CN1768411A - Atmospheric pressure ion source - Google Patents
Atmospheric pressure ion source Download PDFInfo
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- CN1768411A CN1768411A CN 200480009229 CN200480009229A CN1768411A CN 1768411 A CN1768411 A CN 1768411A CN 200480009229 CN200480009229 CN 200480009229 CN 200480009229 A CN200480009229 A CN 200480009229A CN 1768411 A CN1768411 A CN 1768411A
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Abstract
A non-radioactive atmospheric pressure device for ionization of analytes comprises an atmospheric pressure chamber having an inlet for carrier gas, a first electrode at one end, and a counter-electrode at the other end of the chamber for creating an electrical discharge in the carrier gas thus creating metastable neutral excited-state species. Optionally, a grid is provided to generate electrons or ions by contact with the excited-state species. The carrier gas containing the excited-state species or the electrons generated therefrom is directed at an analyte at atmospheric pressure near ground potential to form analyte ions.
Description
CROSS-REFERENCE TO RELATED PATENT
This patent application discloses the 60/460th, No. 179 disclosed theme of submitting on April 14th, 2003 of temporary patent application, and requires the priority based on 35U.S.C. § 119 (e).
Technical field
The present invention relates to utilize metastable atom and molecule atmospheric ionization of analytes.Metastable atom and molecule (M
*) be the long-life excited-state species.When corona discharge or glow discharge, produce metastable species.The additive method that produces excited-state species comprises the mutual controlled operation of electron collision, photo ionization and high-energy particle and reactant.Bump between excited-state species and the ground state material may cause the ionization of ground state material, and discharges electronics because be called as the process of Peng Ning (Penning) ionization, for example:
M
*+ N-〉N
++ M+e-equation 1
Background technology
Because use such as
63Ni,
241Am and
3Adjustment problem and safety problem and other problems that the radioactive material of H produces are so will seek the on-radiation ion source that is used for such as the analytical instrument of ionic mobility spectroanalysis instrument (mobility spectrometer).(title that please refer to people such as Tuner is the 6th of " Corona Discharge Ion Source for Analytical Instruments " the, the title of 225, No. 623 United States Patent (USP)s and Doring is No. 2002/0185593 U.S. Patent Application Publication of " Ion MobilitySpectrometer with Non-Radioactive Ion Source ".)
Certain existing corona discharge ion source of atmospheric ionization (API) mass spectrometer or ionic mobility spectroanalysis instrument (IMS) or chemical agent monitors (CAM) makes analyte (comprising solvent, air and other pollutants) enter the zone of containing the probe that discharges.Produced several problems like this:
1. in air, exist oxygen or other pollutants to cause electrode to degrade.
2. be difficult to when having pollutant, keep discharge, require high potential or pulse potential.
3. airborne corona discharge causes forming such as NO
2 -, NO
3 -And the material of relevant family ion (cluster ion).These ions can reduce reactant ion sensitivity (C.A.Hill and C.L.P.Thomas, Analyst, 2003,128, pp.55-60), and the NO that produces of the reactant that contains nitro functions that may Interference Detection such as nitro explosive
2 -, NO
3 -, perhaps chloride ion disturbs the situation of the chlorate propellant compound relevant with rocket engine or phosphate interference chemical warfare.
4. thereby make air and analyte enter region of discharge and limited the probability that the character control ion that is used to control chemical background forms chemical property.
People's such as Taylor title be " Corona Discharge Ionization Source " the 5th, 684, people's such as No. 300 United States Patent (USP)s and Turner title be " Corona DischargeIonization Source for Analytical Instruments " the 6th, 225, No. 623 United States Patent (USP) has been described corona discharge ion source, is not used for and will produces the device that separate in zone of discharging and the zone of introducing analyte but have to describe.Also please refer to people's such as Zhao paper " LiquidSample Injection Using Atmospheric Pressure Direct Current GlowDischarge Ionization Source " Anal.Chen., 64, pp.1426-1433,1992.
People's such as Bertrand title be " Metastable Atom Bombardment Source " the 6th, 124, No. 675 U.S. Patent Publications a kind of in mass spectrometer with the pressure work that reduces, the metastable atom source that is used to produce ion.Disclosed equipment requires the pressure that reduces basically, and does not describe the device that metastable atom is used for atmospheric pressure ionization mass spectroscopy instrument or ionic mobility spectroanalysis instrument.
People's such as Tsuchiya title be " Apparatus for Producing Sample Ions " the 4th, 546, No. 253 United States Patent (USP) has been described a kind of method of utilizing metastable atom to be produced ion by the sample of introducing at radiation source (emitter) probe tip in the downstream that is positioned at corona discharge.This specification requirement sample is placed on the highfield radiation source probe or near.Please refer to people's such as Otsuka paper " An Interface for Liquid Chromatograph/LiquidIonization Mass Spectrometer " Analytical Sciences, Vol.4, October1988.The present invention avoids using the high potential radiation source probe in the downstream that is positioned at corona discharge source.In addition, the invention provides a kind of neutral analyte molecule that is used to sample, and do not limit the device of reorientating the analyte in their surfaces thereon, position.For example, cocaine and the war of the chemical/biological in military field surface preparation in can Direct Sampling bank note, and the original place that do not need cleaning, perhaps solvent washing should the surface.When reorientating sample, analyte molecule is all lost (is 30% to 100% for trace-level concentrations) at every turn.Therefore, preferably carry out the direct surface sampling all the time.
