CN106093179B - A kind of real-time Mass Spectrometer Method device and method for the constituent analysis of gas anion and its with compound interaction - Google Patents
A kind of real-time Mass Spectrometer Method device and method for the constituent analysis of gas anion and its with compound interaction Download PDFInfo
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- CN106093179B CN106093179B CN201610367472.XA CN201610367472A CN106093179B CN 106093179 B CN106093179 B CN 106093179B CN 201610367472 A CN201610367472 A CN 201610367472A CN 106093179 B CN106093179 B CN 106093179B
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- 150000001450 anions Chemical class 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000004458 analytical method Methods 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 239000000470 constituent Substances 0.000 title claims abstract description 22
- 230000003993 interaction Effects 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000007921 spray Substances 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 149
- 150000002500 ions Chemical class 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 230000009471 action Effects 0.000 claims description 22
- 239000006199 nebulizer Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000001819 mass spectrum Methods 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000004615 ingredient Substances 0.000 abstract description 7
- 238000004451 qualitative analysis Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 2
- 239000003570 air Substances 0.000 description 24
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 14
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- 238000011897 real-time detection Methods 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/68—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
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- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The present invention relates to a kind of real-time Mass Spectrometer Method devices for the constituent analysis of gas anion and its with compound interaction, which includes the gas anion generator being fixed on pedestal；The liquid spray component for being set to the mass detector of face gas anion generator outlet end and being set between gas anion generator outlet end and the arrival end of the mass detector and liquefied compound spray flow capable of being made to mix with the gas flow flowed out from gas anion generator outlet end in right-angled intersection.The invention further relates to a kind of real-time Mass Spectrometry detection methods for carrying out the constituent analysis of gas anion using apparatus of the present invention and its interacting with compound.Device and method provided by the invention can both realize the qualitative analysis to gas anion ingredient, the real-time online detection and qualitative analysis that the process of chemical reaction is participated in gas anion can be realized again, to realize the form and its chemical property for fully understanding gas anion.
Description
Technical field
The invention belongs to gas anion technology fields, and in particular to one kind for the constituent analysis of gas anion and its with
The real-time Mass Spectrometer Method device and method of compound interaction.
Background technique
Studies have shown that negative aeroion, which has, to be improved human health, effectively removes haze, degradation harmful pollution gas and kill
The remarkable advantages such as bacterium, therefore, negative aeroion cause the extensive concern of people, and negative aeroion is Environmental Health field
A kind of potential technological means of novelty is provided, there is boundless application prospect.The way of production of negative aeroion is more
Sample can pass through electricity in modes such as nature such as forests, waterfall either artificial means such as corona discharge, nano material
Son is reacted with the collision of oxygen molecule and a series of subsequent molecular ions and is generated.However it is strong in environment to negative aeroion
The mechanism of action in terms of health is still not clear, need deeper into research negative aeroion property to obtain maximum benefit
With.This to become especially urgent to negative aeroion constituent analysis and its with the research of compound interaction aspect.It is common
Instrument for detecting negative aeroion is Ion Counting instrument, can only carry out quantitative analysis to total ion concentration, can not divide
The various ion component types contained in negative aeroion are precipitated, to greatly limit the application range of this method.
Mass spectrum because its with high specificity, high sensitivity, amount of samples are few, analysis speed is fast, multiple spot multi-analyte immunoassay, can
The advantage of open type operation and real-time detection identification, is widely used in chemical, environmental science, medical science, life science
With the fields such as material science.These mass spectrographic distinguishing features become negative aeroion constituent analysis and its mutual with compound
The powerful of Effect study is conducive to grasp reaction by the real time monitoring that mass spectrum participates in chemical reaction to negative aeroion
Progress and understand its reaction mechanism, negative aeroion form is screened and its research of the mechanism of action has highly important meaning
Justice.
It is had existed in the prior art about the report studied using mass spectrum negative aeroion.In negative aeroion
In terms of constituent analysis, existing apparatus is difficult to realize simultaneously generates negative aeroion and subsequent chemistry instead in certain specific gas
It answers, and cumbersome, at high cost due to processing, is not easy to regulate and control the various parameters for influencing negative aeroion generation.In addition,
Negative aeroion and compound interaction aspect are studied, the compound that existing apparatus is used to react with negative aeroion is by matching
The mode of gaseous mixture processed either heating and gasifying generates, and higher cost is troublesome in poeration, very especially for the higher compound of boiling point
Difficulty is gasified.This makes existing apparatus for the research of negative aeroion by biggish limitation.
