 1 kV; (ii) ± 1-2 kV; (iii) ± 2-3 kV; iv) ± 3-4 kV; (v) ± 4-5 kV; (vi) ± 5-6 kV; (vii) ± 6-7 kV; (viii) ± 7-8 kV; (ix) ± 8- 9 kV; (x) ± 9-10 kV; and (xi)> ± 10 kV or a corresponding potential (preferably against the earth terminal or in an ion block or mass spectrometer) At least preferably relative to each other) relative to the potential at the meter inlet).

  According to another preferred embodiment, the ion source may comprise an atmospheric pressure chemical ionization ion source. The corona discharge device is preferably arranged downstream of the combustion source. The corona discharge device preferably includes a corona pin or a needle. In the mode of operation, preferably (i) <0.1 μA; (ii) 0.1-0.2 μA; (iii) 0.2-0.3 μA; (iv) 0.3-0.4 μA; (v) 0.4-0.5 μA; (vi) 0.5 -0.6 μA; (vii) 0.6-0.7 μA; (viii) 0.7-0.8 μA; (ix) 0.8-0.9 μA; (x) 0.9-1.0 μA; and (xi)> 1 μA An electric current is applied to the corona discharge device.

  In the mode of operation, the voltage is preferably applied to a corona discharge device, or the corona discharge device is (i) <± 1 kV; (ii) ± 1-2 kV; (iii) ± 2-3 kV ; (iv) ± 3-4 kV; (v) ± 4-5 kV; (vi) ± 5-6 kV; (vii) ± 6-7 kV; (viii) ± 7-8 kV; (ix) ± Preferably held at a corresponding potential selected from the group consisting of 8-9 kV; (x) ± 9-10 kV; and (xi)> ± 10 kV (preferably against the ground terminal or ion (For the potential at the entrance of the block or mass spectrometer).

  The first effluent device and / or the second effluent device is, in use, (i) ± 0-100 V; (ii) ± 100-200 V; (iii) ± 200-300 V; (iv) ± 300-400 V; (v) ± 400-500 V; (vi) ± 500-600 V; (vii) ± 600-700 V; (viii) ± 700-800 V; (ix) ± 800-900 V (x) ± 900-1000 V; and (xi)> ± 1000 V may be held at a voltage selected or a corresponding potential (preferably with respect to the ground terminal or ion block or mass). At least preferably with respect to the potential at the entrance of the spectrometer).

  According to at least a preferred embodiment, the ion source comprises: (i) an atmospheric pressure photoionization (APPI) ion source; (ii) a laser desorption ionization (LDI) ion source; (iii) an inductively coupled plasma (ICP) ion source; (iv) Electron impact (EI) ion source; (v) Chemical ionization (CI) ion source; (vi) Field ionization (FI) ion source; (vii) Fast atom bombardment (FAB) ion source; (viii) Liquid 2 Secondary ion mass spectrometry (LSIMS) ion source; (ix) atmospheric pressure ionization (API) ion source; (x) electrolytic desorption (FD) ion source; (xi) matrix-assisted laser desorption ionization (MALDI) ion source; (xii) a silicon surface desorption / ionization (DIOS) ion source; (xiii) a desorption electron spray ionization (DESI) ion source; and (xiv) a nickel-63 radioactive ion source.

  In a further aspect, the present invention provides a mass spectrometer comprising the above ion source.

  It is preferable that the mass spectrometer further includes an ion sampling cone or an ion sampling orifice disposed downstream of the combustion source. The mass spectrometer is such that at least some ions are deflected, attracted, directed, or repelled in use with respect to the ion sampling cone or ion sampling orifice of the mass spectrometer. It may include one or more electrodes disposed opposite or adjacent to the ion sampling cone or the ion sampling orifice.

  According to the preferred embodiment, the ion source is connected to a liquid chromatograph in use. However, according to at least a preferred embodiment, the ion source may be connected to a gas chromatograph in use.

  The mass spectrometer further comprises: (i) an orthogonal acceleration time-of-flight mass analyzer; (ii) an axial acceleration time-of-flight mass analyzer; (iii) a quadrupole mass analyzer; (iv) a Penning mass analyzer; (v) Fourier transform ion cyclotron resonance (FTICR) mass spectrometer; (vi) 2D or linear quadrupole ion trap; (vii) pole or 3D quadrupole ion trap; and (viii) magnetic sector mass spectrometer Preferably, a mass spectrometer selected from the group consisting of:

  In another aspect, the present invention provides an electrospray ionization ion source that includes a probe that includes a first effluent device and a second effluent device, and a combustion source disposed downstream of the probe.

  In another aspect, the present invention provides an atmospheric pressure chemical ionization ion source that includes a probe including a first effluent device and a second effluent device, and a combustion source disposed downstream of the probe.

  In another aspect, the present invention provides an ion source that includes a probe including a first effluent device and a second effluent device, and an ignition source disposed downstream of the probe. However, the combustible gas is supplied to the first outflow device and / or the second outflow device at the time of use.

  Said ignition source preferably comprises a spark gap, a discharge device or an ignition device.

In another aspect, the present invention provides a step of preparing a probe including a first outflow device and a second outflow device,
Supplying a sample to one of the spill devices;
Provided is a method for ionizing a sample, comprising: supplying a first gas or steam to the other outflow device; and combusting the first gas or steam using a combustion source disposed downstream of the probe To do.

  In another aspect, the present invention provides a mass spectral method including the ionization method of the sample.

  In a second main aspect, the present invention provides an ion source that includes three outflow devices (eg, capillary tubes).

  The present invention, in an embodiment, includes a first effluent device, a second effluent device, and a third effluent device, wherein in use, the first gas or vapor is supplied to one of the effluent devices, and further gas Or the vapor provides an ion source that includes a probe fed to another said efflux device.

  The combustion source is preferably arranged downstream of the probe.

  It is preferred that at least a part or substantially the whole of the second effluent device surrounds, encloses or confines at least a part or substantially the whole of the first effluent device. Similarly, at least part or substantially all of the third outflow device surrounds or encloses at least part or substantially all of the second outflow device and / or the first outflow device. It is preferable that it is confined or confined.

  According to a preferred embodiment, the first outflow device and / or the second outflow device and / or the third outflow device are coaxial or substantially coaxial.

  The first outflow device preferably includes one or more capillary tubes or tubes, the second outflow device also preferably includes one or more capillary tubes or tubes, and the third outflow device. The apparatus also preferably includes one or more capillary tubes or tubes.

  According to the preferred embodiment, an analyte solution or liquid or flow is supplied to the first effluent device and / or the second effluent device and / or the third effluent device in use. The analyte solution or liquid or flow is preferably at the time of use: (i) <1 μl / min; (ii) 1-10 μl / min; (iii) 10-50 μl / min; (iv) 50-100 μl / min; (v) 100-200 μl / min; (vi) 200-300 μl / min; (vii) 300-400 μl / min; (viii) 400-500 μl / min; (ix) 500-600 μl / min; (x) 600-700 μl / min; (xi) 700-800 μl / min; (xii) 800-900 μl / min; (xiii) 900-1000 μl / min; and (xiv)> 1000 Supplied at a flow rate selected from the group consisting of μl / min.