Summary of the invention
Put it briefly, according to the present invention, a kind of atmospheric ionization source or interface are provided, comprising: the first normal pressure chamber, have carrying gas access, first electrode and counterelectrode, be used in the carrying gas that produces metastable neutral excited-state species, producing corona discharge or glow discharge; The second normal pressure chamber has the port that is communicated with first Room; And selectable the 3rd normal pressure chamber, have the port that is communicated with second Room, there is the lens electrode of the described port between second Room and the 3rd Room, the 3rd Room has the gas outlet and the selectable electrode that is positioned on this gas outlet of carrying gas.Discharge is limited in first indoor.First electrode is preferably aimed at substantially with port.Power supply is set, with the current potential that on each electrode, keeps respectively selecting.In second Room or the outlet of the 3rd Room, can there be the grid of conduction.Advantageously, the 3rd Room can be the interior slender glass tube of socket that removably inserts second Room.
Atmospheric pressure source or interface can be used to form and be used for the spectroscope of positive ion mode or negative ion mode or the cation or the anion of other instruments.Usually, when analyte contact excited-state species, produce anion and cation simultaneously.Some analyte is electrophilic, therefore, trends towards trapped electrons, to produce electronegative analyte ions, and like this can these analytes of detection and Identification.Other analytes have proton or cation compatibility, therefore, for example, by gather proton [M+H]+, be ionized.The instrument with positive ion mode or negative ion mode is selected in guiding like this.
Power supply preferably makes lens electrode and this electrode be positioned at the gas outlet, with under the situation of not changing first electrode and counterelectrode, and the reverse of polarity.Can between positive ion mode and negative ion mode, select ionization source rapidly like this.Must make first electrode and counterelectrode keep being enough to produce the current potential of discharge.Counterelectrode also is used to filter ionization material.Produce the shape that first required electrode of discharge and the potential difference between the counterelectrode depend on the carrying gas and first electrode, therefore, normally several hectovolts are such as 400 or 1,200 volts.But, for little electronic structure, the electronic structure that for example dull and stereotyped plasma screen TV uses, small voltage is enough.First electrode, for example, probe electrode can have positive potential or negative potential.The common ground connection of counterelectrode, perhaps its polarity is opposite with the polarity of probe electrode.This is with positive ion mode work or with the situation of negative ion mode.Under positive ion mode, lens electrode can be between earth potential and just a few hectovolt, with the anion in the filtering carrying gas.In addition, under negative ion mode, this lens electrode is between earth potential and negative several hectovolts, with the cation in the filtering carrying gas.
According to first embodiment of the invention, near with the charged particle detector of positive ion mode work, for example, and mass spectrometer, ionic mobility spectroanalysis instrument, the perhaps inlet of chemical agent monitors, the equipment that the previous paragraph is described is provided with the outlet of the 3rd Room.With positive ion mode electrode is set.The gas of contain excited-state species, discharging from the gas outlet of the 3rd Room by or be positioned near analyte with the inlet of the detector of negative ion mode.Metastable species and this analyte response in the carrying gas with the formation cation, thereby are analyzed.Analyte molecule generation ion molecule reaction, with form such as [M+H]+material.For example, the form of analyte can be by opening steam, be positioned at lip-deep solid-state form or suck the form of liquid.
According to second embodiment of the invention, above-mentioned equipment is provided with the outlet near the 3rd Room of the inlet that enters the charged particle detector.With negative ion mode electrode is set.The gas of contain excited-state species, discharging from the gas outlet of the 3rd Room by or be positioned near analyte with the inlet of the detector of negative ion mode.Metastable species and this analyte response in the carrying gas with the formation anion, thereby are analyzed.For example, the form of analyte can be by opening steam, be positioned at lip-deep solid-state form or suck the form of liquid.
According to third embodiment of the invention, use above-mentioned equipment with " sniffer " pattern, the outlet of its 3rd Room is near the inlet of charged particle detector.The electrode of outlet can comprise grid, and keeps earth potential or negative potential, perhaps is in the AC current potential that utilizes the direct voltage biasing, so that the reactive material disassociation, thereby assurance is as the electron source collision grid of metastable species.By with gas molecule collision, the electronics of acquisition is arrived heat energy by cooling (cooling) rapidly.With negative ion mode electrode is set.The gas of contain excited-state species, discharging from the gas outlet of the 3rd Room by or be positioned at the normal pressure analyte, and be not positioned at high-intensity magnetic field, but close charged particle detector, for example, one of them is with the mass spectrometer of negative ion mode or the inlet of ionic mobility spectroanalysis instrument.Electronics analyte in the carrying gas is caught, to form the anion by the gas collisions cooling.For example, the form of analyte can be by opening steam, be positioned at lip-deep solid-state form or suck the form of liquid.
Except grid electrode just remains, and gas and analyte formation cation from exporting discharge, thereby outside analyzing under positive ion mode, the 4th embodiment is identical with the 3rd embodiment of " sniffer " pattern.
According to fifth embodiment of the invention, a kind of atmospheric ionization source or interface are provided, it comprises: the first normal pressure chamber, have carrying gas access, electrode and counterelectrode in it, be used in the carrying gas that produces metastable species, ion, electronics, hot atom and molecule and atomic group (radical), producing discharge; The second normal pressure chamber, adjacent with first Room, and have the port that enters first Room, have the selectable inlet and the selectable outlet that are used to cool off reacting gas; And the 3rd normal pressure chamber, adjacent with second Room, and have outlet, this electrode and each port rough alignment of the interaction ionization product of the inlet of the port that enters second Room and carrying gas and metastable species.
According to sixth embodiment of the invention, a kind of atmospheric ionization source or interface are provided, it comprises first Room, has carrying gas access, electrode and counterelectrode in it, is used for producing in the carrying gas that produces metastable species glow discharge or corona discharge; And second Room, adjacent with first Room, and the gas outlet with electronics and/or metastable species, this electrode and each port rough alignment.
Normal pressure in this specification and claims use means near ambient pressure, such as 400 to 1,400 holders.This can comprise the submarine of pressurized aircraft and subduction.For laboratory applications, ambient pressure can be reduced in the scope of 700 to 800 holders.