Therefore, presently, there are the problem of be badly in need of researching and developing it is a kind of it is novel for the constituent analysis of gas anion and its
With the real-time Mass Spectrometer Method device and method of compound interaction.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide one kind for gas bear from
Real-time Mass Spectrometer Method device subconstiuent analysis and its interacted with compound.The device include gas anion generator,
Liquid spray component and mass detector.The constituent analysis of gas anion is carried out using apparatus of the present invention the invention further relates to a kind of
And its real-time Mass Spectrometry detection method with compound interaction.Detection device collection gas anion generator of the invention, liquid
Spray body component and mass detector can not only realize the qualitative analysis to gas anion ingredient in one, but also can realize to gas
Body anion participates in the real-time online detection and qualitative analysis of chemical reaction process, to fully understand the form of gas anion
And its chemical property.
For this purpose, first aspect present invention provide it is a kind of for the constituent analysis of gas anion and its with compound phase interaction
Real-time Mass Spectrometer Method device comprising:
The gas anion generator being fixed on pedestal；
It is set to the mass detector of face gas anion generator outlet end；
It is set between gas anion generator outlet end and the arrival end of the mass detector and liquid can be made
State compound spray stream is sprayed with the gas flow flowed out from gas anion generator outlet end in the liquid that right-angled intersection mixes
Mist component.
According to the present invention, the gas includes but is not limited to the single gas of one of air, oxygen, nitrogen and carbon dioxide
The mixing of body or multiple gases.
In some preferred embodiments of the invention, the gas is air；The air is synthesis of air.The conjunction
Content at nitrogen in air is 79v%, and the content of oxygen is 21v%.
In some embodiments of the invention, gas anion generator outlet end and the mass detector entrance
The distance at end is 0.3-2.0cm.
According to the present invention, the gas anion generator includes that tee tube and the corona being set in the tee tube are put
Acusector and fixed pin and the needle stand that can be connect by conducting wire with high voltage power supply interface；It is located along the same line in the tee tube
Both ends in one end insertion needle stand and guarantee distal portion seal, the other end be gas anion generator outlet end；It is described
It with the perpendicular one end in the both ends that are located along the same line is gas access end in tee tube.
In some embodiments of the invention, the internal diameter of the tee tube is 3-10mm, preferably 5-8mm.If tee tube
Internal diameter be less than 3mm, then the side wall of gas anion generator outlet end is big to the screen effect of gas anion, so that from gas
Gas anion derived from body anion generator outlet end is less, to can not be detected by mass detector.If tee tube
Internal diameter be greater than 10mm, then it is relatively slow and outside air is made to penetrate into and draw to will lead to gas anion generator outlet end gas flow rate
Enter impurity, influences subsequent mass spectrometry results.
In some preferred embodiments of the invention, the tee tube is T-type glass tube.
In some embodiments of the invention, the tip of the corona discharge needle in the tee tube and the gas anion
The distance at generator exports end is 0-4.0cm, preferably 0.8-4.0cm.
In other embodiments of the invention, the material of the corona discharge needle includes in tungsten, iron, stainless steel and copper
It is one or more.In some preferred embodiments of the invention, the corona discharge needle is tungsten needle.
According to the present invention, the liquid spray component includes syringe, syringe pump, pneumatic nebulizer and connection syringe
The conduit of outlet and pneumatic nebulizer entrance.
Second aspect of the present invention provide it is a kind of utilize first aspect present invention described device carry out gas anion ingredient
Analysis and its real-time Mass Spectrometry detection method to interact with compound comprising:
Step A is passed through gas from the gas access end of tee tube, applies voltage to the tip of corona discharge needle, in corona
Under the action of electric discharge, gas flows through the tip of corona discharge needle and generates gas anion at the tip of corona discharge needle；It is described
Gas anion, which enters mass detector after the export of gas anion generator outlet end under the action of gas flow, to carry out
Gas anion constituent analysis；
Step B, under the action of syringe pump, the liquefied compound being loaded into syringe is sent into pneumatic spraying by conduit
In device, in pneumatic nebulizer under the action of stream of nitrogen gas, liquefied compound is sprayed from the outlet end of pneumatic nebulizer with liquid
Mist form export after, with derived from gas anion generator outlet end gas anion interact to be formed product from
Son；The product ion enters mass detector under the action of gas anion generator outlet end gas flow and carries out product
Ion component analysis.
