CN203772818U - Normal-pressure micro-glow discharge desorption mass spectrum ion source and mass spectrometry device formed by same - Google Patents
Normal-pressure micro-glow discharge desorption mass spectrum ion source and mass spectrometry device formed by same Download PDFInfo
- Publication number
- CN203772818U CN203772818U CN201420166654.7U CN201420166654U CN203772818U CN 203772818 U CN203772818 U CN 203772818U CN 201420166654 U CN201420166654 U CN 201420166654U CN 203772818 U CN203772818 U CN 203772818U
- Authority
- CN
- China
- Prior art keywords
- mass spectrometer
- micro
- normal pressure
- glow discharge
- ion gun
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000003795 desorption Methods 0.000 title abstract description 11
- 238000004949 mass spectrometry Methods 0.000 title abstract description 9
- 238000001819 mass spectrum Methods 0.000 title abstract description 6
- 239000012774 insulation material Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 230000008676 import Effects 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 6
- 229920001342 Bakelite® Polymers 0.000 claims description 3
- 239000004637 bakelite Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013519 translation Methods 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000007781 pre-processing Methods 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 84
- 150000002500 ions Chemical class 0.000 description 78
- 239000007789 gas Substances 0.000 description 75
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 12
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 229960005489 paracetamol Drugs 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 239000001307 helium Substances 0.000 description 9
- 229910052734 helium Inorganic materials 0.000 description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- DNXIKVLOVZVMQF-UHFFFAOYSA-N (3beta,16beta,17alpha,18beta,20alpha)-17-hydroxy-11-methoxy-18-[(3,4,5-trimethoxybenzoyl)oxy]-yohimban-16-carboxylic acid, methyl ester Natural products C1C2CN3CCC(C4=CC=C(OC)C=C4N4)=C4C3CC2C(C(=O)OC)C(O)C1OC(=O)C1=CC(OC)=C(OC)C(OC)=C1 DNXIKVLOVZVMQF-UHFFFAOYSA-N 0.000 description 7
- LCQMZZCPPSWADO-UHFFFAOYSA-N Reserpilin Natural products COC(=O)C1COCC2CN3CCc4c([nH]c5cc(OC)c(OC)cc45)C3CC12 LCQMZZCPPSWADO-UHFFFAOYSA-N 0.000 description 7
- QEVHRUUCFGRFIF-SFWBKIHZSA-N Reserpine Natural products O=C(OC)[C@@H]1[C@H](OC)[C@H](OC(=O)c2cc(OC)c(OC)c(OC)c2)C[C@H]2[C@@H]1C[C@H]1N(C2)CCc2c3c([nH]c12)cc(OC)cc3 QEVHRUUCFGRFIF-SFWBKIHZSA-N 0.000 description 7
- 238000000688 desorption electrospray ionisation Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- BJOIZNZVOZKDIG-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C([C]5C=CC(OC)=CC5=N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 BJOIZNZVOZKDIG-MDEJGZGSSA-N 0.000 description 7
- 229960003147 reserpine Drugs 0.000 description 7
- MDMGHDFNKNZPAU-UHFFFAOYSA-N roserpine Natural products C1C2CN3CCC(C4=CC=C(OC)C=C4N4)=C4C3CC2C(OC(C)=O)C(OC)C1OC(=O)C1=CC(OC)=C(OC)C(OC)=C1 MDMGHDFNKNZPAU-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 235000019504 cigarettes Nutrition 0.000 description 6
- 238000000375 direct analysis in real time Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002798 spectrophotometry method Methods 0.000 description 6
- 238000012063 dual-affinity re-targeting Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 4
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000000451 chemical ionisation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- -1 as pottery Substances 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001396 desorption atmospheric pressure chemical ionisation Methods 0.000 description 2
- 238000001601 dielectric barrier discharge ionisation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229960002715 nicotine Drugs 0.000 description 2
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012764 semi-quantitative analysis Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011840 criminal investigation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003255 drug test Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010265 fast atom bombardment Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004186 food analysis Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000010223 real-time analysis Methods 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Abstract
The utility model discloses a normal-pressure micro-glow discharge desorption mass spectrum ion source and a mass spectrometry device formed by the same. The ion source mainly comprises a micro-plasma generating cavity processed on an insulation material base body member, a pair of breakdown electrodes fixed on the wall surface of the micro-plasma generating cavity, and a gas path adapter fixed at the inlet end of the micro-plasma generating cavity and used for connecting a working gas introducing system, wherein the electrodes are connected with an adjustable direct-current voltage-stabilizing power supply. The mass spectrometry device mainly comprises a working gas introducing system, the normal-pressure micro-glow discharge desorption mass spectrum ion source, an adjustable direct-current voltage-stabilizing power supply, a mass spectrometer and a mass spectrometric data processing system. The ion source has the very remarkable advantages of low required power, less required gas, no need of toxic reagents, lower plasma gas temperature, no pollution to the environment, no need of preprocessing a sample and high detection sensitivity, is simple and convenient to operate and is capable of realizing high-flux online detection, and the like.
Description
Technical field
The utility model belongs to normal pressure Ionization Techniques In Mass Spectrometry field, particularly a kind of normal pressure maldi mass spectrometer ion gun based on the micro-glow discharge of normal pressure and the mass spectrometer consisting of it.
