CN104241077B - Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined and mass spectrometer - Google Patents
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined and mass spectrometer Download PDFInfo
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- CN104241077B CN104241077B CN201410383807.8A CN201410383807A CN104241077B CN 104241077 B CN104241077 B CN 104241077B CN 201410383807 A CN201410383807 A CN 201410383807A CN 104241077 B CN104241077 B CN 104241077B
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Abstract
The present invention discloses normal pressure micro-glow discharge maldi mass spectrometer ion gun of a kind of magnetically confined, including the ion gun body for producing the micro-glow discharge of normal pressure, for providing the Helmholtz coil of the uniform magnetic field retraining micro-glow discharge plasma and sample ions, for producing the annular electrode of the assisted focused charged particle of electrostatic field；Ion gun body is in the magnetic field that Helmholtz coil produces, the electric field that the ion stream that ion gun body produces is produced by annular electrode.Invention additionally discloses the mass spectrometer that a kind of normal pressure micro-glow discharge maldi mass spectrometer ion gun using magnetically confined is constituted.Energy consumption of the present invention is low, low-profile, simple in construction, easy and simple to handle, to external world affect little, signal strengthen degree big, without sample pretreatment, analyze rapidly, can reach analyze without wound, cleanliness without any pollution.
Description
Technical field
The present invention relates to detection technique field, particularly relate to normal pressure micro-glow discharge maldi mass spectrometer ion gun and the mass spectrometer of a kind of magnetically confined.
Background technology
Mass spectrometry is a kind of method by the mensuration of the mass-to-charge ratio of sample ion carries out mass spectral analysis.As the important detection instrument in analysis science, mass spectrograph have highly sensitive, analyze that speed is fast, the best, can be used for the advantages such as Chemical Measurement, be widely used in the every field such as chemistry, chemical industry, material, environment, geology, the energy, medicine, criminal investigation, life science, sports medical science, and the qualitative of trace determinand and quantitatively in play huge effect.For a long time, people are devoted to improve mass spectrometric analytical performance always, and the raising of this performance is mainly started with from the mass spectrometric structure of optimization.The structure of mass spectrometer mainly includes ion gun, mass analyzer, detector and vacuum system.For improving the sensitivity of mass spectral analysis, and meet different analysis purposes, it has been developed that various mass analyzer, including ion trap, level Four bar, track trap, time of flight mass analyzer etc..In addition, Ionization Efficiency and the ion efficiency of transmission between ion gun and mass spectrograph injection port of sample is to dominate the key factor of mass spectrum performance.In order to improve Ionization Efficiency, existing business-like electron spray ionisation source (Electrospray ionization, ESI), atmosphere pressure chemical ion source (Atmospheric pressure chemical ionization, APCI), substance assistant laser desorpted ionized source (Matrix assisted laser desorption ionization, MALDI) etc. improves the efficiency of ability transmission to meet the ionization to heterogeneity sample by modes such as electron spray, high-pressure discharge, matrix, laser.Meanwhile, Proton transfer reaction mass spectrometry (PTR-MS) and selection ionization drift tube mass spectrum (SIFT-MS) utilize electrostatic field to extract and focal zone charged particle, thus improve the ion transmission efficiency between ion gun and mass spectrum injection port.Also have been reported that and utilize magnetic field to substitute electrostatic field to realize the focusing to object ion, but to high energy electron and the constraint of ion under up to the present magnetic field is only used for non-atmospheric pressure environment, and magnetic field intensity is often as high as hundreds to thousands Gauss (Gs), this may affect the normal operation of other parts in mass spectrograph.
In recent years, atmospheric pressure ionization technology, because of the operating environment of its normal pressure, without advantages such as sample pretreatment, high flux, quick responses, is paid close attention to widely in fields such as Instrumental Analysis, food analysis, organic chemistry, macromolecule, biologies.Normal pressure Ionization Techniques In Mass Spectrometry (Ambient mass spectrometry) of increasing income starts from Desorption Electrospray Ionization (the Desorption Electrospray Ionization of R.G.Cooks in 2004 et al. report, DESI), and R.B.Cody analyzes ionization technique (Direct Analysis in Real Time, DART) in real time equal to the direct of proposition in 2005.nullOther this type of atmospheric pressure ion source occurred in recent years also has desorption atmospheric chemical ionization (Desorption Atmospheric Pressure Chemical Ionization,DAPCI)、Dielectric barrier discharge ionization (Dielectrical Barrier Discharge Ionization,DBDI)、Flowing atmospheric pressure twilight sunset (Flowing Atmospheric Pressure Afterglow,FAPA)、Desorption atmospheric pressure photoionization (Desorption Atmospheric Pressure Photoionization,DAPPI)、Probe electron spray ionisation (Probe Electrospray Ionization,PESI)、Microwave Induced Plasma desorption ionization (Microwave-Induced Plasma Desorption Ionization,MIPDI) etc..The operation principle of this kind of atmospheric pressure ion source mainly includes desorption and ionization two big processes.Its substantially process producing ion includes: certain light source (infrared, ultraviolet), or certain energy source (electric field, heat energy) acts on certain carrier (gas, reagent) and produces the electrical body with certain energy, act on sample surfaces, while making the molecule of sample surfaces desorb or ionize subsequently.These technology all play significant role in each field, but sample ions is easily made ion transmission efficiency be substantially reduced by external interference under atmospheric pressure environment, thus strongly limit the sensitivity of normal pressure mass spectral analysis.Meanwhile, energy source, high heat that this kind of atmospheric pressure ion source needs are high make mass spectrogram complicate, ion source structure is complicated, cost of manufacture is high, thus also need to improve further and improvement.Therefore, exploitation offer is a kind of ensures that the simple in construction of macroion efficiency of transmission, the atmospheric pressure ionization technology low, soft ionization that consumes energy are significant.