In some embodiments of the invention, in step, the gas access end of the tee tube is passed through the flow velocity of gas
For 0.1-10.0L/min, preferably 5.0-10.0L/min；Tip institute's making alive of the corona discharge needle is 1.0-8.0KV,
Preferably 3.8KV-8.0KV.
In other embodiments of the invention, in stepb, the speed that pushes away of the syringe pump is 0-3000 μ L/h, preferably
For 3-3000 μ L/h；Nitrogen flow rate is 0-3.0L/min, preferably 0.5-3.0L/min in the pneumatic nebulizer.
In other embodiments of the invention, the mass detector uses open type detection mode, convenient in time by the longevity
Of short duration gas anion is ordered to import in mass detector to realize that real-time online detects.It is preferred that the mass detector detection
The mass-to-charge ratio (m/z) of ion is 10-2000.
Since there are error, the error range of the mass-to-charge ratio of the ion measured in experiment is ± 0.1 in test process.Example
Such as, the mass-to-charge ratio that ion is detected in mass detector is respectively 60.00,60.05 and 60.10, then ± 0.1 error model
In enclosing, it is believed that 60.00,60.05 and 60.10 ion can be CO3 -。
For convenient for analysis, the present invention is carrying out gas anion and gas anion and compound interacts the production to be formed
When the qualitative analysis of object ion, mass-to-charge ratio (m/z) the equal round numbers for the ion that mass detector detects.
Unless otherwise specified, the present invention is experimentally this field routine experiment method.
Unless otherwise specified, instrument of the present invention is this field conventional instrument.
Unless otherwise specified, agents useful for same and material of the present invention can be obtained through commercial channels.
" selection ion flow graph " of the present invention is obtained by mass spectral analysis, reflects a certain ion massspectrum peak intensity at any time
Between variation.
Real-time Mass Spectrometer Method provided by the present invention for the constituent analysis of gas anion and its with compound interaction
Device and method have the advantages that
(1) corresponding gas anion, and the complexity shorter to these service life can be generated under specific gas environment
The ingredient of gas anion carry out real-time quick qualitative analysis；
(2) gas anion and compound, the especially chemical reaction with higher-boiling compound interaction may be implemented
Real time monitoring, and then reasonable deduction is made to reaction mechanism；
(3) material therefor is at low cost, and agents useful for same is that chemical laboratory is common, and device package technique is simple, without big
Type, complex instrument equipment.
Detailed description of the invention
Fig. 1 is that interacting for the constituent analysis of gas anion and its with compound for the embodiment of the present invention 1 is real-time
The structural schematic diagram of Mass Spectrometer Method device.The meaning of appended drawing reference is as follows in Fig. 1: 1- tungsten needle；2-T type glass tube；3- needle stand；4-
Conducting wire；5- syringe pump；6- syringe；7- conduit；8- pneumatic nebulizer；9- mass detector.
Fig. 2 be according to the real-time Mass Spectrometer Method device of the embodiment of the present invention 1 to the gas generated in air atmosphere bear from
The mass spectrogram that subconstiuent is analyzed.
Fig. 3 be according to the real-time Mass Spectrometer Method device of the embodiment of the present invention 1 to the gas generated in air atmosphere bear from
Son carries out the selection ion flow graph of reproducibility analysis.
Fig. 4 be according to the real-time Mass Spectrometer Method device of the embodiment of the present invention 1 to the gas generated in air atmosphere bear from
Son carries out the selection ion flow graph of long-time stability analysis.
Fig. 5 be according to the real-time Mass Spectrometer Method device of the embodiment of the present invention 1 to the gas generated in air atmosphere bear from
Mass spectrogram and selection ion flow graph when son is chemically reacted with benzaldehyde interaction.
Fig. 6 be according to the real-time Mass Spectrometer Method device of the embodiment of the present invention 1 to the gas generated in air atmosphere bear from
Mass spectrogram and selection ion flow graph when son is chemically reacted with paraxylene interaction.
Specific embodiment
To keep the present invention easier to understand, next in the following with reference to the drawings and specific embodiments the present invention will be described in detail, these
Embodiment only serves illustrative, it is not limited to application range of the invention.