Before introducing interface, heating carrying gas in the time of perhaps on being positioned at interface is so that be gas phase with analyte vaporization or desorb from the surface.A kind of adjustable adjuster preferably is provided, is used for embedding the electronics in the air-flow and it being quickened, regulate air pressure, to control the speed of ionization electron energy by changing air pressure from carrying.
Description of drawings
According to the detailed description of doing below with reference to accompanying drawing, further feature of the present invention and other purposes and advantage become apparent, and accompanying drawing comprises:
Fig. 1 is according to the schematic diagram that the present invention includes the atmospheric pressure source of aiming at chamber C1, C2 and C3;
Fig. 2 is the schematic diagram of the atmospheric pressure source relevant with mass spectrometer;
Fig. 3 comprises 3 chambers and is used for metastable species is transformed to the atmospheric pressure source of grid of electronics or the schematic diagram of equipment;
Fig. 4 is the schematic diagram that only has the simplification normal pressure equipment of two chambers;
Fig. 5 is with the atmospheric pressure interface according to the present invention shown in 2: 1 ratios or the perspective view of equipment;
Fig. 6 is the broken-open perspective view identical with Fig. 5;
Fig. 7 is the detail drawing of perspective view shown in Figure 6;
Fig. 8 is the circuit theory diagrams according to the power supply of normal pressure equipment of the present invention or atmospheric pressure source;
Fig. 9 is the mass spectrum of nitrogen carrying gas that enters the region of discharge of chamber C1 shown in Figure 2;
Figure 10 is that wherein room air is introduced the mass spectrum that the interior nitrogen of chamber C1 shown in Figure 2 carries gas stream;
Figure 11 is that wherein room air is introduced the interior mass spectrum of chamber C3 shown in Figure 2;
Figure 12 is a mass spectrum of introducing the diethylmethylphosphonothiolate in the C3 of chamber;
Figure 13 is a mass spectrum of introducing the phenyl-hexafluoride in the C3 of chamber;
Figure 14 be wherein eliminated background ions, with the similar mass spectrum of mass spectrum shown in Figure 9;
Figure 15 is that wherein air is introduced the interior mass spectrum of chamber C3;
Figure 16 is that wherein nitrobenzene is introduced the interior mass spectrum of chamber C3;
Figure 17 and 18 is respectively the positive ion mass spectrum of nitromethane and nitrobenzene;
Figure 19 is to use the air mass spectrum of interface shown in the schematic diagram of Fig. 3;
Figure 20 is to use the mass spectrum of the phosphoric acid methyl ethyl ester of interface shown in the schematic diagram of Fig. 3;
Figure 21 is to use the mass spectrum of the p diethylaminobenzoic acid methyl esters (DEMP) of interface shown in the schematic diagram of Fig. 3;
Figure 22 is to use the mass spectrum of the DEMP (cation) of interface shown in the schematic diagram of Fig. 3;
Figure 23 is to use the mass spectrum of the TNT (anion) of interface shown in the schematic diagram of Fig. 3; And
Figure 24 (a) is deposited on the board mass spectrum of the TNT on the passage of aviation, and Figure 24 (b) is the mass spectrum of this passage of boarding.Boarding passage when this source, baseline is being produced overgauge.
Embodiment
Fig. 1 utilizes schematic diagram that the general realization of the present invention is shown.For example, this equipment is provided with N it is applied the probe electrode of current potential in the first normal pressure chamber C1, and carrying gas is introduced in this first normal pressure chamber C1 by inlet G1, and flows out from airtight outlet O1.Electrode N can be point, line, surface or crooked electrode.Probe electrode is an example of point electrode, is the example of line electrode and adjust the wing (trim blade).Really, at a plurality of probes or other electrode of the indoor existence of first normal pressure with a kind of polarity, this arrangement is particularly useful to chemical agent monitors.When using a plurality of electrodes (N), can observe the corresponding raising of detection sensitivity.Counterelectrode E0 contains porose, and gas and charged particle can be passed through this hole.Current potential (for example, earth potential) is set, in the middle of electrode N and counterelectrode E0, to produce corona discharge or glow discharge.This electrode can be a negative electrode of setting up negative potential, or sets up the anode of positive potential.In discharge process, form cation, electronics and metastable excited state atom.Supplemantary electrode E1 is positioned at the outlet of the selectable second Room C2, and this second Room C2 has closed gas inlet G2 and closed gas outlet O2.Electrode E1 also determines the inlet of the 3rd Room C3, and final electrode E2 is positioned at the outlet of the 3rd Room C3.
In a current realization, the carrying gas with malleation from cylinder inlet chamber C1.Make metastable excited state atom inlet chamber C2 and C3 like this.In this was realized, the volume of each chamber was about 1 cubic centimetre.The diameter of the aperture between each chamber is about 3mm, and flows through this aperture with a few ml quantity levels of about per minute.
The carrying gas that the applicant uses is helium and nitrogen.P-10 gas (90% argon gas+10% methane) and He/Ne mist are possible carrying gas.In addition, it is also conceivable that argon gas and krypton gas.Really, to be higher than any gas or the mist of the state of analyte all be possible carrying gas to its metastable state.
Corona discharge or glow discharge take place in the C1 of chamber.Between chamber C1 and chamber C3, chamber C2 provides selectable buffering area, and can independent refrigerating gas of selectable introducing or reacting gas.For example, refrigerating gas comprise utilize metastable atom can ionization to produce the gas of cation or electronics.Can this electronics of thermalization by further bump.Carbon dioxide, methane and air are the examples of refrigerating gas.Reacting gas is to utilize ion molecule reaction suitably to distinguish the gas on ion peak.Usually, can be with a small amount of reacting gas, for example, and ammonia (promoting that ammonium ion is adsorbed onto on the cation), the gas that perhaps produces chloride ion (for example, the carrene of anion, chloroform (chloroform) or carbon tetrachloride) adds in the refrigerating gas.Add chloride ion and show that will detect many nitro explosives significantly strengthens several magnitude.Analyte can be introduced chamber C3, arrive in the mass spectrometer atmospheric pressure interface, perhaps extract in the ionic mobility spectroanalysis instrument drift region by the The ion extraction of the port on the electrode E2 with analyte.Can heat this equipment, perhaps its arbitrary portion is to help under low pressure analysis of compounds and to reduce sample transfer.