Background technology
Mass spectrometry is by the mensuration of the mass-to-charge ratio of sample ion being carried out to a kind of method of mass spectrophotometry.As the important testing tool in analysis science, that mass spectrometer has is highly sensitive, analysis speed is fast, selectivity good, 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 bringing into play huge effect the qualitative of trace determinand and quantitatively.The structure of mass spectrometer mainly comprises ion gun, mass analyzer, detecting device and vacuum system.According to ion gun, mass analyzer, and the difference of application, mass spectrometer can be divided into different kinds.Traditional mass spectrometer ion source for Analysis of Organic Substances comprises electron ionization sources, chemical ionization source, fast atom bombardment source, electron spray ionisation source, Atmosphere Pressure Chemical Ionization (APCI) source, and laser desorption source.Owing to utilizing these traditional ionization sources, or vacuum condition that need to be strict, or sample and processing procedure that need to be complicated, the express-analysis that is unfavorable for actual sample detects, in order to overcome above-mentioned deficiency, people can carry out the ion gun of desorb through exploring to have developed under normal pressure to untreated samples, this normal pressure ionization techniques of increasing income is paid close attention to widely in fields such as instrumental analysis, food analysis, organic chemistry, macromolecule, biologies in recent years.
The normal pressure Ionization Techniques In Mass Spectrometry of increasing income starts from Desorption Electrospray Ionization (the Desorption Electrospray Ionization of the people such as R.G.Cooks in 2004 report, DESI), and R.B.Cody equals the direct real-time analysis ionization technique (Direct Analysis in Real Time, DART) proposing for 2005.This class normal pressure is increased income that Ionization Techniques In Mass Spectrometry can directly be analyzed sample fast and accurately and without sample pretreatment, is a quantum leap progress in mass spectrophotometry field.Other this type of atmospheric pressure ion source occurring in recent years also has desorption atmospheric chemical ionization (Desorption Atmospheric Pressure Chemical Ionization, DAPCI), dielectric barrier discharge ionization (Dielectrical Barrier Discharge Ionization, DBDI), atmospheric pressure twilight sunset (Flowing Atmospheric Pressure Afterglow flows, FAPA), desorb 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.
In DESI technology, the charged droplet being produced by electron spray pin is directly injected to sample surfaces, and being dissolved with the thin liquid layer with analyte at sample surfaces formation one deck, follow-up charged droplet will discharge the secondary droplet that comprises analyte after colliding thin liquid layer from liquid layer.What next secondary droplet experienced is a solvent evaporated ions process similar to traditional ESI source.This technology is applicable to detect the compound with medium or strong polarity.DESI is widely used in the fields such as explosive detection, metabolite analysis, drug test, environmental science at present.But this Technology Need high voltage and may bring on environment the spraying reagent of impact, and because the generation of the generation of polymkeric substance, sample partial solvent, multiple-charged ion etc. causes final gained mass spectrogram comparatively complicated.
Be different from DESI, DART is that the another kind of plasma based on discharge generation carries out solvent-free Ionized normal pressure mass spectrum source to sample.In discharge process, nitrogen, argon gas, helium all can be used as working gas and produce plasma through corona discharge, and the metastable atom of high energy carries out desorption ionization as the main active in gas to determinand.DART source is all insensitive to the position of sample, sample and mass spectrometric distance, angle etc., thereby the utmost point is convenient to debugging.Technique has applicability widely to solid-state, liquid, gaseous sample, and detected object comprises the multiclass materials such as food, spices, medicine, people/animal blood, saliva, urine, tidal air, inorganics.But, due to DART source need to multipair electrode co-operation together with extra heating arrangement, its structure is comparatively complicated, cost is higher, for making, makes troubles.
Other atmospheric pressure ion source and DESI, DART are incomplete same, but also mainly comprise desorb and ionization two large processes.Its roughly process that produces ion comprises: certain light source (infrared, ultraviolet), or certain energy source (electric field, heat energy) acts on certain carrier (gas, reagent) and produces the electrified body with certain energy, act on sample surfaces, when making the molecule generation desorb of sample surfaces or carry out subsequently ionization.These technology are all in each field performance significant role, but because the high energy source of needs, high heat make the defects such as mass spectrogram is complicated, thereby also need further to improve and improve.Therefore, exploitation provides a kind of simple in structure, atmospheric pressure ion source low, soft ionization that consumes energy that can overcome problems to be significant.
Summary of the invention
Present situation and deficiency for existing normal pressure Ionization Techniques In Mass Spectrometry, the utility model aims to provide the micro-glow discharge maldi mass spectrometer of a kind of normal pressure based on the micro-glow discharge plasma of normal pressure ion gun, and the normal pressure maldi mass spectrometer analytical equipment being formed by it, the problem existing to solve existing normal pressure Ionization Techniques In Mass Spectrometry.
The micro-glow discharge maldi mass spectrometer of the normal pressure ion gun that the utility model provides, it is a kind of normal pressure maldi mass spectrometer ion gun based on the micro-glow discharge plasma of normal pressure, it forms and to be mainly included in the microplasma generation cavity that processes on insulation material base member, to be fixedly installed on microplasma generation cavity wall for puncturing pair of electrodes that work gas produces electric discharge and being fixed on microplasma generation cavity entrance point for being connected the gas circuit X-over of work gas drawing-in system, and described electrode is connected with the D.C. regulated power supply of 80～3000V.Described electrode preferably can be connected at the D.C. regulated power supply of 200～500V range regulation with voltage; The import of microplasma generation cavity is preferably connected with the work gas drawing-in system that is designed with gas flow controller by gas circuit X-over, to guarantee that the flow velocity of working gas is controlled in 0.5L/min～2.5L/min scope.The flow velocity of working gas exceeds this scope (lower than 0.5L/min or higher than 2.5L/min), and ion gun provided by the utility model still can normally be worked.Put on the operating voltage of electrode generally in the scope of 200～500V, general power is less than 4W.