Using the 1750N type syringe of Hamilton Co. company production in the present invention.
Using the 100 type syringe pump of KDS of KD Scientific Inc. company production in the present invention.
The production obtained after being reacted with compound using mass detector gas anion or gas anion in the present invention
The ingredient of object ion carries out qualitative analysis, test condition: desolventizing tube temperature degree is 250 DEG C；Heating block temperature is 400 DEG C；It is dry
Pathogenic dryness flow is 0L/min；Full scan time is 0.5sec；Scanning speed is 2142u/sec.
The relative standard deviation calculation formula of ion peak intensity is shown in formula I:
In Formulas I,For the average value of each ion peak intensity；STDEV is the standard deviation of each ion peak intensity, uses Excel
It is calculated.
Embodiment
Embodiment 1: the real-time Mass Spectrometer Method device for the constituent analysis of gas anion and its with compound interaction
Assembling
As shown in Figure 1, one long-channel of processing is 10cm, short channel is the T-type glass tube 2 of 5cm, the T-type glass tube 2
Internal diameter be 8mm.Tungsten needle 1 is fixed on to the tip of needle stand 3, after by needle stand 3 be inserted into T-type glass tube 2 long-channel and be located at axis
At the heart, it is located at 1 tip of tungsten needle in T-type glass tube 2 and apart from 2 gas anion generator outlet end 5mm of T-type glass tube, and
Needle stand 3 and 2 end junction of T-type glass tube are sealed.Needle stand 3 can be connected by conducting wire 4 with negative high voltage power source (- HV) interface
It connects.It is fixed on pedestal (not indicated in figure) with upper-part.Position base is adjusted, the gas anion of T-type glass tube 2 is sent out
The arrival end and distance of raw device outlet end face mass detector 9 are 3mm.The short channel of T-type glass tube 2 passes through conduit and gas cylinder
(not indicating in figure) is connected.Syringe 6 containing liquefied compound is fixed on syringe pump 5, the outlet of syringe 6 passes through
Conduit 7 is connected to the entrance of pneumatic nebulizer 8.Mass detector 9 is operated using open type, is detected using negative ion mode.
According to specific requirement of experiment, the tip institute making alive of tungsten needle 1 is set as 1.0-8.0KV；The gas of T-type glass tube
The flow velocity that arrival end is passed through gas is 0.1-10.0L/min；The speed that pushes away of syringe pump 5 is 0-3000 μ L/h；Nitrogen in pneumatic nebulizer
Gas velocity is 0-3.0L/min；The mass-to-charge ratio for the ion that mass detector 9 detects is 10-2000.
After device is completed and sets each parameter, it can interact to gas anion and its with compound
The product ion and chemical reaction process chemically reacted carries out real-time online detection and analysis.
Embodiment 2: the gas anion ingredient generated in air atmosphere is analyzed
With air (nitrogen content 79v%, oxygen content 21v%) for corona discharge gas, chemical combination is not used at this time
Object.
Real-time Mass Spectrometer Method device is assembled according to the method for embodiment 1, from the gas access end of T-type glass tube with 5.0L/
The gas flow rate of min is passed through air, applies the voltage of 3.8KV to the tip of corona discharge needle, empty under the action of corona discharge
Tip of the air-flow through corona discharge needle simultaneously generates gas anion at the tip of corona discharge needle；Gas anion is in air draught
Under the action of from gas anion generator outlet end export after enter mass detector carry out the constituent analysis of gas anion,
As a result as shown in Figure 2.
Voltage experiments are alternately switched on and off by 12 repetitions, reproducibility analysis, knot are carried out to gas anion
Fruit is as shown in Figure 3.
The ion peak intensity being powered up to the gas anion of 90min is analyzed, result is as shown in Figure 4.
Embodiment 3: the on-line analysis to react to each other to the gas anion and benzaldehyde that are generated under air atmosphere
With air (nitrogen content 79v%, oxygen content 21v%) for corona discharge gas, purified petroleum benzin formaldehyde is used
(99wt%) liquid is used as and uses compound by spraying.
Real-time Mass Spectrometer Method device is assembled according to the method for embodiment 1, it is spraying to negative aeroion and purified petroleum benzin formaldehyde liquid
Reaction carry out on-line analysis.