Summary of the invention
It is desirable to provide normal pressure micro-glow discharge maldi mass spectrometer ion gun of a kind of micro-glow discharge plasma of normal pressure based on magnetically confined, and the normal pressure maldi mass spectrometer analyzer being made up of it, to solve the problem that existing normal pressure Ionization Techniques In Mass Spectrometry exists.
For reaching above-mentioned purpose, the present invention realizes by the following technical solutions:
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of the magnetically confined that the present invention provides, its composition mainly includes providing magnetic field with constraint microplasma and the Helmholtz coil of other charged particle, normal pressure micro-glow discharge plasma ion gun, providing electrostatic field with the annular electrode of assisted focused charged particle, described ion gun body is in the magnetic field that Helmholtz coil produces, the electric field that the ion stream that ion gun body produces is produced by annular electrode.
In the technique scheme of the present invention, the ionogenic composition of the micro-glow discharge plasma of described normal pressure be included on isolation material base member process microplasma generation cavity, be fixedly installed on microplasma generation cavity wall for puncture work gas produce electric discharge pair of electrodes and be fixed on microplasma generation cavity entrance point for connect work gas introduce system gas circuit crossover sub, described electrode and 80～3000V D.C. regulated power supply connection.Described electrode preferably can be connected at the D.C. regulated power supply of 200～500V range regulation with voltage；Microplasma generation cavity import preferably introduces system with the work gas being designed with gas flow controller by gas circuit crossover sub and is connected, to ensure that the flow velocity of working gas is controlled in 0.5L/min～2.5L/min scope.The flow velocity of working gas is beyond this scope (less than 0.5L/min or higher than 2.5L/min), and ion gun provided by the present invention still can normally work.Put on the operating voltage of electrode typically 200～500V scope, general power is less than 4W.
In the technique scheme of the present invention, it is the tube chamber of rectangle that described microplasma generation cavity is paid the utmost attention to use section, and one of the height of tube chamber section or width are less than 1 millimeter.Described electrode preferentially uses pellet electrode.Constitute two plate electrodes of electrode pair to be fixedly installed on the most Face to face in microplasma generation cavity on two walls of two walls distance no more than 1 millimeter.Wall in the microplasma generation cavity being fixedly installed pellet electrode, it is preferably not less than 1 millimeter in the size being perpendicular to tube chamber direction.In described electrode is preferably secured to microplasma generation cavity, its ejiction opening of distance is less than or equal to 10 millimeters of positions, and the distance generally used is 1～3 millimeter.
In the technique scheme of the present invention, the material of described electrode be conduction metal material such as, platinum, copper, silver, preferably purity are not less than 99.99% platinum or brass；The material of described base member be insulating materials such as, alundum (Al2O3), polytetrafluoroethylene (PTFE), quartz or bakelite；Preferably purity be not less than 96% alundum (Al2O3), bakelite, quartz etc..
In the technique scheme of the present invention, the composition of the Helmholtz coil in described offer magnetic field includes insulator support and two coaxial parallel series coils.The coiling on insulating support of described coil forms, two coils connected in series, and number of turns, radius are identical, and the distance between coil is equal to coil radius.Electric current in said two coil in the same direction, is provided by providing the low-voltage dc power supply of electric current in the range of 0～5A.The magnetic field that described coil provides is directly proportional to electric current, and magnetic field is adjustable according to coil current, and scope preferably includes 10～50Gs.The diameter of each coil is not less than the width of microplasma generation cavity matrix.
In the technique scheme of the present invention, the material of described insulator support is pottery, alundum (Al2O3), polytetrafluoroethylene (PTFE), quartz or bakelite；The material of described winding wire be conductive metallic material such as, copper, aluminium, silver.
In the technique scheme of the present invention, described offer electrostatic field does not limits with annular electrode internal-and external diameter, the gauge of assisted focused charged particle, and internal diameter should be not less than described normal pressure micro-glow discharge maldi mass spectrometer ionogenic plasma exit width.The electromotive force of described annular electrode is provided by voltage adjustable high-voltage static power in the range of-1500V～1500V, and the adjustable voltage range of electrostatic power sources preferably includes-400V～400V.
In the technique scheme of the present invention, described offer electrostatic field with the material of the annular electrode of assisted focused charged particle for conductive material such as, copper, steel, iron, aluminium, platinum, silver.
The mass spectrometer being made up of the normal pressure of above-mentioned magnetically confined micro-glow discharge maldi mass spectrometer ion gun, its composition includes that work gas introduces system, sample introduction system, normal pressure micro-glow discharge maldi mass spectrometer ion gun, annular electrode, magnetic field, the D.C. regulated power supply that voltage range includes 80～3000V can be provided, mass spectrograph and mass spectrometric data processing system, described normal pressure micro-glow discharge maldi mass spectrometer ion gun introduces system by its pipeline crossover sub with work gas and is connected, its electrode and described offer voltage range include that the D.C. regulated power supply both positive and negative polarity of 80～3000V connects and composes loop, its microplasma generation cavity ejiction opening and described mass spectrograph plasma gas import are facing to the sample between them, described mass spectrograph is connected with described mass spectrometric data processing system.