In technique scheme of the present utility model, described microplasma generation cavity is paid the utmost attention to and is adopted the tube chamber that section is rectangle, and one of the height of tube chamber section or width are not more than 1 millimeter.Described electrode preferentially adopts pellet electrode.Two plate electrodes that form electrode pair are preferably fixedly installed on two walls that two walls distances in microplasma generation cavity are not more than 1 millimeter Face to face.For being fixedly installed the wall in the microplasma generation cavity of pellet electrode, it is preferably not less than 1 millimeter in the size perpendicular to tube chamber direction.Described electrode is preferably fixed on its ejiction opening of distance in microplasma generation cavity and is not more than 10 millimeters of positions, and the distance conventionally adopting is 1～3 millimeter.
In technique scheme of the present utility model, the material of described electrode is the metal material of conduction, as, platinum, copper, silver etc., preferentially select purity to be not less than 99.99% platinum or brass; The material of described base member is insulating material, as pottery, teflon, quartz or bakelite etc.; Preferentially select alundum (Al2O3) purity to be not less than 96% pottery, bakelite, quartz.
The mass spectrometer being formed by the micro-glow discharge maldi mass spectrometer of above-mentioned normal pressure ion gun, its formation comprises work gas drawing-in system, the micro-glow discharge maldi mass spectrometer of described normal pressure ion gun, D.C. regulated power supply, mass spectrometer and mass spectrometric data disposal system, the micro-glow discharge maldi mass spectrometer of described normal pressure ion gun is connected with work gas drawing-in system by its pipeline X-over, its electrode and D.C. regulated power supply both positive and negative polarity connect and compose loop, described mass spectrometer is connected with described mass spectrometric data disposal system, described direct supply is that voltage can be at the D.C. regulated power supply of 80～3000V range regulation, when mass spectrometer is used, the microplasma generation cavity ejiction opening of its mass ion source and the import of described mass spectrometer plasma gas are facing to the sample between them.
In above-mentioned mass spectrometer of the present utility model, the micro-glow discharge maldi mass spectrometer of described normal pressure ion gun is preferably arranged on can be on the vertical rotary platform of 0～90 ° of scope rotation of vertical plane, described universal stage is arranged on 3 dimension translation stages, so that regulate the relative position between ion gun microplasma generation cavity ejiction opening and sample, the import of mass spectrometer plasma gas, make the plasma gas aligning testing sample from the ejection of microplasma generation cavity ejiction opening.
In above-mentioned mass spectrometer of the present utility model, described work gas drawing-in system is preferably provided with gas flow controller, to guarantee that the flow velocity of working gas is controlled in 0.5L/min～2.5L/min scope.
In above-mentioned mass spectrometer of the present utility model, described direct supply is preferably voltage can be at the D.C. regulated power supply of 200～500V range regulation, putting on electrode makes the Ionized Current Control of working gas in 2～20mA scope, be generally less than 4W for Ionized general power, make to be controlled at 20～100 ℃ of scopes from the temperature of the plasma gas of microplasma generation cavity ejiction opening ejection.
Being applicable to working gas of the present utility model 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 placed in the mass flow controller on pipeline between steel cylinder and ion gun by one and control, the general 0.5～2.5L/min of flow velocity of work gas.
The micro-glow discharge maldi mass spectrometer of the normal pressure analytical equipment that employing is provided by the utility model carries out mass spectrophotometry to sample, and the form of sample can be solid-state, liquid state 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 the import of mass spectrometer plasma gas, from the plasma gas blowout of microplasma generation cavity ejiction opening ejection to testing sample, make the molecule of sample surfaces that desorb, ionization occur under the effect of plasma gas.For gaseous sample, can take sample gas to be diffused in around microplasma generation cavity ejiction opening, allow the gaseous sample effect directly and ambient atmosphere of plasma gas from the ejection of ion gun microplasma generation cavity ejiction opening, make sample ions.After sample is ionized, by the import of mass spectrometer plasma (orifice) gas, enter mass spectrometer, carry out sample mass spectrophotometry.
The micro-glow discharge maldi mass spectrometer of the normal pressure analytical equipment that employing is provided by the utility model carries out mass spectrophotometry to sample, at different working gas flow velocitys with put on electrode and puncture under working gas strength of current, ionic strength and the kind of gained mass spectrogram have difference.This is because under different strength of current, contained active component in plasma, i.e. and metastable atom, content is different, thereby the Ionization Efficiency of sample is had to impact; And under different working gas flow velocitys, the temperature of plasma gas is different, plasma linear velocity is also different, thereby can make the primary desorption mechanism (thermal desorption, momentum desorb) of sample change, thereby further affects follow-up ionization process.Therefore, user can regulate ionogenic strength of current, gas flow rate according to actual conditions, to reach best test effect.