If Fig. 2 illustrate carrying gas (for example, nitrogen or helium) flow into the first Room C1, by medial compartment C2, then, flow out from the C3 of terminal ventricle by the port in the electrode E2, be used for the customized configuration in the atmospheric ionization source of compare operation.All gas outlet O1, O2 and O3 all are closed, and utilize diaphragm seal inlet G3, inject analyte vapor to utilize gastight syringe.Ion and metastable gas molecules flow by the port on electrode E0, E1 and the E2 along the axis from probe electrode N.
The applicant utilizes it to realize that carrying gas of the present invention is helium and nitrogen.They the two all have the high first electron ionization current potential, and under room temperature and constant pressure, do not react with other elements or compound.Because this reason, other inert gases, for example, and argon gas, krypton gas and xenon are suitable carrying gas.
Discharge according to the present invention is corona discharge or glow discharge.Obviously, in discharge process, electronics is accelerated atom or the molecule that enters carrying gas, causes the additional electron freedom, and quickens in the step mode.Except making the electronics freedom and producing the cation, collision makes energy be delivered to atom and molecule, to produce metastable excited-state species.Glow discharge is light emitting discharge, and not by the gas spark jump.Corona be under high pressure, near the faint aura on electric conductor surface.Usually, glow discharge requires high potential, to start, still keeps low-voltage, then, and " puncture ".The internal resistance of the power supply of probe electrode and other effects limit discharging currents.According to the present invention, can not be the high electric current that possible cause sputter or produce arc light.
Equipment shown in the schematic diagram of Fig. 2 is positioned at JEOL AccuTOF
TMThe inlet taper (" aperture ") of flight time (time-of-flight) mass spectrometric atmospheric pressure interface.Operate this aperture at earth potential.Nitrogen enters the first Room C1 by inlet G1, then, flows out from the outlet of electrode E2.Probe electrode N is set to be enough to start the value of gas discharge, and (900V to 1 normally, 500V), and electrode E0, E1 and E2 are set to earth potential.Mass spectrum shown in Figure 9 illustrates the background ions in the carrying gas.Mainly produce ion by the impurity in the region of discharge of chamber C1.Measure according to nominal mass, can specify their elemental composition.
Table 1
| Nominal mass | Composition |
| 26 | |
| 35 | 35Cl - |
| 37 | 37 |
| 42 | CNO - |
| 45 | HCO 2 - |
| 46 | NO 2 - |
| 59 | C 2H 3O 2 - |
| 60 | CO 3 - |
| 61 | |
| 62 | NO 3 - |
Figure 10 and 11 illustrates benefit of the present invention.Figure 10 illustrates the effect in the nitrogen current that the 3cc room air is ejected into by inlet G1.Note that NO
2 -And NO
3 -High abundance (abundance).On the contrary, if by G3 the 3cc room air is sprayed into chamber C3, then the main matter of Chan Shenging is O
2 -, HCO
3 -, CO
3 -, HO
3 -And HCO
4 -, as shown in figure 11.In this case, do not produce a large amount of NO
2 -Perhaps NO
3 -Perhaps relevant family ion.
If electrophilic analyte is introduced inlet G3, then can observe the characteristic ion.For diethylmethylphosphonothiolate[M-C
2H
5]
-, can produce these ions by direct ionization and fragmentation analyte, as shown in figure 12, perhaps, analyte ions and other materials may produce them, shown in the phenyl-hexafluoride among Figure 13 by being reacted.This illustrates addition (adduct) ion, for example, and [M+N]
-, [M+O
2]
-And [M+NO
2]
-By the neutral environment in the C3 of control room (utilize and mix or selection analyte carrying gas or solvent), can control the ion forming process.
Under negative ion mode,, can from mass spectrum, eliminate background ions shown in Figure 13 if electrode E1 or E2 are elevated to more positive potential (please refer to Figure 14, Figure 14 illustrates the mass spectrum of the air of the anion with trapping).Yet, with also producing big analyte signal in the reactant injection inlet G3, because in the C3 of chamber, still there is metastable atom.
Shown in equation 1, utilize the Penning ionization process, metastable atom produces electronics, then, by in several nanoseconds under normal pressure with gas molecule collision, the electronics of acquisition is cooled to heat energy rapidly.Utilize electrophilic reagent to catch these electronics, to produce analyte ions.This analyte ions can be further with chamber C3 in substance reaction, to produce the mass spectrum that obtains.Do not need by port G3, this analyte is introduced in the C3 of chamber.For example, only by making air-flow aim at U.S. dollar, crops leaf, people's finger tip, concrete, pitch or the lip-deep analyte of air ticket, just can long-range sampling analysis thing.
If ion source is biased to the more negative potential more negative than the aperture of spectrometer interface, then anion attracted to this aperture, and signal strength signal intensity is greater than 10 times.
About detecting nitromethane, good selectivity of the present invention is described.If air is injected the corona discharge region in prior art source, then forms a large amount of NO
2 -, NO
3 -With relevant family ion (clusterion).This is shown in Figure 10, and if the NO of hope detection such as the nitro compound deposits yields of nitromethane or nitro explosive
2 -And NO
3 -, then this is not the result who wishes.Yet,, observe inapparent NO if air is sprayed in the C3 of chamber according to the present invention
2 -, NO
3 -(with reference to Figure 15), but NO
2 -, NO
3 -It is the main matter (please refer to Figure 16) that produces when spraying into nitrobenzene by inlet G3.