In the above-mentioned mass spectrometer of the present invention, described normal pressure micro-glow discharge maldi mass spectrometer ion gun is preferably mounted on can be on the vertical rotary platform of vertical plane 0～90 ° of scope rotations, described turntable is arranged on 3-dimensional translation stage, so that regulation normal pressure maldi mass spectrometer ion gun microplasma generation cavity ejiction opening and sample, relative position between mass spectrograph plasma gas import, make the plasma gas alignment testing sample from the ejection of plasma generation cavity ejiction opening and mass spectrograph plasma gas import, plasma generation cavity is made to be on the center line of Helmholtz and annular electrode.Described Helmholtz coil is positioned between mass spectrograph injection port and normal pressure maldi mass spectrometer ion gun or is included by normal pressure maldi mass spectrometer ion gun.Annular electrode is placed in outside the outlet of normal pressure maldi mass spectrometer ion source plasma, and the two direct range is preferably lower than 10mm, and annular electrode coaxial should be parallel to Helmholtz coil.
In the above-mentioned mass spectrometer of the present invention, described work gas introduces system and is preferably provided with gas flow controller, to ensure that the flow velocity of working gas is controlled in 0.5L/min～2.5L/min scope.
In the above-mentioned mass spectrometer of the present invention, described sample introduction system comprises sampling pump, sample introduction needle and capillary, the sample introduction velocity interval of sampling pump preferably includes 0.1 μ L/min～5 μ L/min, the capacity of sample introduction needle is more preferably greater than 5 μ L, capillary is used for connecting sample introduction needle and work gas gas circuit, and its material is PEEK.
In the above-mentioned mass spectrometer of the present invention, described dc source is preferably voltage can be at the D.C. regulated power supply of 200～500V range regulation, put on the electric current that electrode makes working gas ionize and control in 2～20mA scopes, general power for ionization is generally less than 4W, makes the temperature of the plasma gas from the ejection of microplasma generation cavity ejiction opening control 20～100 DEG C of scopes.
The working gas being applicable to the present invention can be helium, argon gas, nitrogen etc., preferentially selects helium, argon gas.The source of the gas of working gas is generally steel cylinder gas, and the flow velocity of working gas can be controlled by a mass flow controller being placed between steel cylinder and ion gun on pipeline, the flow velocity general 0.5～2.5L/min of work gas.
The normal pressure micro-glow discharge maldi mass spectrometer analyzer using magnetically confined provided by the present invention carries out mass spectral analysis to sample, and the form of sample can be solid-state, liquid or gaseous state.For solid-state, liquid sample, sample can be held in place on the supporting body between ion gun microplasma generation cavity ejiction opening and mass spectrograph plasma gas import, from the plasma gas blowout of microplasma generation cavity ejiction opening ejection to testing sample, the molecule of sample surfaces is made to desorb under the effect of plasma gas, ionize.For liquid, gaseous sample, it is also possible to sample introduction needle extraction appropriate amount of sample, after being injected in plasma operation gas gas circuit by capillary by sample by syringe pump coutroi velocity, it is admitted to plasma generation cavity together with work gas.Sample is entered mass spectrograph by mass spectrograph plasma (orifice) gas import after being ionized, and carries out sample mass spectral analysis.
The normal pressure micro-glow discharge maldi mass spectrometer analyzer using magnetically confined provided by the present invention carries out mass spectral analysis to sample, at different working gas flow velocity with put on electrode and puncture under working gas current strength, ionic strength and the kind of gained mass spectrogram have difference.This is because under different current strength, contained active component, i.e. metastable atom in plasma, content is different, thus can have an impact the Ionization Efficiency of sample；And under different working gas flow velocity, the temperature of plasma gas is different, plasma linear velocity is the most different, thus the primary desorption mechanism (thermal desorption, momentum desorption) of sample can be made to change, thus affects follow-up ionization process further.Therefore, user can regulate ionogenic current strength, gas flow rate according to actual conditions, to reach most preferably to test effect.
The normal pressure micro-glow discharge maldi mass spectrometer analyzer using magnetically confined provided by the present invention carries out mass spectral analysis to sample, in the case of not using magnetic field and electrostatic field, under mass spectrographic cation and anion scan pattern, the mass spectrogram of obtained testing sample is the most different.During this is because use ion gun ionized sample of the present invention, the formation mechenism of negative ions is different.The forming process of cation includes that Penning ionization, proton translocation, electric charge shift, and wherein Proton-Transfer Reactions will form [M+H]+Ion, proton is mainly provided by water cluster, and water cluster is mainly by metastable atom (Hem) produced by Penning ionization with the moisture in air.In order to verify ionization mechanism further, the emission spectrum in the range of 200～1100nm of plasma is analyzed (Fig. 4, Fig. 5), N2, NO, and the existence at OI peak demonstrates the existence of charge transfer process, OH peak auxiliary confirms the existence of proton transfer, ArI and HeI is that Penning ionization provides theoretical foundation.In the positive-ion mode, the reaction that the plasma (as a example by helium) sprayed at ion gun provided by the present invention occurs under guiding is as follows:
He*+nH2O→He+(H2O)n-1H++OH-
He*+M→He+M++e-
(H2O)nH++M→M(H2O)n-1H++H2O
In the negative ion mode, O2 -For main active agent, by deprotonation mechanism O2 -By picked-up testing sample molecule on proton thus produce [M-H]-Ion, captures mechanism by electro transfer and electronics and will produce M-Ion.M-The forming process of ion is as follows:
Magnetically confined provided by the present invention based on normal pressure micro-glow discharge plasma maldi mass spectrometer analyzer, if not considering the interference of extraneous component, from microplasma generation cavity ejection micro-plasma air-flow in positive negative charged particles under the effect in the magnetic field that Helmholtz coil is provided by for the helical movement for coiling central axis, as shown in Figure 6.The long-range navigation thatch radius of this motionThe lead of helixWherein the speed v of charged particle approximates the linear velocity of plasma stream.