The micro-glow discharge maldi mass spectrometer of the normal pressure analytical equipment that employing is provided by the utility model carries out mass spectrophotometry to sample, and under mass spectrographic positive ion and negative ion scan pattern, the mass spectrogram of resulting testing sample is also different.When this is because adopts the utility model ion gun ionized sample, the formation mechanism of negative ions is different.The forming process of positive ion comprises that Penning ionization, proton translocation, electric charge shift, and wherein Proton-Transfer Reactions will form [M+H]
+ion, proton is mainly provided by a water bunch group, and water bunch group is mainly by metastable atom (He
m) produce by Penning ionization with the moisture in atmosphere.In order further to verify ionization mechanism, the emission spectrum within the scope of 200～1100nm of plasma is analyzed (Fig. 3, Fig. 4), N
2, NO, and the existence at OI peak proved the existence of charge transfer process, the auxiliary existence that has confirmed proton transfer in OH peak, ArI and HeI provide theoretical foundation for Penning ionization.Under positive ion mode, the reaction occurring under plasma (take helium as the example) guiding of ion gun ejection provided by the utility model is as follows:
He
*+nH
2O→He+(H
2O)
n-1H
++OH
-
He
*+M→He+M
++e
-
(H
2O)
nH
++M→M(H
2O)
n-1H
++H
2O
Under negative ion mode, O
2 -for main active agent, by deprotonation mechanism, O
2 -thereby the proton on picked-up testing sample molecule is produced to [M-H]
-ion, is shifted with electron capture mechanism and will be produced M by electronics
-ion.M
-the forming process of ion is as follows:
Normal pressure based on the micro-glow discharge plasma of the normal pressure provided by the utility model maldi mass spectrometer ion gun of increasing income, compares with existing mass ion source, has following very outstanding technique effect and advantage:
1, the normal pressure maldi mass spectrometer ion gun based on the micro-glow discharge plasma of normal pressure provided by the utility model, can directly be connected with the mass spectrometer with atmospheric pressure interface, can realize the detection to solid, liquid, gaseous sample, and easy disassembling.
2, ion gun outward appearance provided by the utility model is small and exquisite, is applicable to the Application and Development of follow-up portable mass spectrometer.
3, ion gun simple structure provided by the utility model, material is easy to get, easy to make, and manufacturing cost is far below other existing ion guns.
4, the power that maintains the ionogenic direct supply of normal pressure maldi mass spectrometer based on the micro-glow discharge plasma of normal pressure provided by the utility model is not more than 4W, and voltage is generally not more than 500V, and energy resource consumption is low compared with other ion guns.
5, adopt and be equipped with ionogenic mass spectrometer provided by the utility model to detect sample, plasma plume is high-visible, is convenient to the adjustment calibration to sample and ionogenic relative position; Plasma plume energy is low, temperature is low, can sample surfaces not caused and be burnt, and therefore this inspection method is that a kind of nothing is hindered analytical approach.
6, adopt and be equipped with ionogenic mass spectrometer provided by the utility model to detect sample, do not need sample to carry out pre-service, easy and simple to handle, the qualitative analysis time used few (being less than 5s).
7, adopt and be equipped with ionogenic mass spectrometer provided by the utility model to detect sample, sensitive to trace samplings response, reaction is fast, can realize high-throughout on-line analysis.
8, adopt and be equipped with ionogenic mass spectrometer provided by the utility model to detect sample, do not need the auxiliary of reagent of spraying, can be to environment.
Normal pressure maldi mass spectrometer ion gun based on the micro-glow discharge plasma of normal pressure provided by the utility model, its advantage sums up and comprises: energy consumption is low, profile is small and exquisite, simple in structure, easy and simple to handle, without sample pretreatment, analyze rapidly, can reach without wound analysis, cleanliness without any pollution etc.
Accompanying drawing explanation
Accompanying drawing 1-1 is the plan structure schematic diagram of an embodiment of the micro-glow discharge maldi mass spectrometer of normal pressure of the present utility model ion gun; Accompanying drawing 1-2 is the left TV structure schematic diagram of accompanying drawing 1-1; Accompanying drawing 1-3 is the ionogenic inner structure schematic diagram of the micro-glow discharge maldi mass spectrometer of normal pressure shown in accompanying drawing 1-1.
Accompanying drawing 2 is to be equipped with the micro-glow discharge maldi mass spectrometer of the ionogenic normal pressure of the utility model analytical equipment to detect the mode schematic diagram of analyzing solid, fluid sample.
Accompanying drawing 3 is utilizing emitted light spectrograms of the micro-glow discharge argon plasma of normal pressure.
Accompanying drawing 4 is utilizing emitted light spectrograms of the micro-glow discharge helium plasma of normal pressure.
Accompanying drawing 5 is to detect and analyze airborne DMF gas gained mass spectrogram with the mass spectrometer that is equipped with the micro-glow discharge plasma maldi ion source of the utility model normal pressure.
Accompanying drawing 6 is with being equipped with the mass spectrometer of the micro-glow discharge plasma maldi ion source of the utility model normal pressure to detect the methyl alcohol of analyzing paracetamol: water (1:1) solution gained mass spectrogram.
Accompanying drawing 7 is to detect and analyze reserpine powder gained mass spectrogram with the mass spectrometer that is equipped with the micro-glow discharge plasma maldi ion source of the utility model normal pressure.