By changing mass spectrometric polarity, can observe cation.The positive ion mass spectrum of nitromethane (Figure 17) and nitrobenzene (Figure 18) illustrates and comprises tool diagnostic useful [M+H]
+Ion.Do not need to change the current potential of probe electrode N and counterelectrode E0, because probe electrode N all forms metastable atom under negative potential and positive potential.Therefore, can between positive ion mode and negative ion mode, change ion source rapidly, and need not the high pressure conversion, the high pressure conversion need be reset gas discharge after flame-out time.Under positive ion mode, wish bias electrode E1 and E2, so that therefore the current potential of electrode E2, has increased the ion flow of aperture than the current potential corrigendum of aperture.
Other operator schemes also are fine.The electronics of discharge generation in the C1 of chamber can be introduced chamber C2, then, it is cooled to heat energy, carry out electron capture to utilize the analyte molecule in the C3 of chamber.Work the down and metastable atom ion source that be connected to traditional high vacuum mass spectrometer ion source for low temperature (subambient) pressure, Leymarie and partner (N.Leymarie, J.-C.Tabet and M.Bertrand deliver in the annual meeting in 2000 of U.S. mass spectrometer association) reported relevant experiment.Yet this report requires Reduced pressure source, and is not described under the normal pressure and API mass spectrometer or ionic mobility mass spectrometer are used in combination ion source.The present invention utilizes the superelevation electronics cooling effectiveness of normal pressure cooling chamber C2.In one implementation, will utilize the metastable atom can ionized gas, for example, CO
2Introduce chamber C2, in the C2 of this chamber, further cool off electrons emitted.
Fig. 3 and 4 illustrates the schematic diagram that copper mesh orifice plate 40 wherein is used for being produced by metastable species 41 atmospheric pressure interface of electronics.Known metastable (matastable) atom and rydberg (Rydberg) atom discharge electronics by conductive mesh.Can make this mesh remain on certain current potential, this current potential is equivalent to the aperture of spectrometer interface 42 for negative.Negative potential repels electrons is left this grid or mesh, so that this electronics makes analyte ionization.In this case, analyte is not introduced into chamber C3, but by the open spaces internal ionization between interface and mass spectrometer, analyzes with " sniffer (sniffer) " pattern.This space is current potential closely, perhaps is not in the highfield at least.This foundation is effective especially to the negative ion mass spectrum instrument, but it is also effective to align ion mass-spectrometer.Can also be with respect to E2 positive bias mesh, with the material of gathering zone positive electricity, for example, positron or proton.
Under " sniffer " pattern, there is air all the time.Mass spectrum shown in Figure 19 shows the air background spectrum under the negative ion mode.By near the space of the outlet of atmospheric pressure interface and mass spectrometric inlet, placing the open type vial (open vial) of analyte, produce the spectrum (Figure 20 and shown in Figure 21) of phosphoric acid methyl ethyl ester and diethylmethylphosphonothiolate.Obtain the positive ion mode spectrum (shown in Figure 22) of diethylmethylphosphonothiolate in the same way.
Figure 23 illustrates the anion spectrum of TNT.By further studying, dissolve the TNT of 700 nanograms, then, place them in aviation and board on the passage, make their dry weeks.Under negative potential grid situation, in " sniffer " pattern, this passage is positioned at the front of atmospheric pressure interface.Observe mass spectrum (Figure 24 (b)) and IMS spectrum (Figure 24 (a)).
With reference now to Fig. 5,, can comprise the non-conductive shell 10 of tubular type according to the physical configuration (shown in the schematic diagram of Fig. 3) of normal pressure ion device of the present invention, can be by Teflon
Plastic (good temperature tolerance), ceramic material or other non-conducting materials are made the non-conductive shell 10 of this tubular type.What extend from an end of shell is disposable (disposable) glass tube plug-in part 11, and its non-conductive extremity piece 13 is used to make mesh electrodes or grid 14 to remain on the appropriate location.Utilize insulated conductor 15, mesh electrodes 14 is connected to microjack 17 on the shell.In the opposite end of shell 10 are the carrying gas accesses that comprise connector 18, and connector 18 has and is used to make the flexible pipe slide plate to keep thereon corrugated surface.Microjack 21,22,23 and 24 is by shell, and being used for will going between in shell 10 is connected to each electrode from power supply.
With reference now to Fig. 6,, the inside of shell is divided into first Room and second Room.End at each axis is fixed to hollow plug on the shell.At arrival end, connector 26 has the thread that is used to fit into opening connector 18.At the port of export, connector 27 is provided with the inner circular annular groove, is used to hold the logical O ring of dimension (Viton O-ring) 38, and the logical O ring 38 of this dimension is isolated with glass tube plug-in part 11.Non-conductive partition 30 keeps probe electrode 31, and probe electrode 31 is connected to microjack 21, and determines to produce first Room of corona discharge and glow discharge.Conductive spacer and electrode backplate 32 are positioned at shell, and adjacent with the non-conductive partition of supporting this probe.Conductive spacer 32 is connected to microjack 23.Non-conductive partition 33 is positioned at shell, and adjacent with conductive spacer 32, to determine second Room.Another conductive spacer and electrode backplate 34 are positioned near the non-conductive partition 33, to determine the axial port of export of second Room.Conductive spacer 34 is connected to microjack 22 in abutting connection with glass tube plug-in part 11. these conductive spacer.Microjack 24 is communicated with conductivity cell at the port of export that extends axially shell, and wherein it is connected to microjack 17.
With reference to figure 7, be shown in further detail the end of glass tube with non-conductive extremity piece 13.Non-conductive extremity piece 13 makes grid separate with direct node, makes at grid to be difficult to contact high pressure.The hole of this extremity piece makes the excited state escape of gas, with ionization of analytes.Copper is washed the end of device 39 (with reference to figure 7) in abutting connection with glass tube, and welds together with lead-in wire 15.Facing to this copper wash device fixing be grid electrode 14.Hollow glass tube 11 and grid electrode 14 are determined the 3rd Room.