  The first gas or vapor is preferably supplied to the first effluent device and / or the second effluent device and / or the third effluent device in use. The first gas or vapor preferably assists in the atomization of the analyte solution or liquid or flow.

  Said first gas or vapor is preferably flammable, (i) acetone; (ii) acetylene; (iii) benzene; (iv) butane; (v) butyl alcohol (butanol); (vi) diethyl Ether; (vii) ethane; (viii) ethyl alcohol (ethanol); (ix) ethylene; (x) ethylene oxide; (xi) hexane; (xii) hydrogen; (xiii) isopropyl alcohol (isopropanol); (xiv) methane; (xv) methyl alcohol (methanol); (xvi) methyl ethyl ketone; (xvii) n-pentane; (xviii) propane; (xix) propylene; (xx) styrene; (xxi) toluene; (xxii) xylene; (xxiii) (Xxiv) saturated hydrocarbon; (xxv) unsaturated hydrocarbon; (xxvi) alcohol; (xxvii) ester; (xxviii) ether; (xxix) hydrocarbon; (xxx) volatile oil; (xxxi) jet fuel (xxxii) Naphtha; (xxxiii) Turpentine oil; (xxxiv) Cyclic compound; (xxxv) Ketone; (xxxvi) Inorganic gas; (xxxvii) Organic gas (xxxviii) hydrogen sulfide; (xxxix) ammonia; (xxxx) propanol; (xxxxi) ethyl acetate; (xxxxii) heptane; and (xxxxiii) exlene. It is preferable to include.

  According to another embodiment, the first gas supports combustion and therefore preferably comprises air or oxygen.

  The first gas or vapor is preferably in use when in use: (i) <1 bar; (ii) 1-2 bar; (iii) 2-3 bar; (iv) 3-4 bar; (v) 4 -5 bar; (vi) 5-6 bar; (vii) 6-7 bar; (viii) 7-8 bar; (ix) 8-9 bar; (x) 9-10 bar; and (xi)> 10 supplied to the first efflux device and / or the second efflux device and / or the third efflux device at a pressure selected from the group consisting of bar.

  Preferably, the first gas or steam promotes combustion of the second gas or steam by the combustion source. The first gas or vapor preferably provides heat as it burns to aid in the desolvation of the droplets.

  Additional gas or vapor is preferably supplied to the first effluent device and / or the second effluent device and / or the third effluent device in use.

  Said further gas or vapor may at least preferably assist in the atomization of the analyte solution or liquid or flow. Said further gas or vapor may be at least preferably flammable, (i) acetone; (ii) acetylene; (iii) benzene; (iv) butane; (v) butyl alcohol (butanol); (vi) (Vii) ethane; (viii) ethyl alcohol (ethanol); (ix) ethylene; (x) ethylene oxide; (xi) hexane; (xii) hydrogen; (xiii) isopropyl alcohol (isopropanol); (xiv) methane (xv) methyl alcohol (methanol); (xvi) methyl ethyl ketone; (xvii) n-pentane; (xviii) propane; (xix) propylene; (xx) styrene; (xxi) toluene; (xxii) xylene; (xxiii) (Xxiv) saturated hydrocarbons; (xxv) unsaturated hydrocarbons; (xxvi) alcohols; (xxvii) esters; (xxviii) ethers; (xxix) hydrocarbons; (xxx) volatile oils; (xxxi) jets Fuel; (xxxii) Naphtha; (xxxiii) Turpentine oil; (xxxiv) Cyclic compound; (xx xv) ketones; (xxxvi) inorganic gases; (xxxvii) organic gases; (xxxviii) hydrogen sulfide; (xxxix) ammonia; (xxxx) propanol; (xxxxi) ethyl acetate; (xxxxii) heptane; and (xxxxiii) excelen One or more gases or vapors selected from the group consisting of (exlene) may be included.

  More preferably, however, the additional gas supports combustion and thus includes air or oxygen.

  Said further gas or vapor is preferably, in use, (i) <1 bar; (ii) 1-2 bar; (iii) 2-3 bar; (iv) 3-4 bar; (v) 4-5 (vi) 5-6 bar; (vii) 6-7 bar; (viii) 7-8 bar; (ix) 8-9 bar; (x) 9-10 bar; and (xi)> 10 bar A pressure selected from the group is supplied to the first outflow device and / or the second outflow device and / or the third outflow device.

  The additional gas or steam preferably promotes the combustion of the second gas or steam by the combustion source in use. The additional gas or vapor may at least preferably provide heat as it burns to aid in the desolvation of the droplets.

  Preferably, the ion source further includes a combustion source selected from the group consisting of (i) a blue flame ignition rod, (ii) a gas ignition rod, and (iii) a blow lamp. The combustion source is preferably arranged for directly burning the second gas or steam.

  The combustion source may be directly supplied with the second gas or steam. Said second gas or vapor is preferably flammable and is (i) acetone; (ii) acetylene; (iii) benzene; (iv) butane; (v) butyl alcohol (butanol); (vi) diethyl Ether; (vii) ethane; (viii) ethyl alcohol (ethanol); (ix) ethylene; (x) ethylene oxide; (xi) hexane; (xii) hydrogen; (xiii) isopropyl alcohol (isopropanol); (xiv) methane; (xv) methyl alcohol (methanol); (xvi) methyl ethyl ketone; (xvii) n-pentane; (xviii) propane; (xix) propylene; (xx) styrene; (xxi) toluene; (xxii) xylene; (xxiii) (Xxiv) saturated hydrocarbon; (xxv) unsaturated hydrocarbon; (xxvi) alcohol; (xxvii) ester; (xxviii) ether; (xxix) hydrocarbon; (xxx) volatile oil; (xxxi) jet fuel (xxxii) Naphtha; (xxxiii) Turpentine oil; (xxxiv) Cyclic compound; (xxxv) Ketone; (xxxvi) Inorganic Selected from the group consisting of: (xxxvii) organic gases; (xxxviii) hydrogen sulfide; (xxxix) ammonia; (xxxx) propanol; (xxxxi) ethyl acetate; (xxxxii) heptane; and (xxxxiii) exlene One or more gases or vapors may be included.

  The probe preferably has a first longitudinal axis, and the combustion source preferably has a second longitudinal axis. The angle between the first longitudinal axis and the second longitudinal axis is: (i) 0-10 °; (ii) 10-20 °; (iii) 20-30 °; (iv) 30-40 °; (v) 40-50 °; (vi) 50-60 °; (vii) 60-70 °; (viii) 70-80 °; (ix) 80-90 °; (x) 85-95 °; (xi) 90-100 °; (xii) 100-110 °; (xiii) 110 ° -120 °; (xiv) 120-130 °; (xv) 130-140 °; (xvi) 140-150 °; ( xvii) 150-160 °; (xviii) 160-170 °; and (xix) 170-180 °.

  Preferably, the ion source further includes an enclosure for enclosing the probe and / or combustion source. The enclosure preferably includes a gas inlet and a gas outlet. Background gas is preferably introduced into the enclosure via the gas inlet when in use. The background gas preferably supports combustion, and thus the background gas preferably includes air or oxygen.