Accompanying drawing 8 is to detect and analyze cigarette cut tobacco gained mass spectrogram with the mass spectrometer that is equipped with the micro-glow discharge plasma maldi ion source of the utility model normal pressure.
Accompanying drawing 9 is with being equipped with the mass spectrometer of the micro-glow discharge plasma maldi ion source of the utility model normal pressure to carry out the quantitative curve of semi-quantitative analysis gained and corresponding mass spectrogram to phenaetin solution.
In above-mentioned accompanying drawing, the object of each shown by reference numeral sign is respectively: 1-ion gun base member; 2-electrode; 3-gas circuit X-over; 4-microplasma generation cavity ejiction opening; 5-gas circuit X-over air intake opening; 6-microplasma generation cavity; 7-plasma plume; The import of 8-mass spectrometer plasma gas; 9-sample ions body; 10-sample; 11-sample supporting body; 12-mass spectrometer.
Embodiment
Below in conjunction with embodiment, the utility model is described in further detail; it is important to point out; following embodiment is only described further invention; scope of the present utility model is not subject to the restriction of illustrated embodiment; be familiar with one of ordinary skill in the art according to the content of foregoing invention; the utility model is made some nonessential improvement and adjusted and concrete enforcement, must belong to protection domain of the present utility model.
Embodiment 1
The present embodiment based on the micro-glow discharge maldi mass spectrometer of normal pressure ion gun, its structure is as accompanying drawing 1-1, shown in accompanying drawing 1-2 and accompanying drawing 1-3, form and be mainly included in the microplasma generation cavity processing on base member 1, be embedded in face-to-face the pellet electrode 2 that produces a pair of platinum product matter of electric discharge in microplasma generation cavity on upper and lower two walls for puncturing work gas, with be fixed on microplasma generation cavity entrance point for being connected the gas circuit X-over 3 of work gas drawing-in system, described base member is that alundum (Al2O3) purity is not less than 96% pottery, the both positive and negative polarity of described electrode 2 and the D.C. regulated power supply that can regulate between 80～3000V connects and composes loop, two platinum electrode sheets are arranged on apart from 4 approximately 1 millimeters of places of microplasma generation cavity ejiction opening, to reduce the interference of outer gas stream to discharge generation, and guarantee can extend to micro-plasma generation cavity from the plasma plume of micro-plasma generation cavity ejiction opening 4 ejections, with calibration sample and ionogenic relative position.The channel size of described plasma generation cavity: long 26.6 millimeters, wide 2.4 millimeters, high 0.7 millimeter.High-temperature-resistant epoxy resin glue sealed attachment for described gas circuit conversion head and the import of microplasma generation cavity, to guarantee the impermeability of microplasma generation cavity inner air path.While detecting sample with this ion gun, working gas (argon gas or helium) is entered in microplasma generation cavity 6 by the air intake opening 5 of described gas circuit conversion head end, flowing through the micro-glow discharge of the two electrode 2 breakdown generation normal pressures in place, thus produce ionized sample institute necessary microplasma 7.
Embodiment 2
The micro-glow discharge maldi mass spectrometer of the normal pressure analytical equipment of the present embodiment, its form mainly comprise the micro-glow discharge maldi mass spectrometer of normal pressure ion gun described in work gas drawing-in system, embodiment 1, voltage can be in direct supply, mass spectrometer and the mass spectrometric data disposal system of 80～3000V range regulation.The micro-glow discharge maldi mass spectrometer of described normal pressure ion gun is clamped on the vertical rotary platform that can rotate within the scope of 0～90 ° of vertical direction, and described vertical rotary platform is placed on 3 dimensions (3D) translation stage.Described work gas drawing-in system is helium or the argon gas steel cylinder that is provided with mass flowmeter, usings and guarantees as the helium of working gas or the flow control of argon gas in microplasma generation cavity in 0.5～2.5L/min scope.The micro-glow discharge maldi mass spectrometer of described normal pressure ion gun is connected with work gas drawing-in system by its pipeline X-over 3, ionogenic two pellet electrodes of the micro-glow discharge maldi mass spectrometer of normal pressure and described voltage can connect and compose loop at the direct supply both positive and negative polarity of 80～3000V range regulation, the plasma ejiction opening 4 of the ionogenic plasma generation cavity of the micro-glow discharge maldi mass spectrometer of normal pressure and described mass spectrometric sample plasma gas entrance 8 are facing to being held in place the sample on supporting body 11 10 between them, described mass spectrometer 12 is connected with described mass spectrometric data disposal system.
Embodiment 3
Described in utilization embodiment 2, the micro-glow discharge maldi mass spectrometer of normal pressure analytical equipment is analyzed solid-state, liquid sample.Solid-state (or liquid) sample 10 is held in place on the supporting body 11 between ion source plasma ejiction opening and mass spectrometer plasma gas import 8, allow and aim at testing sample from the plasma gas of ion gun ejiction opening ejection, make the molecule of sample surfaces that desorb, ionization occur under the effect of plasma gas.Carrier for bulk, paste, liquid sample, can be simple glass microslide, filter paper, potsherd, stainless steel substrates etc., liquid sample also can directly be placed in vessel, powdered samples need be fixed on above-mentioned carrier and detect with double faced adhesive tape, in case powdered sample enters mass spectrometer with air-flow, stop up mass spectrometer entrance.The horizontal range of sample and mass spectrometer entrance is 5～20 millimeters, and vertical range is 2～10 millimeters.The horizontal range of ion gun and sample is generally 1～5 millimeter, and vertical range is 1～5 millimeter, and the horizontal range of ion gun and mass spectrometer entrance is generally 10～20 millimeters.The plasma gas bundle that ion gun sprays and the angle of sample surfaces are adjustable flexibly within the scope of 0～90 °, to guarantee obtaining optimum spectrum signal in actual testing process.