With reference to figure 8, utilize schematic diagram that the example of the power supply of atmospheric pressure ion source is shown.The AC electric current passes through switch S
1With fuse F
1, then, be applied to change over switch power supply SPS.15 volts of DC outputs are applied to filtering capacitor C
1To current regulator CR.By filtering capacitor C
2Apply the electric current of adjustment to HVDC (High Voltage Direct Current) converter DC-HVDC.By current-limiting resistor R
1, this electrode is applied the high pressure of this equipment, be used to produce corona discharge or glow discharge.15 volts output also is applied to a plurality of general big current positive voltage regulators VR.The output of this voltage regulator is applied to filtering capacitor C
3, so that electric current is by HVDC (High Voltage Direct Current) converter DC-HVDC
2The output of this converter is applied to voltage divider R
7, this voltage divider R
7Be used to regulate the current potential of lens electrode.The technical staff of power supply design field understands how to dispose the negative output potential circuit.
Atmospheric pressure ion source described here is used for ion is introduced mass spectrometer and ionic mobility spectroanalysis instrument, is used for detecting and discerning interested analyte, for example, medicine, explosive, chemical weapons, poisonous industrial materials etc.It is inactive, and in the headspace sampling process, it guarantees rapid sample gas and steam.It is the lip-deep chemicals of Direct Sampling rapidly.This feature makes ion source described here replace the radiation source on the IMS detector very effectively.
Can use more than one ion source described here or equipment effectively simultaneously.For example, the applicant has carried out wherein using two ion sources mass spectrometer to be provided the experiment of ion simultaneously.In one case, utilize two ion sources, analyze acetone with positive ion mode.Use two ionogenic ion flows near using ionogenic total ion current separately.In another experiment, detect oxonium ion with negative ion mode.In addition, use two ionogenic ion flows near using ionogenic total ion current separately.
" atmospheric ionization source " is the ionization source that does not need vacuum pump as used herein.Certainly, analyzer (mass spectrometer) can require vacuum pump, but can form ion with slightly above and below the pressure of normal pressure.
Although the specific requirement according to Patent Law describes the present invention in detail, following claim limits the claimed content of patent certificate.
Claims (35)
1. on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The first normal pressure chamber has carrying gas access, first electrode, is positioned at an end and counterelectrode, is positioned at the other end, is used for producing in the carrying gas that produces metastable neutral excited-state species discharge;
The second normal pressure chamber, adjacent with first Room, and at one end have the port that enters first Room, and in the gas outlet that the other end has electrode and carries gas, determine the size of port, with limited flow, described first electrode and port are aimed at substantially; And
Be used for the gas that contains excited-state species that will flow out from the gas outlet with under normal pressure near the contacted device of earthy analyte.
2. on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The first normal pressure chamber has carrying gas access, first electrode and counterelectrode in it, is used for producing in the carrying gas that produces metastable neutral excited-state species discharge;
The second normal pressure chamber, adjacent with first Room, and at one end have the port that enters first Room, and have electrode at the other end;
The 3rd normal pressure chamber, adjacent with second Room, and have port that enters second Room and the gas outlet of carrying gas, described first electrode is almost aimed at port; And
Be used for the gas that contains excited-state species that will flow out from the gas outlet with under normal pressure near the contacted device of earthy analyte.
3. on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The first normal pressure chamber has carrying gas access, first electrode, is positioned at an end and counterelectrode, is positioned at the other end, is used for producing in the carrying gas that produces metastable neutral excited-state species discharge;
The second normal pressure chamber, adjacent with first Room, and at one end have the port that enters first Room, in the gas outlet that the other end has electrode and carries gas, determine the size of port, with limited flow; And
Ground connection or charged grid electrode are positioned at output port, so that at contact radiation charged particle during excited-state species, described first electrode and port are aimed at substantially.
4. on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The first normal pressure chamber has carrying gas access, first electrode, is positioned at an end and counterelectrode, is positioned at the other end, is used for producing in the carrying gas that produces metastable neutral excited-state species discharge;
The second normal pressure chamber, adjacent with first Room, and at one end have the port that enters first Room, in the gas outlet that the other end has electrode and carries gas, determine the size of port, with limited flow; And
Ground connection or electronegative grid electrode are positioned at output port, so that at contact radiating electron during excited-state species, described first electrode and port are aimed at substantially.
5. on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The first normal pressure chamber has carrying gas access, first electrode and counterelectrode in it, is used for producing in the carrying gas that produces metastable neutral excited-state species discharge;
The second normal pressure chamber, adjacent with first Room, and at one end have the port that enters first Room, and have electrode at the other end;
The 3rd normal pressure chamber, adjacent with second Room, and have port that enters second Room and the gas outlet of carrying gas; And
Ground connection or electronegative grid electrode are positioned at output port, so that in contact radiating electron during excited-state species, described first electrode and port rough alignment.
6. on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The first normal pressure chamber has carrying inlet of gas and exhaust outlet, first electrode and counterelectrode in it, is used for producing in the carrying gas that produces metastable neutral excited-state species discharge;
The second normal pressure chamber, adjacent with first Room, and at one end have the flow restriction port that enters first Room and have electrode at the other end, and have the entrance and exit that is used for selectable cooling reacting gas;
The 3rd normal pressure chamber, adjacent with second Room, and have the flow restriction port that enters second Room, and have the entrance and exit of analytical gas or steam; And
The gas outlet of the interactional ionization product of carrying gas and analytical gas or steam, described first electrode and port rough alignment.