  The enclosure is preferably, in use, (i) <100 mbar; (ii) 100-500 mbar; (iii) 500-600 mbar; (iv) 600-700 mbar; (v) 700-800 mbar; ( vi) 800-900 mbar; (vii) 900-1000 mbar; (viii) 1000-1100 mbar; (ix) 1100-1200 mbar; (x) 1200-1300 mbar; (xi) 1300-1400 mbar; (xii) Held at a pressure selected from the group consisting of 1400-1500 mbar; (xiii) 1500-2000 mbar; and (xiv)> 2000 mbar.

  According to an embodiment, the ion source comprises an electrospray ion source. The ion source preferably includes a spray device for spraying the sample and for causing droplet formation of the sample. The first efflux device and / or the second efflux device and / or the third efflux device are preferably (i) <± 1 kV; (ii) ± 1-2 kV; iii) ± 2-3 kV; (iv) ± 3-4 kV; (v) ± 4-5 kV; (vi) ± 5-6 kV; (vii) ± 6-7 kV; (viii) ± 7- 8 kV; (ix) ± 8-9 kV; (x) ± 9-10 kV; and (xi)> ± 10 kV or a corresponding potential (preferably with respect to the ground terminal or At least preferably with respect to the potential at the entrance of the ion block or mass spectrometer).

  According to another preferred embodiment, the ion source may comprise an atmospheric pressure chemical ionization ion source. The ion source preferably includes a corona discharge device disposed downstream of the combustion source. The corona discharge device preferably includes a corona pin or a needle. In the mode of operation, preferably (i) <0.1 μA; (ii) 0.1-0.2 μA; (iii) 0.2-0.3 μA; (iv) 0.3-0.4 μA; (v) 0.4-0.5 μA; (vi) 0.5 -0.6 μA; (vii) 0.6-0.7 μA; (viii) 0.7-0.8 μA; (ix) 0.8-0.9 μA; (x) 0.9-1.0 μA; and (xi)> 1 μA An electric current is applied to the corona discharge device.

  In the mode of operation, the voltage is preferably applied to a corona discharge device, or the corona discharge device is (i) <± 1 kV; (ii) ± 1-2 kV; (iii) ± 2-3 kV ; (iv) ± 3-4 kV; (v) ± 4-5 kV; (vi) ± 5-6 kV; (vii) ± 6-7 kV; (viii) ± 7-8 kV; (ix) ± It is preferably held at a corresponding potential selected from the group consisting of 8-9 kV; (x) ± 9-10 kV; and (xi)> ± 10 kV (preferably with respect to the earth terminal or ion (For the electric potential at the entrance of the block or mass spectrometer).

  The first efflux device and / or the second efflux device and / or the third efflux device are preferably (i) ± 0-100 V; (ii) ± 100-200 V; (iii) ± 200-300 V; (iv) ± 300-400 V; (v) ± 400-500 V; (vi) ± 500-600 V; (vii) ± 600-700 V; (viii) ± 700 -800 V; (ix) ± 800-900 V; (x) ± 900-1000 V; and (xi)> ± 1000 V or a corresponding potential (preferably At least preferably with respect to the earth terminal or with respect to the potential at the entrance of the ion block or mass spectrometer).

  According to at least a preferred embodiment, the ion source comprises: (i) an atmospheric pressure photoionization (APPI) ion source; (ii) a laser desorption ionization (LDI) ion source; (iii) an inductively coupled plasma (ICP) ion source; (iv) Electron impact (EI) ion source; (v) Chemical ionization (CI) ion source; (vi) Field ionization (FI) ion source; (vii) Fast atom bombardment (FAB) ion source; (viii) Liquid 2 Secondary ion mass spectrometry (LSIMS) ion source; (ix) atmospheric pressure ionization (API) ion source; (x) electrolytic desorption (FD) ion source; (xi) matrix-assisted laser desorption ionization (MALDI) ion source; (xii) a silicon surface desorption / ionization (DIOS) ion source; (xiii) a desorption electron spray ionization (DESI) ion source; and (xiv) a nickel-63 radioactive ion source.

  The present invention, in an aspect, provides a mass spectrometer comprising the above ion source.

  It is preferable that the mass spectrometer further includes an ion sampling cone or an ion sampling orifice disposed downstream of the combustion source.

  The mass spectrometer is preferably configured such that at least some ions are deflected, attracted, directed or repelled with respect to the ion sampling cone or the ion sampling orifice of the mass spectrometer. It includes one or more electrodes disposed opposite or adjacent to the ion sampling cone or the ion sampling orifice.

  The ion source is preferably connected to a liquid chromatograph in use. However, according to at least a preferred embodiment, the ion source may be connected to a gas chromatograph in use.

  The mass spectrometer further comprises: (i) an orthogonal acceleration time-of-flight mass analyzer; (ii) an axial acceleration time-of-flight mass analyzer; (iii) a quadrupole mass analyzer; (iv) a Penning mass analyzer; (v) Fourier transform ion cyclotron resonance (FTICR) mass spectrometer; (vi) 2D or linear quadrupole ion trap; (vii) pole or 3D quadrupole ion trap; and (viii) magnetic sector mass spectrometer Preferably, a mass spectrometer selected from the group consisting of:

  The present invention, in an embodiment, includes a first effluent device, a second effluent device, and a third effluent device, wherein in use, the first gas or vapor is supplied to one of the effluent devices, and further gas Or the vapor provides an electrospray ionization ion source that includes a probe fed to another said effluent device.

  The present invention, in an embodiment, includes a first effluent device, a second effluent device, and a third effluent device, wherein in use, the first gas or vapor is supplied to one of the effluent devices, and further gas Or the vapor provides an atmospheric pressure chemical ionization ion source that includes a probe fed to another said effluent device.

  The present invention, in an embodiment, includes a first effluent device, a second effluent device, and a third effluent device, wherein in use, the first gas or vapor is supplied to one of the effluent devices, and further gas Or the vapor provides an ion source that includes a probe fed to another said effluent device and an ignition source located downstream of said probe.

  The ignition source is preferably selected from the group consisting of (i) a spark gap, (ii) a discharge device, and (iii) an ignition device.

The present invention provides, in an aspect, a step of preparing a probe including a first outflow device, a second outflow device, and a third outflow device;
A method for ionizing a sample is provided, comprising: supplying a first gas or vapor to one of the effluent devices; and supplying another gas or vapor to another effluent device.

  The present invention, in an aspect, provides a mass spectral method including a sample ionization method as described above.

  Various embodiments of the present invention, provided for purposes of illustration along with other arrangements, are now described by way of example only with reference to the accompanying drawings.

Figure 1 shows a conventional electrospray ion source,
FIG. 2 shows a temperature profile as a function of axial distance from the probe tip of a conventional electrospray ion source and ion source according to a preferred embodiment;
FIG. 3 shows a preferred electrospray ion source having two capillary tubes,
FIG. 4A shows the mass spectrum obtained using a conventional ion source, FIG. 4B shows the mass spectrum obtained using a preferred electrospray ion source including a combustion source, and FIG. 4C shows the mass spectrum shown in FIG. Shows a control mass spectrum (using non-combustible nitrogen gas) obtained using an ion source as shown
FIG. 5 shows an electrospray ion source according to another embodiment having three capillary tubes, and
FIG. 6 illustrates an atmospheric pressure chemical ionization ion source according to a further embodiment.