Embodiment 4
The micro-glow discharge plasma maldi mass spectrometer of normal pressure analytical equipment described in Application Example 2 is analyzed gaseous sample, mode of operation is substantially the same manner as Example 3, can directly will container and the ion source plasma generation cavity ejiction opening surrounding environment UNICOM of gaseous sample be housed, make gaseous sample diffuse to ion source plasma generation cavity ejiction opening ambient atmosphere, ion gun can produce responsive response to the trace samplings in atmosphere.Gaseous sample also can import the space between ion source plasma generation cavity ejiction opening and the import of mass spectrometer plasma by conduit or sample introduction needle, by adjusting the relative position of plasma gas bundle and the import of mass spectrometer plasma gas, obtains best mass signal.
Embodiment 5
The airborne organic gas of the micro-glow discharge plasma maldi mass spectrometer of normal pressure analytical equipment testing environment described in Application Example 2, the airborne DMF (DMF) of specifically take is detected object.
DMF is scientific experiment, conventional organic reagent while manufacturing, this reagent highly volatile, by human body, sucked or skin contact after will work the mischief to human body.With ion gun provided by the utility model, detect airborne DMF, adopt argon gas as plasma work gas, the strength of current that setting puts on plasma work gas is 14mA, argon gas flow velocity 1.5L/min, is placed on the reagent bottle that DMF solvent is housed apart from approximately 1 meter of of ion gun, opens wide bottle cap contact atmosphere and removes after 5 seconds, approximately 3 seconds time delay, DMF gas diffuse to around ion gun, and mass spectrometer obtains rapidly the mass spectrogram of DMF, as shown in Figure 5.In figure, DMF corresponding to peak that m/z is 74, i.e. [M+H]
+, the peak corresponding [M-CO+H] that m/z is 46
+.
Embodiment 6
The micro-glow discharge plasma maldi mass spectrometer of normal pressure analytical equipment tracer liquid sample described in Application Example 2, the solution of paracetamol of specifically take is detected object.
Pure paracetamol powder is dissolved in to methyl alcohol: water is 50:50(v:v) solvent in make the solution that paracetamol content is 30mg/L.With liquid-transfering gun, pipette 2 these solution of μ L and drip on the microslide with little groove, or other any can be used for, hold in the opening vessel of reagent.The vessel that carried fluid sample are placed between ion gun microplasma gas generation cavity ejiction opening and mass spectrometer plasma gas entrance, regulate as the helium flow velocity of work gas and the strength of current puncturing, to obtain best mass signal.The final gained mass spectrogram of aforesaid operations as shown in Figure 6, the protonated dimer [2M+H] of the corresponding paracetamol in peak, m/z=303 place
+, peak, m/z=270 place is the protonated molecular ion peak of plastifier neck dibatyl phithalate, and this ion all may be introduced in detection system when using most of experiment equipment containing plasticiser, and the peak at m/z=152 place belongs to [M+H] of paracetamol
+peak.By the clear and definite easily identification of the whole peak of the paracetamol solution mass spectrogram shown in accompanying drawing 6 type, impurity peaks and fragment peak are less, therefore with ion gun provided by the utility model, fluid sample are carried out to qualitative analysis tool and have great advantage.
Embodiment 7
The micro-glow discharge plasma maldi mass spectrometer of normal pressure analytical equipment described in Application Example 2 detects solid sample, specifically take reserpine powder as detected object.Reserpine powder is spread upon equably on the microslide that posts double faced adhesive tape, with the light pressure-like product of spoon, to guarantee that powder is adsorbed on double faced adhesive tape securely, use ion gun provided by the utility model to analyze reserpine powder composition.In the mass spectrogram of reserpine (accompanying drawing 7), topmost peak is the reserpine [M+H] at m/z=610 place
+peak, the fragment peak that the peak of all the other several obvious use " * " marks is reserpine, the wherein corresponding [M-COOCH in the peak at m/z=536 place
3-CH
3+ H]
+.
Embodiment 8
The micro-glow discharge plasma maldi mass spectrometer of normal pressure analytical equipment described in Application Example 2, analyzes the complex sample in real life, and the cigarette that shop buys that specifically take is monitoring target.Cut the cigarette of buying from shop open cigarette paper, get appropriate pipe tobacco and adhere on the microslide that has pasted double faced adhesive tape, use ion gun provided by the utility model to analyze the principal ingredient in pipe tobacco.Mass spectrogram (accompanying drawing 8) by pipe tobacco can be seen obvious nicotine protonated molecular ion peak (m/z=163), and the CID figure that figure is m/z=163 place parent ion is inserted in upper right side, is the feature fragment peak of nicotine molecule shown in figure.The peak at m/z=149 place belongs to adjuvant contained in cigarette paper, the variant of ethyl benzoate.Due to cigarette complicated component, in accompanying drawing 8, also to there be many other not belong to peak, in practical operation, can need to be optimized instrument condition according to detecting, and by means such as tandem mass spectrums, each peak be belonged to.