7. on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The first normal pressure chamber has inlet, first electrode and counterelectrode in it of carrying gas, is used for producing in the carrying gas that produces metastable neutral excited-state species discharge;
The normal pressure chamber is adjacent with first Room in the middle of at least one, and one of normal pressure chamber has the flow restriction port that enters first Room in the middle of described, and has the inlet that is used for selectable cooling reacting gas;
Final normal pressure chamber, adjacent with one of described medial compartment, have the port that enters medial compartment, and have the inlet of analytical gas or steam; And
The gas outlet of the interactional ionization product of carrying gas and analytical gas or steam, described first electrode and port are aimed at substantially.
8. according to the arbitrary described equipment of claim 1 to 5, further comprise the device that is used for gas is introduced second Room, utilization can this gas of ionization in the excited-state species of the first indoor generation, producing cation and electronics, so that by further this electronics of collision thermalization.
9. according to claim 1,2,6 or 7 arbitrary described equipment, further comprise grid, arrange it with the contact excited-state species.
10. according to the arbitrary described equipment of claim 1 to 7, further comprise the current potential that is used to regulate on the described electrode, with the device of the speed of control ionization electron energy.
11. according to the arbitrary described equipment of claim 1 to 7, comprise being used for regulating the carrying gas pressure,,, and make its acceleration by changing air pressure because carrying embeds the electronics in the air-flow with the device of the speed of control ionization electron energy.
12. according to the arbitrary described equipment of claim 1 to 6, wherein the second indoor electrode is a lens electrode.
13. according to the arbitrary described equipment of claim 1 to 7, wherein regulate electrode potential, to promote to produce positive analysis thing, fragment or addition ion.
14. according to the arbitrary described equipment of claim 1 to 6, wherein regulate electrode potential, to promote to produce negative analyte, fragment or addition ion.
15.,, with the trapping positron and repel free electron, thereby make ion source be in negative ion mode wherein with the negative potential second indoor electrode of setovering according to the arbitrary described equipment of claim 1 to 6.
16.,, with the trapping negatron and repel the cation material, and excited-state species is passed through, thereby is made ion source be in positive ion mode wherein with the positive potential second indoor electrode of setovering according to the arbitrary described equipment of claim 1 to 6.
17. a generation is used for the method for analyte, analyte fragment and/or the analyte addition ion of spectrum analysis, comprises step:
To carry gas and introduce the first normal pressure chamber, the first normal pressure chamber has first electrode, is positioned at an end and counterelectrode, is positioned at the other end, and first electrode and counterelectrode applied current potential, in the carrying gas that produces metastable neutral excited-state species, to produce discharge;
To carry gas and metastable species and introduce the second normal pressure chamber, wherein metastable species reacts with carrying gas, to produce cation and thermalized electron; And
The carrying gas contact that is come out in second Room keeps normal pressure and approaching earthy reactant, to form analyte ions, analyte fragment ion and/or analyte addition ion.
18. method according to claim 17, wherein carrying gas is helium, and make first electrode keep than negative approximately 400 volts more negative, and make counterelectrode keep closely current potential.
19. method according to claim 17, wherein carrying gas is helium, and first electrode is kept than positive approximately 400 volts of corrigendums, and makes counterelectrode keep closely current potential.
20. method according to claim 17, wherein carrying gas is nitrogen, and first electrode than negative approximately 1,200 volt more negative, and make counterelectrode keep closely current potential.
21. equipment according to claim 17, wherein carrying gas is nitrogen, and first electrode is than about 1,200 volt of corrigendum, and makes counterelectrode keep closely current potential.
22. a generation is used to carry out the method for analyte, analyte fragment and/or the analyte addition ion of spectrum analysis, comprises step:
To carry gas and introduce the first normal pressure chamber, the first normal pressure chamber has first electrode, is positioned at an end and counterelectrode, is positioned at the other end, and first electrode and counterelectrode applied current potential, in the carrying gas that produces metastable neutral excited-state species, to produce discharge;
To carry gas and metastable species and introduce the second normal pressure chamber, wherein metastable species reacts with carrying gas, to produce cation and thermalized electron;
To carry gas, cation and/or thermalized electron and introduce the 3rd normal pressure chamber; And
Gaseous analytes or vaporization analyte are introduced the 3rd Room, to form analyte ions, analyte fragment ion and/or analyte addition ion.
23. method according to claim 22, wherein carrying gas is helium, make first electrode keep than negative approximately 400 volts more negative, and make counterelectrode keep closely current potential.
24. method according to claim 22, wherein carrying gas is helium, first electrode is kept than positive approximately 400 volts of corrigendums, and make counterelectrode keep closely current potential.
25. method according to claim 22, wherein carrying gas is nitrogen, first electrode than negative approximately 1,200 volt more negative, and make counterelectrode keep closely current potential.
26. equipment according to claim 22, wherein carrying gas is nitrogen, and first electrode is than positive approximately 1,200 volt of corrigendum, and makes counterelectrode keep closely current potential.
27. a generation is used to carry out the method for analyte, analyte fragment and/or the analyte addition ion of spectrum analysis, comprises step:
To carry gas and introduce the first normal pressure chamber, the first normal pressure chamber has first electrode, is positioned at an end and counterelectrode, is positioned at the other end, and first electrode and counterelectrode applied current potential, in the carrying gas that produces metastable neutral excited-state species, to produce discharge;
The grid electrode that carrying gas and metastable species directive are biased is to produce electronics or ion; And then
Under normal pressure, make carrying gas haptoreaction thing, to form analyte ions, analyte fragment ion and/or analyte addition ion.
28. a generation is used for comprising step in the method for carrying out analyte, analyte fragment and/or the analyte addition ion of spectrum analysis near normal temperature and earthy lip-deep analyte:
To carry gas and introduce the first normal pressure chamber, the first normal pressure chamber has first electrode, is positioned at an end and counterelectrode, is positioned at the other end, and first electrode and counterelectrode applied current potential, in the carrying gas that produces metastable neutral excited-state species, to produce discharge;
Make carrying gas and metastable species directive grid electrode, thereby cause when being impacted, sending electronics by metastable species with the negative potential biasing; And then
The electronics directive that makes carrying gas and send is under normal pressure and near earthy surface, to form analyte ions, analyte fragment ion and/or analyte addition ion.