Magnetically confined provided by the present invention based on normal pressure micro-glow discharge plasma maldi mass spectrometer analyzer, when low magnetic field intensity is 0～50Gs, mass signal increases with the increase of magnetic field intensity, and when magnetic field intensity is higher than 40Gs, mass signal increases and slows down, as shown in Figure 7.According to the most hundreds of Gs magnetic field gained mass signal enhancing degree on the contrary not as 50Gs time signal amplification factor, this is owing to high-intensity magnetic field may excessive focal zone charged particle, Ion-ion/electron collision frequency increases, the movement locus of object ion is collided upset or electric charge quencher is directly occurred, thus causes the reduction of mass signal.
Magnetically confined provided by the present invention based on normal pressure micro-glow discharge plasma maldi mass spectrometer analyzer, the electrostatic field provided by annular electrode by focus on by the plasma flow of electrode centers with identical electrical particle, the most discrete and bury in oblivion the particle of band opposite-sign, thus auxiliary magnetic field constrained objective ion reduce the loss of charge caused by Ion-ion/electron collision.When annular electrode is applied positive potential, under the magnetic field of 50Gs, electrostatic field does not affect the intensification factor of mass signal, and when annular electrode is applied negative potential, under the magnetic field of 50Gs, mass signal strengthens with the enhancing of electrostatic field 0～-600V compared to without intensification factor during magnetic field, and reaches maximum (Fig. 8) in-600V.But the object ion of band opposite-sign is buried in oblivion in the too strong meeting of electromotive force, causing the reduction (Fig. 9) of mass signal, while ensureing mass signal intensity, the electrostatic field of-100V～-400V coordinates 50Gs magnetic field energy to obtain preferable mass signal enhancing effect.
The normal pressure based on the micro-glow discharge plasma of normal pressure of magnetically confined provided by the present invention is increased income maldi mass spectrometer ion gun, compared with existing mass ion source, has the most prominent following technique effect and an advantage:
1, the normal pressure maldi mass spectrometer ion gun based on the micro-glow discharge plasma of normal pressure of magnetically confined provided by the present invention, can be directly connected to the mass spectrograph with atmospheric pressure interface, can realize solid, liquid, the detection of gaseous sample, and easy disassembling.
2, the normal pressure maldi mass spectrometer ion gun based on the micro-glow discharge plasma of normal pressure of magnetically confined provided by the present invention, has tested the magnetic field constraint to charged particle under normal pressure, has improve the ion transmission efficiency between mass spectrum injection port and atmospheric pressure ion source.
3, ion gun simple structure provided by the present invention, Helmholtz coil, electrode material are easy to get, easy to make, and manufacturing cost is far below other existing ion guns.
4, maintaining the power of the ionogenic dc source of normal pressure maldi mass spectrometer based on the micro-glow discharge plasma of normal pressure provided by the present invention to be not more than 4W, voltage is generally no greater than 500V, and energy resource consumption is low compared with other ion guns.
5, sample is detected by employing equipped with ionogenic mass spectrometer provided by the present invention, and under the low-intensity magnetic field of tens Gs, the signal enhancing degree of sample is up to tens times, and low-intensity magnetic field is little on the impact of other parts and surrounding environment in mass spectrograph.
6, sample is detected by employing equipped with ionogenic mass spectrometer provided by the present invention, and plasma plume is high-visible, it is simple to calibrate sample with the adjustment of ionogenic relative position；Plasma plume energy is low, temperature is low, will not cause sample surfaces and burn, and the most this inspection method is a kind of without hindering analysis method.
7, sample is detected by employing equipped with ionogenic mass spectrometer provided by the present invention, it is not necessary to pre-process sample, easy and simple to handle, the time used by qualitative analysis few (less than 5s).
8, sample is detected by employing equipped with ionogenic mass spectrometer provided by the present invention, and sensitive to trace samplings response, reaction is fast, can realize high-throughout on-line analysis.
9, sample is detected by employing equipped with ionogenic mass spectrometer provided by the present invention, it is not necessary to the auxiliary of spraying reagent, will not be to environment.
10, ion gun outward appearance provided by the present invention is small and exquisite, and Helmholtz coil, annular electrode are quick detachable, it is adaptable to the exploitation application of follow-up portable mass spectrometer.
The normal pressure maldi mass spectrometer ion gun based on the micro-glow discharge plasma of normal pressure of magnetically confined provided by the present invention, its advantage sums up and includes: energy consumption is low, low-profile, simple in construction, easy and simple to handle, to external world affect little, signal strengthen degree big, without sample pretreatment, analyze rapidly, can reach without wound analysis, cleanliness without any pollution etc..
Accompanying drawing explanation
Accompanying drawing 1 is normal pressure micro-glow discharge ionogenic schematic diagram of maldi mass spectrometer of the magnetically confined of the present invention.
Accompanying drawing 2-1 is the plan structure schematic diagram of normal pressure micro-glow discharge one embodiment of maldi mass spectrometer ion gun of the present invention；
Accompanying drawing 2-2 is the left view structural representation of accompanying drawing 2-1；
Accompanying drawing 2-3 is the ionogenic internal TV structure schematic diagram of the micro-glow discharge maldi mass spectrometer of normal pressure shown in accompanying drawing 2-1.