  A conventional electrospray ionization ion source is shown in FIG. The conventional arrangement includes an electrospray probe 1 that includes an inner capillary tube 2 and an outer capillary tube 3. A first gas stream A of unheated nitrogen is introduced into the outer capillary tube 3 in use to aid the electrospray atomization process. The capillary tubes 2 and 3 are surrounded by a recessed conical heater 4 having an annular outlet. The heater 4 has a single gas inlet and the second nitrogen gas stream B is arranged to enter the heater 4. The nitrogen gas in the heater 4 is heated as it passes through the resistance heater, so that the nitrogen gas in the second nitrogen gas stream B comes out of the annular outlet in a heated state. .

  The first gas stream A of unheated nitrogen serves as a high-speed jet of gas that breaks down the liquid droplets that escape from the inner capillary 2 to the nebulizer. That is, the purpose of the first gas stream A is to assist nebulization. The second gas flow B is directed to the outlet of the electron spray probe 1, and the temperature of the portion between the electron spray probe 1 and the ion sampling cone 5 disposed downstream of the electron spray probe 1 Has the main purpose of raising the environment. Thus, the main purpose of the heated gas stream B is to aid the desolvation of the droplets and subsequent ion formation.

  For the purpose of forming a very fine spray or mist of micro-droplets, the droplets should ideally be separated due to Coulomb repulsion where the charged droplet exceeds the surface tension of the droplet. Should be made as small as possible.

  FIG. 2 shows a typical temperature profile along the axis from the tip of the electron spray probe 1 of a conventional ion source as shown in FIG. To discuss in more detail with respect to FIG. 3, the temperature profile with a preferred ion source is also shown in FIG. The distance X shown in FIG. 2 is a displacement measurement from the tip of the electrospray probe 1 shown in FIG. The temperature data of the conventional ion source shows that there is no liquid flow, the first nitrogen spray flow rate A supplied to the outer capillary 3 of 100 l / hr, and the second nitrogen desolvation of 500 l / hr Obtained by the function of a conventional electrospray probe with a sum flow velocity B. The second nitrogen stream B was arranged for heating at 500 ° C. and was therefore supplied via a heater 4 that sufficiently heats the second nitrogen stream B.

  It is clear from FIG. 2 that the rapid decrease in temperature displacement is proportional to the distance from the probe tip 1 (or more precisely from the heating source 4). As is well known to those skilled in the art, due to many limitations of mechanical and high pressure designs, it is practically impossible to attach the heater 4 closer to the electrospray probe 1 .

  When a relatively high liquid flow rate is used in a conventional electrospray probe 1 such as the electrospray ion source shown in FIG. 1, it is disadvantageous, especially when the ionized sample has a relatively high water content. It is considered that the desolvated ions exist substantially only around the outer periphery of the spray emitted from the electron spray probe 1. Under such circumstances, the center of the spray is believed to remain substantially unsolvated. Although the heating and desolvation steps are relatively effective around the perimeter of the discharged spray, it may be less effective for the center of the spray.

  A schematic diagram of an ion source according to a preferred embodiment is shown in FIG. 3 and discussed herein. Preferred embodiments include a combustion assisted electrospray ionization (ESI) interface or ion source. The interface or ion source is preferably coupled to a mass spectrometer in use. A preferred interface or ion source preferably has an electrospray probe 1. The electrospray probe 1 preferably includes an inner stainless steel capillary tube 2 and an outer stainless steel capillary tube 3. According to at least another preferred embodiment, the inner capillary tube 2 and / or the outer capillary tube 3 may be made of other substances. The inner capillary 2 is preferably approximately 200 mm long and has an inner diameter of 130 μm and an outer diameter of 230 μm. Said outer capillary 3 is preferably approximately 30 mm long and has an inner diameter of 330 μm and an outer diameter of 630 μm.

  The blue flame gas igniter 6 is preferably arranged downstream of the outlet of the electrospray probe 1 or otherwise provided. The inlet to the ion sampling cone 5 or another mass spectrometer body is preferably located downstream of the blue flame gas igniter 6.

  The electron spray probe 1, the blue flame gas ignition rod 6 and the ion sampling cone 5 are preferably enclosed in an enclosure 8 or at least partially enclosed. The ion sampling cone 5 preferably includes an ion sampling orifice 11. The enclosure 8 preferably includes a gas inlet 9 and a gas outlet 10. The gas outlet 10 preferably facilitates undesired gas exiting to a suitable extractor system.

  The bore of the capillary tube 2 inside the probe 1 preferably serves as a conduit for the analyte solution, while the bore of the outer capillary tube 3 preferably serves as a spray / combustion gas or vapor conduit.

  An important feature of the preferred embodiment is the measure of the more direct heating method of the droplets ejected from or exiting the electrospray probe 1. The preferred ion source exhibits a significantly enhanced or another improved desolvation process. This can be achieved by providing a gas combustion source between the outlet of the electrospray probe tip 1 and the ion sampling cone 5.

  According to a preferred embodiment, a spray and combustible gas, such as methane, assists in droplet formation at the tip of the probe 1 and, when burned by the blue flame igniter 6, undergoes combustion and ambient In order to serve the two purposes of supplying heat to the oxygen-containing air, it may be supplied or provided to the outer capillary 3. The reaction of methane with oxygen has an exotherm of 802 kJ / mole, and complete combustion of 100 l / hr of methane is approximately 1 kW for the purpose of increasing the desolvation of the droplets emitted from the electrospray probe 1. Will produce no active power. Assuming an acetonitrile: water ratio of 1: 1 and a flow rate of 1 ml / min in both cases, this can be compared to a power of only about 200 W in a conventional system. Even though the complete combustion of the combustion gas does not need to be inferred due to limited oxygen ingress, the heating has been significantly improved due to the very small probe injection volume and high power density Limited to produce desolvation.

  Referring back to FIG. 2, the temperature profile along the axis of the electrospray probe when using a preferred ion source (as shown in FIG. 3) is shown. The temperature profile for the preferred ion source was obtained when 40 l / hr of methane was fed to the outer capillary tube 3 of the ion source as shown in FIG. The methane gas serves as both atomizing and atmospheric combustion gas.

  As judged from FIG. 3, for example, the combustion of the gas supplied to the outer capillary 3 such as methane is caused by, for example, a blue flame butane gas ignition rod 6 intersecting the methane injection adjacent to the probe tip. May be started and sustained. Comparison of the temperature profiles as shown in FIG. 2 demonstrates the effectiveness of the heating method according to the preferred embodiment, with gas temperatures above 300 ° C. near the ion sampling cone 5, ie, 10 downstream of the probe tip. It shows what can be achieved at -15mm. The ion sampling cone 5 that forms the entrance of the mass spectrometer 12 is preferably made of stainless steel, and preferably has an orifice 11 with a diameter of 0.3-0.5 mm. Some ions emitted from the electrospray probe 1 preferably pass through the orifice 11 of the ion sampling cone 5 towards the first low pressure stage of the mass spectrometer 12.

  The axes of the electrospray probe 1 and the ion sampling cone 5 are preferably located approximately or substantially in the same geometric plane and / or intersect at a generally or substantially 90 ° angle. Is preferred. However, according to at least other preferred embodiments, the axes of the electrospray probe 1 and the ion sampling cone 5 may be located in different planes and / or intersect at an angle of 90 ° or less.