Air is passed through with the gas flow rate of 5L/min from the gas access end of T-type glass tube, to the tip of corona discharge needle
Apply the voltage of 3.8KV, under the action of corona discharge, air flows through the tip of corona discharge needle and the point in corona discharge needle
End generates gas anion；Gas anion exports under the action of gas flow from gas anion generator outlet end.
Purified petroleum benzin formaldehyde liquid, under the action of syringe pump, the liquid chemical combination that is loaded into syringe are sucked in syringe 6
Object is sent into pneumatic nebulizer by conduit, and it is 3 μ L/h that the liquid of syringe pump 5, which pushes away speed,.Nitrogen flow rate is in pneumatic nebulizer
Under the action of the stream of nitrogen gas of 0.5L/min, benzaldehyde is exported in the form of liquid spray from the outlet end of pneumatic nebulizer
Afterwards, with derived from gas anion generator outlet end gas anion interact to form product ion, product ion exists
Enter mass detector under the action of the gas flow of gas anion generator outlet end and carries out product ion constituent analysis.
In experimentation, syringe pump 5 is opened in 7min, and syringe pump 5 is closed in 14min.Connected since 0min
Continuous on-line mass spectroscopy analysis tracking reaction process, as a result as shown in Figure 5.
Embodiment 4: the on-line analysis to react to each other to the gas anion and paraxylene that are generated under air atmosphere
With air (nitrogen content 79v%, oxygen content 21v%) for corona discharge gas, paraxylene is used
(99wt%) liquid is used as and uses compound by spraying.
Real-time Mass Spectrometer Method device is assembled according to the method for embodiment 1, to negative aeroion and paraxylene liquid spray
Reaction carry out on-line analysis.
Air is passed through with the gas flow rate of 5.0L/min from the gas access end of T-type glass tube, to the point of corona discharge needle
End applies the voltage of 3.8KV, and under the action of corona discharge, air flows through the tip of corona discharge needle and in corona discharge needle
Tip generates gas anion；The gas anion is led under the action of gas flow from gas anion generator outlet end
Out.
Paraxylene liquid, under the action of syringe pump, the liquid chemical combination that is loaded into syringe are sucked in syringe 6
Object is sent into pneumatic nebulizer by conduit, and it is 3000 μ L/h that the liquid of syringe pump 5, which pushes away speed,.The nitrogen flow rate in pneumatic nebulizer
Under the action of the stream of nitrogen gas of 0.5L/min, paraxylene is led in the form of liquid spray from the outlet end of pneumatic nebulizer
After out, with derived from gas anion generator outlet end gas anion interact to form product ion, product ion
Enter mass detector under the action of gas anion generator outlet end gas flow and carries out product ion constituent analysis.
In experimentation, syringe pump 5 is opened in 3min, and syringe pump 5 is closed in 8min.It is carried out since 0min continuous
On-line mass spectroscopy analysis tracking reaction process, as a result as shown in Figure 6.
Figure it is seen that in air atmosphere, a single quasi-molecular ions m/z 60 is detected, and the ion is only
Carbon, hydrogen, oxygen or nitrogen can be contained, derive it for CO in conjunction with mass-to-charge ratio (m/z 60)3 -.Embedding figure in Fig. 2 is parent ion
The second order ms figure of m/z 60, a quasi-molecular ions m/z 16 are detected, and are O-, and CO3 -O is generated in second order ms collision-
And CO2, to further prove that the ion of m/z 60 is CO3 -。
From figure 3, it can be seen that in pressurization, due to generating the gas anion (CO of m/z 603 -), mass spectrum peak intensity is by 0
It is quickly raised to stablize；And when closing high pressure, mass spectrum peak intensity is reduced to rapidly 0.Be computed, peak intensity shown in Fig. 3 it is opposite
Standard deviation (RSD) is 4.81%, the results showed that each quasi-molecular ions intensity is essentially identical, there is preferable reproducibility.
From fig. 4, it can be seen that in energization 90min, the ion (CO of m/z 603 -) peak intensity is basicly stable, ion spike
Dynamic property is small, has long-time stability.
Complex chart 3 and Fig. 4 can be seen that device and method provided by the invention and can carry out to the ingredient of gas anion
Analysis real-time, quickly, and show preferable reproducibility and stability.