Accompanying drawing 3 is equipped with the detection of the ionogenic normal pressure of the present invention micro-glow discharge maldi mass spectrometer analyzer and analyzes solid, the mode schematic diagram of fluid sample.
Accompanying drawing 4 is the emission spectrum figure of normal pressure micro-glow discharge argon plasma.
Accompanying drawing 5 is the emission spectrum figure of normal pressure micro-glow discharge helium plasma.
Accompanying drawing 6 is charged particle screw schematic diagram in uniform magnetic field.
Accompanying drawing 7 be in mass spectrum Background the intensity of modal m/z279 ion with a schematic diagram of the change in Helmholtz coil magnetic field.
Accompanying drawing 8 is equipped with the mass spectrum total ion current of the mass spectrometer of normal pressure micro-glow discharge plasma maldi ion source of the magnetically confined of the present invention increase multiple under the external magnetic field of the 50Gs variation diagram with ring electrode electromotive force.
Accompanying drawing 9 be equipped with the mass spectrum total ion current of the mass spectrometer of normal pressure micro-glow discharge plasma maldi ion source of magnetically confined of the present invention respectively when 50Gs and 0Gs with the variation diagram of ring electrode electromotive force.
Accompanying drawing 10 is the methyl alcohol detecting with the mass spectrometer equipped with normal pressure of the present invention micro-glow discharge plasma maldi ion source and analyzing paracetamol: water (1:1) solution gained mass spectrogram.
Accompanying drawing 11 is, with the mass spectrometer equipped with normal pressure of the present invention micro-glow discharge plasma maldi ion source, phenaetin solution carries out semi-quantitative analysis gained quantitation curves and corresponding mass spectrogram.
Toluene gained mass spectrogram analyzed in the case of being not added with external magnetic field by the mass spectrometer of normal pressure micro-glow discharge plasma maldi ion source that accompanying drawing 12-1 is equipped with magnetically confined of the present invention；
Accompanying drawing 12-2 is to analyze toluene gained mass spectrogram when adding 50Gs external magnetic field；
Accompanying drawing 12-3 is toluene [M+CH3+H]+Ionic strength is with the variation diagram in Helmholtz coil magnetic field.
Cigarette filtrate gained mass spectrogram analyzed in the case of being not added with external magnetic field by the mass spectrometer of normal pressure micro-glow discharge plasma maldi ion source that accompanying drawing 13-1 is equipped with magnetically confined of the present invention；
Accompanying drawing 13-2 is to analyze cigarette filtrate gained mass spectrogram when adding 50Gs external magnetic field.
In figure: 1-ion gun body；2-Helmholtz coil；3-annular electrode；4-ion gun base member；5-electrode；6-gas circuit crossover sub；7-microplasma generation cavity ejiction opening；8-gas circuit crossover sub air inlet；9-microplasma generation cavity；10-microplasma plumage；11-mass spectrograph plasma air inlet；12-sample ions；13-sample；14-sample supporting body；.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing, the present invention is further elaborated.
Magnetically confined disclosed by the invention based on normal pressure micro-glow discharge maldi mass spectrometer ion gun, as shown in Figure 1, structure mainly includes producing the ion gun body 1 of the micro-glow discharge of normal pressure, providing the Helmholtz coil 2 of the uniform magnetic field retraining micro-glow discharge plasma and sample ions, and produces the electrostatic field annular electrode 3 with assisted focused charged particle.The electric current of Helmholtz coil 2 provides by can provide the low-voltage dc power supply of electric current in the range of 0～5A.One feasible size of Helmholtz coil 2 is internal diameter 160mm, external diameter 220mm, and the centre-to-centre spacing of two coils is 80mm.As it is shown on figure 3, Helmholtz coil 2 is placed in Helmholtz coil 2 away from mass spectrograph injection port 5mm, normal pressure micro-glow discharge ion source body 1, mass spectrograph plasma air inlet 11 and ion gun body 1 are on the center line of Helmholtz coil 2.Annular electrode 3 overlaps with Helmholtz coil 2 center line away from ion source outlet 5mm, annular electrode 3 center line.
nullSuch as accompanying drawing 2-1、Shown in accompanying drawing 2-2 and accompanying drawing 2-3，The composition of ion gun body 1 specifically includes that the microplasma generation cavity 9 processed on the ion gun base member 4 of ceramic material、For puncturing the pellet electrode 5 that work gas produces a pair platinum product matter of electric discharge on upper and lower two walls in being embedded in microplasma generation cavity 9 face-to-face，Be fixed on microplasma generation cavity entrance point for connect work gas introduce system gas circuit crossover sub 6，Described pellet electrode 5 and the both positive and negative polarity of dc source that can regulate between 80～3000V connect and compose loop，Two pellet electrodes 5 are arranged at distance microplasma generation cavity ejiction opening 7 about 1 millimeters，To reduce the interference that electric discharge is produced by outer gas stream，And ensure that the plasma plume from the ejection of micro-plasma generation cavity ejiction opening 7 can extend to micro-plasma generation cavity，With calibration sample and ionogenic relative position.The channel size of plasma generation cavity is: long 26.6 millimeters, wide 2.4 millimeters, high 0.7 millimeter.Gas circuit conversion head 6 sealingly connects with microplasma generation cavity import high-temperature-resistant epoxy resin glue, to ensure the air-tightness of microplasma generation cavity 9 inner air path.During with this ion gun detection sample, working gas (argon gas or helium) is entered in microplasma generation cavity 9 by the air inlet 8 of gas circuit conversion head 6 end, flow through the breakdown micro-glow discharge of generation normal pressure at two pellet electrodes 2, thus produce the microplasma that ionized sample institute is necessary.