Embodiment 9
The micro-glow discharge plasma maldi mass spectrometer of normal pressure analytical equipment described in Application Example 2, can carry out semi-quantitative analysis to sample separately, specifically take phenaetin as analytic target.
Phenaetin powder is dissolved in to the solution that is configured to a series of variable concentrations in pure methyl alcohol, as adding a certain amount of paracetamol as internal standard compound in every a solution, and the concentration that guarantees paracetamol in every a solution is all identical, and each duplicate samples is detected successively from low concentration to high concentration.Input mode can be directly solution is contained in uncovered vessel, or by 5 μ L sample drops on filter paper, use ion gun provided by the utility model to analyze sample.The attached quantitative curve that adopts argon plasma gained phenaetin that Figure 9 shows that, sample introduction carrier used is filter paper, on linear regression line, the concentration of each point is the concentration of phenaetin sample, and each puts the ratio that corresponding intensity is phenaetin and the peak area of paracetamol in sample gained mass spectrum ion flow graph.Under this sets, the sensing range of phenaetin is 10
4, each sampled point all repeats sample introduction 8 times, and RSD scope corresponding to each point is 10%～20%.It should be noted that, this is exemplified as sample introduction manually, thereby human factor is disturbed very large to the degree of accuracy detecting, repeatability.Introduce automatic sampling apparatus (as peristaltic pump, mechanical pump, chromatogram relevant apparatus) and will improve significantly and be equipped with the utility model that ionogenic mass spectrometric quantitative performance is provided, thereby suction ion gun provided by the utility model has distinguished potential in scientific quantitative analysis analysis.
Claims (10)
1. the micro-glow discharge maldi mass spectrometer of a normal pressure ion gun, it is characterized in that, mainly be included in the microplasma generation cavity (6) that processes in insulation material base member (1), be fixedly installed on microplasma generation cavity wall for puncturing pair of electrodes (2) that work gas produces electric discharge and being fixed on microplasma generation cavity entrance point for being connected the gas circuit X-over (3) of work gas drawing-in system, described electrode is connected at the adjustable D.C. regulated power supply of 80～3000V with voltage can be provided.
2. the micro-glow discharge maldi mass spectrometer of normal pressure according to claim 1 ion gun, is characterized in that, the section configuration of described microplasma generation cavity (6) is rectangle tube chamber, and one of the height of tube chamber section or width are not more than 1 millimeter.
3. the micro-glow discharge maldi mass spectrometer of normal pressure according to claim 2 ion gun, is characterized in that, described electrode is pellet electrode, and two plate electrodes are fixedly installed on two walls that two walls distances in microplasma generation cavity are not more than 1 millimeter Face to face.
4. the micro-glow discharge maldi mass spectrometer of normal pressure according to claim 3 ion gun, is characterized in that, described microplasma generation cavity is used for the fixedly wall of pellet electrode and is not less than 1 millimeter in the size perpendicular to runner direction.
5. according to the micro-glow discharge maldi mass spectrometer of the normal pressure one of claim 1 to 4 Suo Shu ion gun, it is characterized in that, described electrode is fixedly installed on its ejiction opening of distance in microplasma generation cavity and is not more than in the position of 10 millimeters.
6. the micro-glow discharge maldi mass spectrometer of normal pressure according to claim 5 ion gun, is characterized in that, the material of described electrode is conductive metallic material, and the material of described base member is pottery, teflon, quartz or bakelite.
7. the mass spectrometer being formed by the micro-glow discharge maldi mass spectrometer of the described normal pressure of one of claim 1 to 6 ion gun, it is characterized in that, comprise work gas drawing-in system, the micro-glow discharge maldi mass spectrometer of described normal pressure ion gun, D.C. regulated power supply, mass spectrometer and mass spectrometric data disposal system, the micro-glow discharge maldi mass spectrometer of described normal pressure ion gun is connected with work gas drawing-in system by its pipeline X-over, its electrode and described D.C. regulated power supply both positive and negative polarity connect and compose loop, described mass spectrometer is connected with described mass spectrometric data disposal system, described direct supply is that voltage can be at the D.C. regulated power supply of 80～3000V range regulation, when mass spectrometer is used, the microplasma generation cavity ejiction opening of its mass ion source and the import of described mass spectrometer plasma gas are facing to the sample between them.
8. the micro-glow discharge maldi mass spectrometer of normal pressure according to claim 7 analytical equipment, it is characterized in that, described normal pressure maldi mass spectrometer ion gun is arranged on can be on the vertical rotary platform of 0～90 ° of scope rotation of vertical plane, described universal stage is arranged on 3 dimension translation stages, so that regulate the relative position between normal pressure maldi mass spectrometer ion gun microplasma generation cavity ejiction opening and sample, the import of mass spectrometer plasma gas, make the plasma gas aligning testing sample from the ejection of plasma generation cavity ejiction opening.
9. the micro-glow discharge maldi mass spectrometer of normal pressure according to claim 7 analytical equipment, is characterized in that described work gas drawing-in system is provided with gas flow controller, to guarantee that the flow velocity of working gas is controlled in 0.5L/min～2.5L/min scope.