  The direction of the blue flame gas igniter 6 is such that its axis is located in a geometric plane generally or substantially the same as the axis of the electrospray probe 1 and / or the axis of the sampling cone 5. preferable. The axis of the blue flame gas igniter 6 is also substantially or generally at a position downstream of the probe tip, and preferably at a position upstream of the ion sampling cone orifice 11 and ion sampling cone 5. It is preferred to generally or substantially intersect the axis of the spray probe 1. The orthogonality between the axes of the electrospray probe 1 and the gas ignition rod 6 is preferred but not essential. According to at least another preferred embodiment, the gas ignition rod 6 rotates around a rotation axis point formed, for example, by intersecting the axis of the electrospray probe 1 and the axis of the gas ignition rod 6. Also good. It is preferable that at least a part of the blue flame portion 13 of the gas ignition rod 6 intersects with the gas injection dispersion discharged from the tip of the electron spray probe.

Various geometric parameters may vary depending on experimental conditions such as liquid flow rate and gas flow rate. For example, as shown in FIG. 3, the distance Y ₁ from the tip of the main part of the blue flame gas ignition rod 6 to the axis of the electrospray probe ₁ is preferably 10-50 mm, more preferably 25 mm. Distance Y ₂ from the electronic spray probe 1 axial to the inlet of the ion sampling cone 5 or ion sampling cone orifice 11 is preferably 0-10Mm, more preferably from 3 mm. Distance X ₁ to the axis of the blue flame torches 6 from the outlet of the electrospray probe 1 is preferably 0-30Mm, more preferably from 4 mm. Distance X ₂ from the outlet of the electrospray probe 1 to the axis of the ion sampling cone 5 is preferably 5-30Mm, more preferably from 12 mm.

  In operation, the analyte-containing solution is preferably fed through the inner capillary 2 via or using the solvent transport system 14 at a flow rate in the range of 1-1000 μl / min. In cation analysis, a voltage of +3 kV is preferably applied to the inner capillary 2 via the high voltage power supply 15, i.e. the inner capillary is preferably to the ground terminal or to the ion It is held at a potential of +3 kV with respect to the potential at the entrance of the block or mass spectrometer. A combustible gas such as methane is preferably supplied through the outer capillary 3 via the pressurized gas cylinder 16 and the pressure regulator 17. The gas flow rate is preferably determined by the regulator pressure adjusted between 3-7 bar. If the gas supplied to the outer capillary 3 is purely combustible gas, oxygen may be further supplied to the system via the gas inlet 9 of the enclosure 8. The oxygen supplied via the gas inlet 9 may be supplied at ambient atmospheric pressure, either as air, as produced air or as pressure gas containing oxygen. The enclosure volume 8 preferably remains substantially or generally at atmospheric pressure.

  According to other embodiments, gases other than pure gas may be used as atomization and combustion gases. The atomization and combustion gas is preferably supplied to the outside of the capillary 3 via the pressure regulator 17. For example, in addition to the combustion support gas (ie, oxygen), a combustible gas-containing mixture may be used. Preferred combustible gases include saturated hydrocarbons such as methane, hydrogen, carbon monoxide, butane and unsaturated hydrocarbons such as ethylene and acetylene. However, at least other preferred gases or vapors may be used.

  Electrosprayed droplets emerging from the probe tip generally generally move slightly or substantially along the probe axis towards the ion sampling cone 5. At this time, it is preferable that the droplets obtain sufficient heat when they reach the range of the axis of the blue flame gas ignition rod 6 that intersects the axis of the electron spray probe 1. The heat is supplied to facilitate further desolvation of the droplets. Further downstream desolvation continues as a result of further combustion in the region of the gas injection where oxygen ingress is sufficient. Preferably, at least some of the gas phase ions or microdroplets exiting downstream of the blue flame ignition rod 6 enter the ion sampling cone 5 of the mass spectrometer via the ion sampling cone orifice 11. The ions are immediately subjected to mass analysis by the mass spectrometer 12.

  The combustion assisted electrospray ionization ion source method according to a preferred embodiment of the present invention was implemented using a number of different organic analytes including reserpine, gramicidin-S, raffinose and verapamil. Electrospray ionization of these analytes using a conventional electrospray ionization ion source has shown that reserpine exhibits a strong dependence on the heating of the droplets, ie, a high desolvation temperature that results in high ionic strength. Consistent with this, reserpine has been found to most benefit from the strong heating and accelerated desolvation associated with the combustion-assisted electrospray ionization ion source according to the preferred embodiment.

  FIGS. 4A, 4B and 4C show optimized mass spectral ions observed using a conventional electrospray ionization ion source and a combustion-assisted electrospray ionization ion source according to the preferred embodiment as shown in FIG. Intensity comparison is shown. Data was obtained by injecting 330 pg / μl reserpine solution with a flow rate of 30 μl / min and a acetonitrile: water ratio of 1: 1. Mass spectra over the range of 606.5-611.5 were recorded due to the almost concentrated molecular ion (MH +) with a mass / charge ratio of 609.3 Da. All mass spectra were obtained by operation of the mass spectrometer 12 in the MS operating configuration. Although the mass spectrometer 12 includes a 3D quadrupole mass spectrometer, the mass spectrometer is preferably not limited to such a design. The intensity scale (obtained by the detector) is the same for all three mass spectra shown in FIGS. 4A-4C.

FIG. 4A shows the optimized ion signal obtained using a conventional electrospray ionization ion source as shown in FIG. In the ion source, a non-heated nitrogen first flow A with a flow rate of 100 l / hr is supplied to the outer capillary 3 of the probe 1 to atomize the liquid emerging from the inner capillary tube 2. The A heater 4 held at a temperature of 500 ^° C. was used to heat the second flow B of nitrogen gas. The second stream B of nitrogen gas had a flow rate of 800 l / hr and was first provided to support desolvation.

FIG. 4B shows a combustion assisted electrospray ionization ion source that uses pure methane as the nebulization and combustible gas supplied to the outer capillary 3 of the ion source as shown in FIG. 3 according to the preferred embodiment. The optimized ion signal obtained using is shown. The pure methane was supplied at a flow rate of 40 l / hr. An outside air inlet 9 and a blue flame butane ignition rod 6 were used. Comparison of the ¹³ C isotope of the data shown in FIG. 4A with the data shown in FIG. 4B despite the saturation of the ion signal as shown in FIG. It was shown that the ion source provided at least a 4-fold improvement in the reserpine ion signal intensity. Thus, it is clear that the preferred ion source shows a significant improvement over conventional ion sources.

  FIG. 4C shows the ion signal obtained using a combustion assisted electrospray ionization ion source as shown in FIG. 3 for control purposes. However, in the ion source, an incombustible nitrogen gas was used as the atomizing gas supplied to the outer capillary 3. The ion signal shown in FIG. 4C shows an approximately 100-fold decrease in the ion signal compared to using methane gas as the nebulization and combustion gas according to the preferred embodiment.