29. a method that is used to replace the radioactive source in the charged particle detector comprises:
Remove radioactive source, and the on-radiation normal pressure equipment that is used for ionization of analytes replaces it, this on-radiation normal pressure equipment comprises:
The first normal pressure chamber has carrying gas access, first electrode and counterelectrode in it, is used for producing in the carrying gas that produces metastable neutral excited-state species discharge; And
The normal pressure chamber is communicated with first Room, and has the flow restriction port that enters first Room, and has the inlet of analytical gas or steam and the gas outlet that is communicated with the charged particle detector in the middle of at least one.
30. according to the described equipment of claim 1 to 7, the electrode that wherein is positioned at the other end of second Room is connected to power supply, this power supply of counterelectrode can be changed the polarity of this electrode and not change the polarity of first electrode and counterelectrode, therefore can rapidly this equipment be changed to negative ion mode from positive ion mode, vice versa.
31. a generation is used for comprising the step of using more than one on-radiation atmospheric ionization equipment as claimed in claim 1 simultaneously in the method for carrying out analyte, analyte fragment and/or the analyte addition ion of spectrum analysis near normal temperature and earthy lip-deep analyte.
32. an on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The normal pressure chamber, the device that has the carrying gas access and be used for producing metastable neutral excited-state species at carrying gas; And
Be used to make the device of the gas contact approaching earthy analyte under normal pressure that contains excited-state species.
33. an on-radiation normal pressure equipment that is used for ionization of analytes comprises:
The normal pressure chamber, the device that has the carrying gas access and be used for producing metastable neutral excited-state species at carrying gas; And
Ground connection or charged grid electrode are used for sending the particle of change when the contact excited-state species; And
Be used to make the device of the gas contact approaching earthy analyte under normal pressure that contains described charged particle.
34. a method that is used to produce the analyte, analyte fragment and/or the analyte addition ion that carry out spectrum analysis comprises step:
To carry gas and introduce the normal pressure chamber, and in described carrying gas, produce the neutral excited-state species of metastable normal pressure; And
Make from the contact of the carrying gas of this chamber with normal pressure and the analyte that keeps of current potential closely, with formation analyte ions, analyte fragment ion and/or analyte addition ion.
35. a generation is used to carry out the method for analyte, analyte fragment and/or the analyte addition ion of spectrum analysis, comprises step:
To carry gas and introduce the normal pressure chamber, to produce metastable neutral excited-state species;
The grid electrode that carrying gas and metastable species directive are biased is to produce electronics or ion; And then
Make the reactant of carrying gas contact under normal pressure, to form analyte ions, analyte fragment ion and/or analyte addition ion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46017903P | 2003-04-04 | 2003-04-04 | |
| US60/460,179 | 2003-04-04 | ||
| US10/732,205 | 2003-12-10 |
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| Publication Number | Publication Date |
|---|---|
| CN1768411A true CN1768411A (en) | 2006-05-03 |
| CN100514539C CN100514539C (en) | 2009-07-15 |
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| CN101542319B (en) * | 2006-11-20 | 2012-11-21 | 威苏雷有限公司 | A method of downhole, non-isotopic generation of ionised radiation and an apparatus for use when practising the method |
| CN103623925A (en) * | 2013-11-14 | 2014-03-12 | 中国科学院合肥物质科学研究院 | Bipolar charging device for atmospheric particulates |
| CN105632876A (en) * | 2016-03-08 | 2016-06-01 | 江苏德佐电子科技有限公司 | Collision cavity used for anion and gas collision |
| CN106687807A (en) * | 2014-09-04 | 2017-05-17 | 莱克公司 | Soft ionization based on conditioned glow discharge for quantitative analysis |
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2004
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| CN101542319B (en) * | 2006-11-20 | 2012-11-21 | 威苏雷有限公司 | A method of downhole, non-isotopic generation of ionised radiation and an apparatus for use when practising the method |
| CN103623925A (en) * | 2013-11-14 | 2014-03-12 | 中国科学院合肥物质科学研究院 | Bipolar charging device for atmospheric particulates |
| CN103623925B (en) * | 2013-11-14 | 2015-12-30 | 中国科学院合肥物质科学研究院 | Atmospheric particulates bipolarity charge device |
| CN106687807A (en) * | 2014-09-04 | 2017-05-17 | 莱克公司 | Soft ionization based on conditioned glow discharge for quantitative analysis |
| CN106687807B (en) * | 2014-09-04 | 2018-09-04 | 莱克公司 | The soft ionization based on modulated glow discharge for quantitative analysis |
| US10192723B2 (en) | 2014-09-04 | 2019-01-29 | Leco Corporation | Soft ionization based on conditioned glow discharge for quantitative analysis |
| US10373814B2 (en) | 2014-09-04 | 2019-08-06 | Leco Corporation | Soft ionization based on conditioned glow discharge for quantitative analysis |
| CN105632876A (en) * | 2016-03-08 | 2016-06-01 | 江苏德佐电子科技有限公司 | Collision cavity used for anion and gas collision |
| CN105632876B (en) * | 2016-03-08 | 2017-09-15 | 江苏德佐电子科技有限公司 | It is a kind of to be used for anion and the collision chamber of gas collisions |
| CN111316088A (en) * | 2017-11-30 | 2020-06-19 | 德国元素分析系统公司 | Spark emission spectrometer and method of operating the same |
| CN111316088B (en) * | 2017-11-30 | 2023-04-07 | 德国元素分析系统公司 | Spark emission spectrometer and method of operating the same |
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| CN100514539C (en) | 2009-07-15 |
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