10. the micro-glow discharge maldi mass spectrometer of normal pressure according to claim 7 analytical equipment, is characterized in that, described D.C. regulated power supply is that voltage can be at the D.C. regulated power supply of 200～500V range regulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420166654.7U CN203772818U (en) | 2014-04-08 | 2014-04-08 | Normal-pressure micro-glow discharge desorption mass spectrum ion source and mass spectrometry device formed by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420166654.7U CN203772818U (en) | 2014-04-08 | 2014-04-08 | Normal-pressure micro-glow discharge desorption mass spectrum ion source and mass spectrometry device formed by same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN203772818U true CN203772818U (en) | 2014-08-13 |
Family
ID=51289996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201420166654.7U Expired - Lifetime CN203772818U (en) | 2014-04-08 | 2014-04-08 | Normal-pressure micro-glow discharge desorption mass spectrum ion source and mass spectrometry device formed by same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN203772818U (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104749139A (en) * | 2015-03-26 | 2015-07-01 | 四川大学 | Matrix-assisted excitation spectrum detection system adopting plasma surface sample injection |
| CN107643357A (en) * | 2016-07-21 | 2018-01-30 | 中国石油化工股份有限公司 | The analysis method of steroid alkyl compound in a kind of petroleum geology sample |
| CN111929354A (en) * | 2020-07-02 | 2020-11-13 | 东华理工大学 | Rare earth ore sample ionization analytical instrument in order |
| CN114544795A (en) * | 2020-11-25 | 2022-05-27 | 豪夫迈·罗氏有限公司 | Anomaly detection of gas flow parameters in mass spectrometry |
-
2014
- 2014-04-08 CN CN201420166654.7U patent/CN203772818U/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104749139A (en) * | 2015-03-26 | 2015-07-01 | 四川大学 | Matrix-assisted excitation spectrum detection system adopting plasma surface sample injection |
| CN104749139B (en) * | 2015-03-26 | 2018-08-03 | 四川大学 | Plasma surface sample introduction excitation spectrum detecting system under matrix auxiliary |
| CN107643357A (en) * | 2016-07-21 | 2018-01-30 | 中国石油化工股份有限公司 | The analysis method of steroid alkyl compound in a kind of petroleum geology sample |
| CN111929354A (en) * | 2020-07-02 | 2020-11-13 | 东华理工大学 | Rare earth ore sample ionization analytical instrument in order |
| CN111929354B (en) * | 2020-07-02 | 2021-09-17 | 东华理工大学 | Rare earth ore sample ionization analytical instrument in order |
| CN114544795A (en) * | 2020-11-25 | 2022-05-27 | 豪夫迈·罗氏有限公司 | Anomaly detection of gas flow parameters in mass spectrometry |
| CN114544795B (en) * | 2020-11-25 | 2024-01-05 | 豪夫迈·罗氏有限公司 | Anomaly detection of gas flow parameters in mass spectrometry |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102129950B (en) | Microwave plasma ordinary-pressure desorption ionization source and application thereof in mass spectrum analysis | |
| CN103901145A (en) | Normal-pressure micro-glow discharge desorption mass spectrum ion source and mass spectrometry device composed of ion source | |
| US8461523B2 (en) | Ionizer for vapor analysis decoupling the ionization region from the analyzer | |
| CN104241077B (en) | Normal pressure micro-glow discharge maldi mass spectrometer ion gun of magnetically confined and mass spectrometer | |
| CN101770924B (en) | Desorbing ionization device | |
| EP3069375B1 (en) | Concentric apci surface ionization ion source, ion guide, and method of use | |
| CN101113970B (en) | Mass spectra ion source without external high pressure and ionization analytical method thereof | |
| CN203772818U (en) | Normal-pressure micro-glow discharge desorption mass spectrum ion source and mass spectrometry device formed by same | |
| EP2435166A1 (en) | Direct atmospheric pressure sample analyzing system | |
| CN101211741A (en) | Mass spectrometer multifunctional multichannel ion source | |
| CN106841367A (en) | A kind of Ion transfer spectrum detection method of time resolution Dynamic Thermal parsing | |
| CN102768236A (en) | Multifunctional multi-channel ion source for mass spectrometer and mass spectrum analysis method for trace components in original sample | |
| CN202111053U (en) | Surface extraction chemical ionization source | |
| CN103779170B (en) | A kind of electrospray ion source device | |
| CN109643636A (en) | Low temperature plasma probe with auxiliary heating gas jet flow | |
| CN201185172Y (en) | Surface desorption atmospheric chemical ionization source | |
| CN106876241A (en) | Ultrasonic atomizatio Atomospheric pressure glow discharge ionization device | |
| CN103236394A (en) | Microwave plasma based atmospheric pressure desorption ion source and application thereof | |
| US20150144777A1 (en) | Multiple solid phase micro-extraction thermal desorption ionization device, mass spectrometer and analytical method for mass spectrometry | |
| CN102938360B (en) | A kind of mass spectrum ionization source of large area in situ detection explosive and application thereof | |
| Xu et al. | Online coupling techniques in ambient mass spectrometry | |
| CN111540665A (en) | Ionization device and application thereof | |
| CN108008001A (en) | Improve three peroxidating diamines of hexa-methylene（HMTD）The detection method of dosing accuracy | |
| Zhang et al. | Exploiting the native inspiratory ability of a mass spectrometer to improve analysis efficiency | |
| CN115116819A (en) | Electrospray extraction ionization source |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20140813 |