  The raffinose results (data not shown) show that combustion-assisted electrospray ionization according to the preferred embodiment, using pure methane as the atomization and combustion gas, is equally effective in the anionic form. Indicated. Thus, the significant increase in ionic strength when using the ion source according to the preferred embodiment is not simply due to cation gas phase chemical ionization of the analyte in methane reagent ions, but precisely to the preferred This is due to the atomization of droplets coming out from the electronic spray probe 1 according to the embodiment and the promotion of heating. It is also important to note that for many test analytes no thermal degradation was observed.

  A further advantage of the electrospray ionization ion source according to the preferred embodiment is that the combustion-assisted electrospray ionization ion source according to the preferred embodiment has a sufficiently low overall flow rate compared to a conventional electrospray ionization ion source. It is possible to use typical gas. In the example with respect to FIGS. 4A and 4B, the overall gas flow of the conventional electrospray ionization ion source is 900 l / hr, whereas the overall combustion-assisted electrospray ionization ion source according to the preferred embodiment is The gas flow was only 40 l / hr. Thus, the preferred ion source not only allows a significant increase in ionic strength by a factor of 4, but also allows a significant decrease in the overall gas flow rate by approximately 20 times. Thus, the preferred embodiment also makes it possible to achieve a significant reduction in operating costs. Thus, the ion source according to the preferred embodiment represents a significant advancement in technology.

  The improvement of the dual capillary of the embodiment shown and described with respect to FIG. 3 will now be discussed with reference to FIG. FIG. 5 shows a triaxial capillary system with an inner capillary 2, an intermediate capillary 3, and an outer capillary 3 ′. The inner capillary 2 and / or the intermediate capillary 3 and / or the outer capillary 3 ′ are preferably concentric or substantially coaxial. The inner capillary 2 preferably carries or supplies an analyte solution. According to an embodiment, the intermediate capillary 3 preferably carries or supplies a combustible gas or gas mixture, while the outer capillary 3 ′ carries a flow of air, oxygen or an oxygen-containing mixture. Or supply. However, according to other embodiments, the intermediate capillary 3 may carry or supply a flow of air, oxygen or an oxygen-containing mixture, and the outer capillary 3 ′ may contain a combustible gas or gas mixture. You may carry or supply.

  A further embodiment for an atmospheric pressure chemical ionization (APCI) ion source is shown in FIG. According to this embodiment, the corona discharge device 19 is provided downstream of the blue flame ignition rod 6. The electrons shown and described with respect to FIGS. 3 and 5, wherein the inner capillary 2 was held at a potential of +3 kV with respect to a ground terminal or to an ion block or the entrance of the mass spectrometer 12 In contrast to the spray ionization ion source, the inner capillary 2 of the probe 1 is preferably grounded or held at a relative potential of 0 V with respect to the ion block or the mass spectrometer 12 inlet. (Or at least preferably held at a relatively low potential relative to the ground terminal). According to this embodiment, a combination of the flammable probe gas supplied to the outer capillary 3 and the blue flame ignition rod 6 is used. For example, the combustible gas such as methane is preferably supplied to the outer capillary 3, and is preferably used for pneumatic atomization of the analyte solution supplied to the inner capillary 2. The inner capillary 2 is preferably grounded. And the desolvation of the resulting droplets coming out of the probe 1 is sufficiently promoted by the blue flame ignition rod 6 as in the embodiment shown and described with respect to FIGS. Is preferred. However, ionization is preferably performed first by use of a corona discharge device 19 located downstream of the blue flame ignition rod 6 (at least preferably it may be located upstream of the combustion source 6). . The corona discharge device 19 is preferably located substantially or generally adjacent to or facing the ion sampling cone 5 and the ion sampling cone orifice 11, but according to another embodiment, the corona discharge device 19 may be located upstream or slightly downstream of the inlet 11 of the mass spectrometer 12. Corona discharge can be caused, for example, by applying a relatively high pressure of + 3-5 kV to the ground terminal (or to the potential of the inlet of the ion block or mass spectrometer 12) to the corona discharge device 19. Is preferred. The corona discharge device 19 preferably has a corona needle. The corona needle 19 is preferably supported by an insulating flange 20 and is preferably supplied with high pressure by a high pressure source 15.

  Further non-illustrated embodiments include three capillaries 2, 3, 3 ′ similar to the embodiment shown and described with respect to FIG. 5 instead of the dual capillary system 2, 3 as shown in FIG. The atmospheric pressure chemical ionization ion source. According to this further embodiment, the analyte solution is preferably provided to the inner capillary tube 2 as before. The atomization and combustion gas is preferably supplied to the intermediate capillary 3 and the combustion support gas (ie oxygen) is supplied to the outer capillary 3 ′. Alternatively, the atomization and combustion gas may be supplied to the outer capillary 3 ′, and the combustion support gas (ie oxygen) may be supplied to the intermediate capillary 3.

  Although the invention has been described with reference to preferred embodiments, it is to be understood that various changes in form and detail may be made without departing from the spirit of the invention as set forth in detail in the dependent claims. It will be understood by the contractor.

FIG. 1 shows a conventional electrospray ion source. FIG. 2 shows a temperature profile as a function of axial distance from the probe tip of a conventional electrospray ion source and ion source according to a preferred embodiment. FIG. 3 shows a preferred electrospray ion source having two capillary tubes. FIG. 4A shows a mass spectrum obtained using a conventional ion source, FIG. 4B shows a mass spectrum obtained using a preferred electrospray ion source including a combustion source, and FIG. 2 shows a control mass spectrum obtained using an ion source as shown (using non-combustible nitrogen gas). FIG. 5 shows an electrospray ion source according to another embodiment having three capillary tubes. FIG. 6 shows an atmospheric pressure chemical ionization ion source according to a further embodiment.

Claims (59)