As shown in Figure 3, the analyzer that normal pressure micro-glow discharge maldi mass spectrometer ion gun of employing magnetically confined disclosed by the invention is constituted, its composition mainly includes that work gas introduces system, sample introduction system, normal pressure micro-glow discharge maldi mass spectrometer ion gun, voltage can be in the dc source of 80～3000V range regulation, mass spectrograph and mass spectrometric data processing system.Normal pressure micro-glow discharge maldi mass spectrometer ion gun is clamped on the vertical rotary platform that can rotate in the range of vertical direction 0～90 °, described vertical rotary platform is placed on 3-dimensional (3D) translation stage, makes plasma generation cavity 9 be on the center line of Helmholtz coil 2 and annular electrode 3.It is to be provided with helium or the argon gas steel cylinder of mass flowmenter that work gas introduces system, to ensure as the helium of working gas or argon gas flow control in microplasma generation cavity in 0.5～2.5L/min scope.Described sample introduction system comprises sampling pump, sample introduction needle and capillary, and the sample introduction speed of sampling pump is adjustable at 0.1 μ L/min～5 μ L/min scopes, and the capacity of sample introduction needle is 5ml, and capillary is used for connecting sample introduction needle and work gas gas circuit, and its material is PEEK.Normal pressure micro-glow discharge maldi mass spectrometer ion gun introduces system by its gas circuit crossover sub 6 with work gas and is connected, ionogenic two pellet electrodes of normal pressure micro-glow discharge maldi mass spectrometer and voltage can connect and compose loop at the dc source both positive and negative polarity of 80～3000V range regulation, the plasma ejiction opening 7 of normal pressure micro-glow discharge maldi mass spectrometer ionogenic plasma generation cavity and mass spectrograph plasma air inlet are facing to placing, being placed on sample supporting body 14 at the sample A10 between them, sample B13, mass spectrograph is connected with mass spectrometric data processing system.
When the mass spectrometer using the present invention to provide analyzes solid-state, liquid sample, solid-state (or liquid) sample 13 is held in place on the supporting body 14 between ion source plasma ejiction opening and mass spectrograph plasma gas import 11, allow the plasma gas from the ejection of ion gun ejiction opening be directed at testing sample, make the molecule of sample surfaces desorb under the effect of plasma gas, ionize.For bulk, paste, the carrier of liquid sample, can be simple glass slide, filter paper, potsherd, stainless steel substrates etc., liquid sample also can be placed directly within vessel, powdered samples need to be fixed on above-mentioned carrier with double faced adhesive tape and detect, in case powder sample enters mass spectrograph with air-flow, block mass spectrometer inlet.Sample is 5～20 millimeters with the horizontal range of mass spectrometer inlet, and vertical range is 2～10 millimeters.Ion gun is usually 1～5 millimeter with the horizontal range of sample, and vertical range is 1～5 millimeter, and ion gun is usually 10～20 millimeters with the horizontal range of mass spectrometer inlet.The plasma gas bundle that ion gun is sprayed and the angle of sample surfaces are the most adjustable in the range of 0～90 °, to ensure to obtain optimum spectrum signal during actually detected.
Mass spectrometer analyzing liquid or the gaseous sample gaseous sample of present invention offer are provided, also can extract appropriate amount of sample by sample introduction needle, after being injected in plasma operation gas gas circuit by capillary by sample by syringe pump coutroi velocity, be admitted to plasma generation cavity together with work gas.Sample is entered mass spectrograph by mass spectrograph plasma (orifice) gas import after being ionized, and carries out sample mass spectral analysis.
The mass spectrometer using the present invention to provide detect fluid sample in the case of not complementary field and electrostatic field, specifically with the solution of paracetamol for detecting object.
Pure paracetamol powder is dissolved in methyl alcohol: water be 50:50 (v:v) solvent in make the solution that paracetamol content is 30mg/L.Pipette 2 these solution of μ L with liquid-transfering gun to drip on the slide with little groove, or in other any opening vessel that can be used for holding reagent.The vessel carrying fluid sample are placed between ion gun microplasma gas generation cavity ejiction opening and mass spectrograph plasma gas entrance, regulate as work gas helium flow velocity and the current strength that punctures, to obtain optimal mass signal.Aforesaid operations final gained mass spectrogram as shown in Figure 10, the protonation dimer [2M+H] of peak correspondence paracetamol at m/z=303+, at m/z=279, peak is the protonated molecular ion peak of plasticizer neck dibatyl phithalate, and this ion all may be introduced in detecting system when the experiment equipment using great majority containing plasticiser, and the peak at m/z=152 belongs to [M+H] of paracetamol+Peak.The most easily being recognized by the paracetamol solution mass spectrogram entirety peak type shown in accompanying drawing 10, impurity peaks and fragment peak are less, therefore with ion gun provided by the present invention, fluid sample are carried out qualitative analysis tool and have great advantage.
Use the mass spectrometer that the present invention provides in the case of not complementary field and electrostatic field, individually sample can be carried out semi-quantitative analysis, specifically with phenaetin for analyzing object.