The embedding figure of Fig. 5 is (the gas anion CO of m/z 603 -) and 121 (product ion of m/z) selection ion
Flow graph.In 0-7min, the ion peak intensity of m/z 60 is very high, and the quasi-molecular ions intensity of m/z 121 is essentially 0, only has at this time
Gas anion CO3 -Generation and be detected.In 7min to 14min, benzaldehyde liquid, the quasi-molecular ions of m/z 60 have been used
Intensity gradually decreases and keeps stable, and the ion peak intensity of m/z 121 significantly increases and keeps stable, therebetween mass spectrogram such as Fig. 5
Master map shown in, it is seen that gas anion CO3 -React with benzaldehyde liquid and generate the product of new m/z 121 from
Son.In 14min to 20min, benzaldehyde liquid is stopped using, the quasi-molecular ions strength reduction most 0 of m/z 121 is simultaneously kept not
Become, it is seen that interaction reaction stops, at this time only gas anion CO3 -Generation and be detected.
The embedding figure of Fig. 6 is (the gas anion CO of m/z 603 -) and 135 (product ion of m/z) choosing
Select ion flow graph.In 0-3min, the ion peak intensity of m/z 60 is very high, and the quasi-molecular ions intensity of m/z 135 is essentially 0, this
When there was only gas anion CO3 -Generation and be detected.In 3min to 8min, paraxylene liquid, m/z 60 have been used
Ion peak intensity gradually decrease and keep stable, the ion peak intensity of m/z 135 significantly increases and keeps stable, therebetween mass spectrum
Figure is as shown in the master map of Fig. 6, it is seen that gas anion CO3 -It reacts with paraxylene liquid and generates new m/z 135
Product ion.In 8min to 10min, paraxylene liquid, the quasi-molecular ions strength reduction most 0 of m/z 135 are stopped using
And remain unchanged, it is seen that interaction reaction stops, at this time only gas anion CO3 -Generation and be detected.
From figs. 5 and 6, it can be seen that device and method provided by the invention can be mutual to gas anion and compound
Effect carries out on-line analysis, can deduce gas anion and compound phase interaction by the constituent analysis to product ion
Mechanism is laid a good foundation to carry out the property research of gas anion.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (15)
1. a kind of real-time Mass Spectrometer Method device for the constituent analysis of gas anion and its with compound interaction, packet
It includes:
The gas anion generator being fixed on pedestal；
It is set to the mass detector of face gas anion generator outlet end；
It is set between gas anion generator outlet end and the mass detector arrival end and liquid chemical combination can be made
The liquid spray component that object spray flow is mixed with the gas flow flowed out from gas anion generator outlet end in right-angled intersection；
The liquid spray component is by syringe, syringe pump, pneumatic nebulizer and connection syringe outlet and pneumatic nebulizer
The conduit of entrance forms；
The liquid compound spray flow is liquid spray stream.
2. the apparatus according to claim 1, which is characterized in that gas anion generator outlet end and the mass spectrum
The distance of detector arrival end is 0.3-2.0cm.
3. the apparatus according to claim 1, which is characterized in that the gas anion generator includes tee tube, setting
In the corona discharge needle and fixed pin in the tee tube and the needle stand that connect with high voltage power supply interface of conducting wire can be passed through；It is described
One end in the both ends being located along the same line in tee tube is inserted into needle stand and guarantees that distal portion seals, and the other end is negative for gas
Ion generator outlet end；It with the perpendicular one end in the both ends that are located along the same line is gas access end in the tee tube.
4. device according to claim 3, which is characterized in that the internal diameter of the tee tube is 3-10mm.
5. device according to claim 4, which is characterized in that the internal diameter of the tee tube is 5-8mm.
6. device according to claim 4, which is characterized in that the tip of the corona discharge needle in the tee tube with it is described
The distance of gas anion generator outlet end is 0-4.0cm.
7. device according to claim 6, which is characterized in that the tip of the corona discharge needle in the tee tube with it is described
The distance of gas anion generator outlet end is 0.8-4.0cm.
8. the device according to any one of claim 3-7, which is characterized in that the material of the corona discharge needle includes
One of tungsten, iron, stainless steel and copper are a variety of.