A first outflow device, a second outflow device, and a third outflow device, wherein in use, a first gas or vapor is supplied to one of the outflow devices and a further gas or vapor is supplied to another outflow device An ion source that includes a probe that is fed into the chamber. The ion source of claim 1, further comprising a combustion source disposed downstream of the probe. 2. At least a portion or substantially the entire second effluent device surrounds, encloses or confines at least a portion or substantially the entire first effluent device. Or the ion source of 2. At least a part or substantially the whole of the third outflow device surrounds or encloses at least a part or substantially the whole of the second outflow device and / or the first outflow device; 4. The ion source according to claim 1, 2 or 3, which is confined. An ion source according to any preceding claim, wherein the first efflux device and / or the second efflux device and / or the third efflux device are coaxial or substantially coaxial. The ion source according to any preceding claim, wherein the first effluent device comprises one or more capillary tubes or tubes. An ion source according to any preceding claim, wherein the second effluent device comprises one or more capillary tubes or tubes. The ion source according to any preceding claim, wherein the third effluent device comprises one or more capillary tubes or tubes. An analyte solution or liquid or flow is supplied to the first effluent device and / or the second effluent device and / or the third effluent device, in use, in any of the preceding claims. Ion source. The analyte solution or liquid or flow is in use at (i) <1 μl / min; (ii) 1-10 μl / min; (iii) 10-50 μl / min; (iv) 50-100 μl / min min; (v) 100-200 μl / min; (vi) 200-300 μl / min; (vii) 300-400 μl / min; (viii) 400-500 μl / min; (ix) 500-600 μl / min; (x) 600-700 μl / min; (xi) 700-800 μl / min; (xii) 800-900 μl / min; (xiii) 900-1000 μl / min; and (xiv)> 1000 μl / min 10. The ion source of claim 9, wherein the ion source is supplied at a flow rate selected from the group consisting of min. The first gas or steam according to any of the preceding claims, wherein a first gas or vapor is supplied in use to the first effluent device and / or the second effluent device and / or the third effluent device. Ion source. 12. The ion source of claim 11, wherein the first gas or vapor assists in the atomization of an analyte solution or liquid or flow. 13. The ion source according to claim 11 or 12, wherein the first gas or vapor is flammable. The first gas or vapor is: (i) acetone; (ii) acetylene; (iii) benzene; (iv) butane; (v) butyl alcohol (butanol); (vi) diethyl ether; (vii) ethane; (viii) Ethyl alcohol (ethanol); (ix) Ethylene; (x) Ethylene oxide; (xi) Hexane; (xii) Hydrogen; (xiii) Isopropyl alcohol (isopropanol); (xiv) Methane; (xv) Methyl alcohol (methanol ); (xvi) methyl ethyl ketone; (xvii) n-pentane; (xviii) propane; (xix) propylene; (xx) styrene; (xxi) toluene; (xxii) xylene; (xxiii) carbon monoxide; (xxiv) saturated (Xxv) unsaturated hydrocarbon; (xxvi) alcohol; (xxvii) ester; (xxviii) ether; (xxix) hydrocarbon; (xxx) volatile oil; (xxxi) jet fuel; (xxxii) naphtha; ( xxxiii) Turpentine oil; (xxxiv) Cyclic compound; (xxxv) Ketone; (xxxvi) Inorganic gas; (xxxvii) Organic gas (Xxxviii) hydrogen sulfide; (xxxix) ammonia; (xxxx) propanol; (xxxxi) ethyl acetate; (xxxxii) heptane; and (xxxxiii) exlene The ion source according to claim 11, 12 or 13. 13. The ion source according to claim 11 or 12, wherein the first gas supports combustion. 16. The ion source according to claim 15, wherein the first gas includes air or oxygen. (I) <1 bar; (ii) 1-2 bar; (iii) 2-3 bar; (iv) 3-4 bar; (v) 4-5 bar (vi) 5-6 bar; (vii) 6-7 bar; (viii) 7-8 bar; (ix) 8-9 bar; (x) 9-10 bar; and (xi)> 10 bar The ion source according to any of claims 11 to 16, wherein the ion source is supplied to the first efflux device and / or the second efflux device and / or the third efflux device at a pressure selected from a group. The first gas or vapor provides heat when burning to promote combustion of a second gas or vapor by the combustion source or to assist in desolvation of droplets. The ion source according to any one of 11-17. Ion source according to any of the preceding claims, wherein further gas or vapor is supplied in use to the first effluent device and / or the second effluent device and / or the third effluent device. . 20. The ion source of claim 19, wherein the additional gas or vapor assists in the atomization of the analyte solution or liquid or flow. 21. An ion source according to claim 19 or 20, wherein the further gas or vapor is flammable. The further gas or vapor is (i) acetone; (ii) acetylene; (iii) benzene; (iv) butane; (v) butyl alcohol (butanol); (vi) diethyl ether; (vii) ethane; (viii) Ethyl alcohol (ethanol); (ix) Ethylene; (x) Ethylene oxide; (xi) Hexane; (xii) Hydrogen; (xiii) Isopropyl alcohol (isopropanol); (xiv) Methane; (xv) Methyl alcohol (methanol); ( (xvi) methyl ethyl ketone; (xvii) n-pentane; (xviii) propane; (xix) propylene; (xx) styrene; (xxi) toluene; (xxii) xylene; (xxiii) carbon monoxide; (xxiv) saturated hydrocarbon; (xxv) unsaturated hydrocarbon; (xxvi) alcohol; (xxvii) ester; (xxviii) ether; (xxix) hydrocarbon; (xxx) volatile oil; (xxxi) jet fuel; (xxxii) naphtha; (xxxiii) turpentine oil (xxxiv) cyclic compounds; (xxxv) ketones; (xxxvi) inorganic gases; (xxxvii) organic (Xxxviii) hydrogen sulfide; (xxxix) ammonia; (xxxx) propanol; (xxxxi) ethyl acetate; (xxxxii) heptane; and (xxxxiii) exlene. The ion source according to claim 19, 20 or 21, comprising: 21. An ion source according to claim 19 or 20, wherein the additional gas supports combustion. 24. The ion source of claim 23, wherein the additional gas comprises air or oxygen. Said further gas or vapor is in use (i) <1 bar; (ii) 1-2 bar; (iii) 2-3 bar; (iv) 3-4 bar; (v) 4-5 bar; (vi) 5-6 bar; (vii) 6-7 bar; (viii) 7-8 bar; (ix) 8-9 bar; (x) 9-10 bar; and (xi)> 10 bar 25. The ion source according to any of claims 19-24, wherein the ion source is supplied to the first efflux device and / or the second efflux device and / or the third efflux device at a selected pressure. The additional gas or vapor provides heat as it burns to promote combustion of a second gas or vapor by the combustion source or to assist in desolvation of droplets. The ion source according to any one of 25 The ion source of any preceding claim, wherein the ion source further comprises a combustion source selected from the group consisting of (i) a blue flame ignition rod, (ii) a gas ignition rod, and (iii) a blow lamp. Ion source. An ion source according to any preceding claim, wherein the ion source further comprises a combustion source arranged to burn a second gas or steam. 29. The ion source of claim 28, wherein the combustion source is directly supplied with the second gas or steam. 30. An ion source according to claim 28 or 29, wherein the second gas or vapor is flammable. The second gas or vapor is (i) acetone; (ii) acetylene; (iii) benzene; (iv) butane; (v) butyl alcohol (butanol); (vi) diethyl ether; (vii) ethane; viii) Ethyl alcohol (ethanol); (ix) Ethylene; (x) Ethylene oxide; (xi) Hexane; (xii) Hydrogen; (xiii) Isopropyl alcohol (isopropanol); (xiv) Methane; (xv) Methyl alcohol (methanol) (xvi) methyl ethyl ketone; (xvii) n-pentane; (xviii) propane; (xix) propylene; (xx) styrene; (xxi) toluene; (xxii) xylene; (xxiii) carbon monoxide; (xxiv) saturated carbonization (Xxv) unsaturated hydrocarbon; (xxvi) alcohol; (xxvii) ester; (xxviii) ether; (xxix) hydrocarbon; (xxx) volatile oil; (xxxi) jet fuel; (xxxii) naphtha; (xxxiii) ) Turpentine oil; (xxxiv) Cyclic compound; (xxxv) Ketone; (xxxvi) Inorganic gas; (xxxvii) Organic gas (xxxviii) hydrogen sulfide; (xxxix) ammonia; (xxxx) propanol; (xxxxi) ethyl acetate; (xxxxii) heptane; and (xxxxiii) exlene. 