Phenaetin powder is dissolved in the solution being configured to a series of variable concentrations in pure methyl alcohol, a certain amount of paracetamol is added as internal standard compound in every a solution, and ensure that in every a solution, the concentration of paracetamol is the most identical, detects from low concentration to high concentration successively to every a sample.Input mode can be directly to be contained in uncovered vessel by solution, or drips on filter paper by 5 μ L sample, uses ion gun provided by the present invention to be analyzed sample.Accompanying drawing 11 show the quantitation curves using argon plasma gained phenaetin, sample introduction carrier used is filter paper, on linear regression line, concentration of each point is the concentration of phenaetin sample, and intensity that each point is corresponding is the ratio of phenaetin and the peak area of paracetamol in sample gained mass ions flow graph.Under setting at this, the detection range of phenaetin is 104, each sampled point all repeats sample introduction 8 times, and RSD scope corresponding to each point is 10%～20%.It should be strongly noted that this example is artificial hand sampling, thus human factor is the biggest to accuracy, the repeatability interference of detection.Introduce automatic sampling apparatus (such as peristaltic pump, mechanical pump, chromatogram relevant apparatus) will significantly increase equipped with ionogenic mass spectrometric quantitative performance provided by the present invention, thus the component that is sucked away from provided by the present invention has distinguished potential in scientific quantitative analysis analysis.
Use the mass spectrometer that the present invention provides, the detection signal of sample can be improved by the effect of contraction in magnetic field, specifically using toluene as analyzing object:
5mL sample introduction needle extracts a certain amount of toluene, after draining the bubble in needle tubing, sample introduction needle is connected with the capillary of UNICOM plasma work gas gas circuit, promotes sample introduction needle to be squeezed in gas circuit by fluid sample with pump.Arranging sampling pump speed is 1 μ L/min, and work gas (helium) flow velocity is 1.2L/min, and micro-glow current is 12mA.Regulation Helmholtz coil electric current, makes coil produce the uniform magnetic field that can produce 0～50Gs, and annular electrode provides the electromotive force of-100V.The mass spectrogram of gained toluene such as Figure 12-1 under 0Gs and 50Gs magnetic field respectively by aforesaid operations, shown in 12-2, [M-H] of the most corresponding toluene of peak m/z 91, m/z 94, m/z 108+, [M+2H]+, [M+CH3+H]+Product ion.The mass signal of three kinds of ions improves 10,11,15 times from 0Gs to 50Gs successively.Accompanying drawing 12-3 show the intensity change with coil magnetic field of peak m/z94, it can be seen that external magnetic field can be obviously enhanced the mass signal of sample ions to the confined focusing effect of ion.
Using the mass spectrometer that the present invention provides, analyze the complex sample in detection real life, the cigarette specifically bought with shop is for detection object.Cutting the cigarette bought from shop open cigarette paper, take after appropriate pipe tobacco soaks 1 hour in 40ml methyl alcohol, suction filtration soak is to remove solid impurity therein.Directly filtrate being injected in plasma operation gas gas circuit by the mode of pump sample introduction, arranging flow rate pump is 0.5 μ L/min, other condition of work with using toluene as analyze object time identical.Accompanying drawing 13-1,13-2 are respectively without the mass spectrogram of composition, [M+H] of the principal component nicotine during wherein m/z163 is cigarette in gained cigarette filtrate when magnetic field and 50Gs magnetic field+Peak, m/z79 is the fragment peak of nicotine, and m/z149 is the fragment peak of the plasticiser in cigarette paper and carrier gas channel.The ordinate contrasting two width figures understands, and compared to when being not added with magnetic field, under the external magnetic field of 50Gs, in cigarette filtrate, the mass signal of each composition all has enhancing in various degree, and wherein the intensity of m/z163 increases about 6 times, and m/z79 increases about 10 times.
Certainly; the present invention also can have other various embodiments; in the case of without departing substantially from present invention spirit and essence thereof; those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but these change accordingly and deform the protection domain that all should belong to appended claims of the invention.
Claims (21)
1. the normal pressure of a magnetically confined micro-glow discharge maldi mass spectrometer ion gun, it is characterised in that include
For producing the ion gun body of the micro-glow discharge of normal pressure, for providing constraint micro-glow discharge plasma
With the Helmholtz coil of the uniform magnetic field of sample ions, be used for producing electrostatic field assisted focused band electrochondria
The annular electrode of son；Described ion gun body is in the magnetic field that Helmholtz coil produces, and ion gun is originally
The electric field that the ion stream that body produces is produced by annular electrode.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined the most according to claim 1,
It is characterized in that, described ion gun body be included in process on base member microplasma generation cavity,
It is fixed on microplasma generation cavity wall the pair of electrodes discharged for puncturing work gas to produce and fixes
In the gas circuit crossover sub of the system that introduces for connecting work gas of microplasma generation cavity entrance point, institute
State electrode to be connected with output voltage electrodeless adjustable D.C. regulated power supply in the range of 80～3000V.
Normal pressure the most according to claim 2 micro-glow discharge maldi mass spectrometer ion gun, it is characterised in that
The tube chamber that section configuration is rectangle of described microplasma generation cavity, the height of tube chamber section or width it
One is less than 1 millimeter, and described electrode is pellet electrode, and two electrodes are separately fixed at microplasma generation cavity
Interior distance is not more than in the opposing sidewalls of 1 millimeter, and microplasma generation cavity is for fixing pellet electrode
Wall is not less than 1 millimeter in the size being perpendicular to runner direction, electrode and the spray of microplasma generation cavity
The distance of outlet is not more than 10 millimeters.