9. a kind of carry out the constituent analysis of gas anion and its and compound using any one of claim 1-8 described device
The real-time Mass Spectrometry detection method of interaction comprising:
Step A is passed through gas from the gas access end of tee tube, applies voltage to the tip of corona discharge needle, in corona discharge
Under the action of, gas flows through the tip of corona discharge needle and generates gas anion at the tip of corona discharge needle；The gas
Anion enters mass detector after the export of gas anion generator outlet end under the action of gas flow and carries out gas
Anion constituent analysis；
Step B, under the action of syringe pump, the liquefied compound being loaded into syringe is sent into pneumatic nebulizer by conduit
In, in pneumatic nebulizer under the action of stream of nitrogen gas, by liquefied compound from the outlet end of pneumatic nebulizer with liquid spray
Form export after, with derived from gas anion generator outlet end gas anion interact to form product ion；
The product ion under the action of gas anion generator outlet end gas flow enter mass detector carry out product from
Subconstiuent analysis.
10. according to the method described in claim 9, it is characterized in that, in step, the gas access end of the tee tube is logical
The flow velocity for entering gas is 0.1-10.0L/min；Tip institute's making alive of the corona discharge needle is 1.0-8.0KV.
11. according to the method described in claim 10, it is characterized in that, in step, the gas access end of the tee tube is logical
The flow velocity for entering gas is 5.0-10.0L/min；Tip institute's making alive of the corona discharge needle is 3.8-8.0KV.
12. according to the method described in claim 9, it is characterized in that, in stepb, the speed that pushes away of the syringe pump is 0-3000 μ
L/h；Nitrogen flow rate in the pneumatic nebulizer is 0-3.0L/min.
13. according to the method for claim 12, which is characterized in that in stepb, the speed that pushes away of the syringe pump is 3-3000
μL/h；Nitrogen flow rate in the pneumatic nebulizer is 0.5-3.0L/min.
14. the method according to any one of claim 9-13, which is characterized in that the mass detector is using unlimited
Formula detection mode.
15. according to the method for claim 14, which is characterized in that the mass-to-charge ratio of the ion of mass detector detection is
10-2000。
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| CN113176325B (en) * | 2021-04-14 | 2023-05-12 | 北京师范大学 | Normal pressure mass spectrum online monitoring system for accelerating degradation of organic pollutants by plasmas in milliseconds |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1862760A (en) * | 2006-03-24 | 2006-11-15 | 清华大学 | Chemical ioning method based on dielectric blocking discharge and mass ion source |
| CN101587038A (en) * | 2009-06-26 | 2009-11-25 | 中国科学院合肥物质科学研究院 | Liquid sample desorption ionization method under atmospheric pressure |
| CN102280347A (en) * | 2010-07-06 | 2011-12-14 | 东华理工大学 | Normal pressure chemical extraction ionization source and normal pressure extraction ionization mass spectrometry method |
| CN102792416A (en) * | 2010-02-12 | 2012-11-21 | 国立大学法人山梨大学 | Ionization device and ionization analysis device |
-
2016
- 2016-05-30 CN CN201610367472.XA patent/CN106093179B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1862760A (en) * | 2006-03-24 | 2006-11-15 | 清华大学 | Chemical ioning method based on dielectric blocking discharge and mass ion source |
| CN101587038A (en) * | 2009-06-26 | 2009-11-25 | 中国科学院合肥物质科学研究院 | Liquid sample desorption ionization method under atmospheric pressure |
| CN102792416A (en) * | 2010-02-12 | 2012-11-21 | 国立大学法人山梨大学 | Ionization device and ionization analysis device |
| CN102280347A (en) * | 2010-07-06 | 2011-12-14 | 东华理工大学 | Normal pressure chemical extraction ionization source and normal pressure extraction ionization mass spectrometry method |
Non-Patent Citations (3)
| Title |
|---|
| Interaction of multiple reaction ions with 2,4,6-trinitrotoluene studied by corona discharge ion mobility-mass spectrometry;Martin Sabo et.al;《International Journal of Mass Spectrometry》;20150321;第13页左栏倒数第2段-第19页右栏第3段 |
| Transport and stability of negative ions generated by negative corona discharge in air studied using ion mobility-oaTOF spectrometry;Martin Sabo et.al;《International Journal of Mass Spectrometry》;20121018;全文 |
| Using corona discharge-ion mobility spectrometry for detection of 2,4,6-Trichloroanisole;Zuzana Lichvanova et.al;《Talanta》;20140424;全文 |
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