31. An ion source according to claim 28, 29 or 30 comprising. The probe has a first longitudinal axis, the combustion source has a second longitudinal axis, and an angle between the first longitudinal axis and the second longitudinal axis is (i) 0-10 (Ii) 10-20 °; (iii) 20-30 °; (iv) 30-40 °; (v) 40-50 °; (vi) 50-60 °; (vii) 60-70 °; (viii) 70-80 °; (ix) 80-90 °; (x) 85-95 °; (xi) 90-100 °; (xii) 100-110 °; (xiii) 110 ° -120 °; ( xiv) 120-130 °; (xv) 130-140 °; (xvi) 140-150 °; (xvii) 150-160 °; (xviii) 160-170 °; and (xix) 170-180 ° An ion source according to any of the preceding claims, selected from: An ion source according to any preceding claim, further comprising an enclosure for enclosing the probe and a combustion source, the enclosure comprising a gas inlet and a gas outlet. 34. The ion source of claim 33, wherein background gas is introduced into the enclosure via the gas inlet when in use. 35. The ion source of claim 34, wherein the background gas supports combustion. 36. An ion source according to claim 34 or 35, wherein the background gas comprises air or oxygen. (I) <100 mbar; (ii) 100-500 mbar; (iii) 500-600 mbar; (iv) 600-700 mbar; (v) 700-800 mbar; (vi) 800 -900 mbar; (vii) 900-1000 mbar; (viii) 1000-1100 mbar; (ix) 1100-1200 mbar; (x) 1200-1300 mbar; (xi) 1300-1400 mbar; (xii) 1400-1500 37. The ion source according to any of claims 33-36, wherein the ion source is maintained at a pressure selected from the group consisting of: mbar; (xiii) 1500-2000 mbar; and (xiv)> 2000 mbar. An ion source according to any preceding claim, wherein the ion source comprises an electrospray ion source. An ion source according to any of the preceding claims, wherein the ion source comprises a spray device for spraying the sample and causing droplet formation of the sample. In use, the first efflux device and / or the second efflux device and / or the third efflux device are: (i) <± 1 kV; (ii) ± 1-2 kV; (iii) ± 2-3 kV; (iv) ± 3-4 kV; (v) ± 4-5 kV; (vi) ± 5-6 kV; (vii) ± 6-7 kV; (viii) ± 7-8 kV; Ion source according to any of the preceding claims, held at a voltage of (ix) ± 8-9 kV; (x) ± 9-10 kV; and (xi)> ± 10 kV or a corresponding potential . 38. The ion source according to any of claims 1-37, wherein the ion source comprises an atmospheric pressure chemical ionization ion source. 42. The ion source of claim 41, wherein the ion source includes a corona discharge device disposed downstream of the combustion source. 43. The ion source of claim 42, wherein the corona discharge device comprises a corona pin or a needle. (I) <0.1 μA; (ii) 0.1-0.2 μA; (iii) 0.2-0.3 μA; (iv) 0.3-0.4 μA; (v) 0.4-0.5 μA; (vi) 0.5-0.6 μA (vii) 0.6-0.7 μA; (viii) 0.7-0.8 μA; (ix) 0.8-0.9 μA; (x) 0.9-1.0 μA; and (xi)> 1 μA 44. An ion source according to claim 42 or 43, wherein the ion source is applied to the corona discharge device. In operating mode, a voltage is applied to the corona discharge device or the corona discharge device is (i) <± 1 kV; (ii) ± 1-2 kV; (iii) ± 2-3 kV; (iv ) ± 3-4 kV; (v) ± 4-5 kV; (vi) ± 5-6 kV; (vii) ± 6-7 kV; (viii) ± 7-8 kV; (ix) ± 8-9 45. Ion source according to claim 42, 43 or 44, held at a corresponding potential selected from the group consisting of kV; (x) ± 9-10 kV; and (xi)> ± 10 kV. The first effluent device and / or the second effluent device and / or the third effluent device are in use when: (i) ± 0-100 V; (ii) ± 100-200 V; (iii) ± 200-300 V; (iv) ± 300-400 V; (v) ± 400-500 V; (vi) ± 500-600 V; (vii) ± 600-700 V; (viii) ± 700-800 V (ix) ± 800-900 V; (x) ± 900-1000 V; and (xi)> ± 1000 V. Any of the preceding claims held at a voltage selected from the group or corresponding potential An ion source according to the above. The ion source comprises: (i) atmospheric pressure photoionization (APPI) ion source; (ii) laser desorption ionization (LDI) ion source; (iii) inductively coupled plasma (ICP) ion source; (iv) electron impact (EI (V) Chemical ionization (CI) ion source; (vi) Field ionization (FI) ion source; (vii) Fast atom bombardment (FAB) ion source; (viii) Liquid secondary ion mass spectrometry (LSIMS) (Ix) Atmospheric pressure ionization (API) ion source; (x) Electrolytic desorption (FD) ion source; (xi) Matrix-assisted laser desorption ionization (MALDI) ion source; (xii) Silicon surface desorption 38. The ionization (DIOS) ion source; (xiii) a desorption electron spray ionization (DESI) ion source; and (xiv) a nickel-63 radioactive ion source. Mass spectrometer. A mass spectrometer comprising an ion source according to any of the preceding claims. 49. A mass spectrometer according to claim 48, further comprising an ion sampling cone or ion sampling orifice disposed downstream of the combustion source. Further, facing or against the ion sampling cone or the ion sampling orifice such that at least some ions are deflected, attracted, directed or repelled relative to the ion sampling cone or the ion sampling orifice 50. The mass spectrometer of claim 49, comprising one or more electrodes arranged adjacent to each other. 51. A mass spectrometer as claimed in any of claims 48, 49 or 50, wherein the ion source is connected to a liquid chromatograph in use. 51. A mass spectrometer according to any of claims 48, 49 or 50, wherein the ion source is connected to a gas chromatograph in use. In addition, (i) orthogonal acceleration time-of-flight mass spectrometer; (ii) axial acceleration time-of-flight mass spectrometer; (iii) quadrupole mass analyzer; (iv) Penning mass spectrometer; (v) Fourier transform ions Selected from the group consisting of a cyclotron resonance (FTICR) mass spectrometer; (vi) a 2D or linear quadrupole ion trap; (vii) a pole or 3D quadrupole ion trap; and (viii) a magnetic sector mass spectrometer 53. A mass spectrometer according to any of claims 48-52, comprising a mass spectrometer. A first outflow device, a second outflow device, and a third outflow device, wherein in use, a first gas or vapor is supplied to one of the outflow devices and a further gas or vapor is supplied to another outflow device An electrospray ionization ion source including a probe supplied to the device. A first outflow device, a second outflow device, and a third outflow device, wherein in use, a first gas or vapor is supplied to one of the outflow devices and a further gas or vapor is supplied to another outflow device An atmospheric pressure chemical ionization ion source comprising a probe fed into the chamber. A first outflow device, a second outflow device, and a third outflow device, wherein in use, a first gas or vapor is supplied to one of the outflow devices and a further gas or vapor is supplied to another outflow device A probe supplied to, and
An ion source including an ignition source disposed downstream of the probe. 57. The ion source of claim 56, wherein the ignition source is selected from the group consisting of (i) a spark gap, (ii) a discharge device, and (iii) an ignition device. Preparing a probe including a first outflow device, a second outflow device, and a third outflow device;
A sample ionization method comprising the steps of: supplying a first gas or vapor to one of the effluent devices; and supplying another gas or vapor to another effluent device. 59. A mass spectral method comprising the sample ionization method of claim 58.

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