Normal pressure the most according to claim 2 micro-glow discharge maldi mass spectrometer ion gun, its feature exists
In, the material of described electrode is conductive metallic material, and the material of described base member is insulating materials.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined the most according to claim 4,
It is characterized in that, the material of described electrode is platinum, copper or silver, the material of described base member be pottery, three
Al 2 O, polytetrafluoroethylene (PTFE), quartz or bakelite.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined the most according to claim 2,
It is characterized in that, the output of described D.C. regulated power supply is electrodeless adjustable in the range of 200～500V.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined the most according to claim 1,
It is characterized in that, described Helmholtz coil is coaxial parallel by a pair and that the number of turn is identical series conductor circle
Composition, the distance between two coils is equal to size of current, direction phase in coil radius, and two coils
With.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined the most according to claim 7,
It is characterized in that, the electric current of described Helmholtz coil is 0～5A.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined the most according to claim 1,
It is characterized in that, the radius of described Helmholtz coil is not less than the width of described ion gun body.
10. according to normal pressure micro-glow discharge solution of the magnetically confined described in claim 7～9 any one
Inhale mass ion source, it is characterised in that described Helmholtz coil produce magnetic field range be 10～
50Gs。
11. according to normal pressure micro-glow discharge solution of the magnetically confined described in claim 7～9 any one
Inhale mass ion source, it is characterised in that the heart yearn material of the wire of Helmholtz coil described in coiling is for leading
Electric metal material, the skeleton supporting coil is insulating materials.
Normal pressure micro-glow discharge maldi mass spectrometer ion of 12. magnetically confineds according to claim 11
Source, it is characterised in that the heart yearn material of the wire of Helmholtz coil described in coiling is copper, aluminium or silver,
The material of the skeleton supporting coil is pottery, alundum (Al2O3), polytetrafluoroethylene (PTFE), quartz or bakelite.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of 13. magnetically confineds according to claim 1,
It is characterized in that, the electromotive force of described annular electrode by output voltage in the range of-1500V～1500V adjustable
Electrostatic power sources provide.
Normal pressure micro-glow discharge maldi mass spectrometer ion of 14. magnetically confineds according to claim 13
Source, it is characterised in that the adjustable output voltage range of described electrostatic power sources is-400V～400V.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of 15. magnetically confineds according to claim 2,
It is characterized in that, the internal diameter of described annular electrode is not less than the ejiction opening of described microplasma generation cavity
Width.
Normal pressure micro-glow discharge maldi mass spectrometer ion of 16. magnetically confineds according to claim 15
Source, it is characterised in that the material of described annular electrode is conductive material.
Normal pressure micro-glow discharge maldi mass spectrometer ion gun of 17. magnetically confineds according to claim 1,
It is characterized in that, the material of described annular electrode is copper, steel, iron, aluminium, platinum or silver.
The micro-aura of normal pressure of 18. 1 kinds of magnetically confineds comprised as described in claim 2～6 any one
The electric discharge ionogenic mass spectrometer of maldi mass spectrometer, it is characterised in that include that work gas introduces system, sample
Product introduce system, normal pressure micro-glow discharge maldi mass spectrometer ion-source mass spectrometer and mass spectrometric data processing system,
Described normal pressure micro-glow discharge maldi mass spectrometer ion gun introduces system even by pipeline crossover sub and work gas
Connecing, described mass spectrograph is connected with mass spectrometric data processing system；The setting of sample include following two ways it
One:
Mode 1: between ejiction opening and the mass spectrograph plasma gas import of described microplasma generation cavity
Place sample；
Mode 2: microplasma generation cavity is directly facing to mass spectrograph plasma gas import, and sample is by noting
Penetrate pump to be directly injected in gas channels.
19. mass spectrometers according to claim 18, it is characterised in that described magnetically confined
Normal pressure micro-glow discharge maldi mass spectrometer ion gun be arranged on D translation platform.
20. mass spectrometers according to claim 19, it is characterised in that described work gas draws
Enter system and be provided with gas flow controller, the flow velocity of working gas be controlled in 0.5L/min～
2.5L/min scope.
21. mass spectrometers according to claim 19, it is characterised in that described sample introduces system
System comprises sampling pump, sample introduction needle and capillary, and the sample introduction speed of sampling pump is 0.1 μ L/min～5 μ
L/min, the capacity of sample introduction needle is more than 5 μ L, and described capillary is used for connecting sample introduction needle and work gas gas circuit,
Capillary material is PEEK.
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| CN106601584B (en) * | 2016-12-22 | 2018-01-19 | 中国科学院西安光学精密机械研究所 | Atmospheric pressure magnetic strengthens and magnetic confinement direct current glow discharge ion gun |
| CN108305826A (en) * | 2018-04-03 | 2018-07-20 | 常州英诺激光科技有限公司 | External electromagnetic field normal pressure open-type laser mass spectrograph |
| JP6396618B1 (en) * | 2018-04-03 | 2018-09-26 | グローテクノロジー株式会社 | Glow discharge system and glow discharge mass spectrometer using the same |
| CN108615668A (en) * | 2018-04-04 | 2018-10-02 | 中国科学院上海硅酸盐研究所 | Enhance the device and method of radio frequency glow discharge mass ions signal strength with toroidal magnetic field |
| CN108648981A (en) * | 2018-04-04 | 2018-10-12 | 中国科学院上海硅酸盐研究所 | Enhance the device and method of radio frequency glow discharge mass signal intensity with adjustable magnetic fields |
| CN108519565B (en) * | 2018-04-09 | 2021-01-22 | 四川大学 | Low-intensity magnetic field intensity measurement analyzer and method based on quantum weak measurement |
| EP3987079A4 (en) * | 2019-06-24 | 2023-03-01 | TRUMPF Huettinger Sp. Z o. o. | Method of adjusting the output power of a power supply supplying electrical power to a plasma, plasma apparatus and power supply |
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