CN110400740A - A kind of method and apparatus using solvent and gas double auxiliary flame direct ion sample - Google Patents
A kind of method and apparatus using solvent and gas double auxiliary flame direct ion sample Download PDFInfo
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- CN110400740A CN110400740A CN201910665891.5A CN201910665891A CN110400740A CN 110400740 A CN110400740 A CN 110400740A CN 201910665891 A CN201910665891 A CN 201910665891A CN 110400740 A CN110400740 A CN 110400740A
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- 239000002904 solvent Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000001819 mass spectrum Methods 0.000 claims abstract description 35
- 241000894007 species Species 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 94
- 239000000446 fuel Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 229920002521 macromolecule Polymers 0.000 abstract description 6
- 238000004445 quantitative analysis Methods 0.000 abstract description 6
- 238000006053 organic reaction Methods 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 4
- 239000000523 sample Substances 0.000 description 111
- 150000002500 ions Chemical class 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000010183 spectrum analysis Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 10
- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 description 10
- 238000005070 sampling Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 102000015427 Angiotensins Human genes 0.000 description 8
- 108010064733 Angiotensins Proteins 0.000 description 8
- 239000002416 angiotensin derivative Substances 0.000 description 8
- DOMXUEMWDBAQBQ-WEVVVXLNSA-N terbinafine Chemical compound C1=CC=C2C(CN(C\C=C\C#CC(C)(C)C)C)=CC=CC2=C1 DOMXUEMWDBAQBQ-WEVVVXLNSA-N 0.000 description 8
- 238000012546 transfer Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000000375 direct analysis in real time Methods 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 229960000699 terbinafine hydrochloride Drugs 0.000 description 6
- 238000005615 Borsche-Drechsel cyclization reaction Methods 0.000 description 5
- 239000002828 fuel tank Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000065 atmospheric pressure chemical ionisation Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005251 capillar electrophoresis Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000752 ionisation method Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229960002722 terbinafine Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000972155 Moschus Species 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 flame Substances 0.000 description 1
- 238000004186 food analysis Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- G01N27/626—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 heat to ionise a gas
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a kind of method and apparatus using solvent and gas double auxiliary flame direct ion sample, the method is that the energy for generating flame and active specy are pushed under the common push of secondary solvent and auxiliary sheath gas to sample to be tested, ionizes sample to be tested.Described device includes flame, sample to be tested, mass spectrum sample intake passage, secondary solvent channel and auxiliary sheath gas channel, auxiliary sheath gas channel is sheathed on the outside in secondary solvent channel, the outlet end of the outlet end and secondary solvent channel that assist sheath gas channel is respectively positioned near flame, and sample to be tested is located between the outlet end in auxiliary sheath gas channel and the outlet end and mass spectrum sample intake passage in secondary solvent channel.The present invention can not only realize the ionisation mass spectrometry to effective component, macromolecular compound and difficult volatilization, easily cracking compound in actual sample, but also can be used for quantitative analysis, especially can analyze organic reaction with direct-on-line, universality is strong.
Description
Technical field
The present invention relates to a kind of method and apparatus using solvent and gas double auxiliary flame direct ion sample, belong to
In analytical technique of mass spectrum field.
Background technique
Mass spectrum (MS) be it is a kind of can analyze complex mixture, provide related molecular weight information, element composition and analyte
The important tools of analysis of chemical structure, specificity and sensitivity with height.The basic principle of mass spectral analysis is made in sample
Each component ionizes in an ion source, generates the positively charged ion of different charge-mass ratios, and the effect of accelerated electric field is formed
Then in the mass analyser ion beam, recycles electric and magnetic fields to make that opposite speed color occurs into mass analyzer
It dissipates, they is focused respectively and obtains mass spectrogram, so that it is determined that its quality.Therefore, ionization techniques have mass spectrometry results
It has a major impact.In recent years, it constantly bringing forth new ideas and improving with ionization techniques and mass analyzer as compound is desorbed, mass spectrum
As one of most rapid analytical technology is developed, at present mass-spectrometric technique chemistry and chemical industry, biology and life science, medicine,
The fields such as pharmacy, material science, environmental protection using more and more extensive.
Plasma (plasma) this term is put forward for the first time by Tang Kesi and bright wrong that in nineteen twenty-nine.Plasma be after
The 4th state of substance after solid-state, liquid, gaseous state, when applied voltage reaches breakdown voltage, gas molecule is ionized, and generates packet
Include the mixture including electronics, ion, atom and atomic group.Plasma has unique physicochemical properties, therefore is based on
The ionization techniques of plasma obtain great development in organic mass spectrometry field and are widely applied.
Traditional Ionization Techniques In Mass Spectrometry based on plasma, which mainly has, induces corona discharge based on high pressure
(CoronaDischarge) the atmospheric pressure chemical ionization technology (APCI) of plasma is formed and in atmospheric pressure chemical ionization skill
The Direct Analysis in Real Time ionization techniques (DART) researched and developed on the basis of art (APCI).Due to requiring low, high pass to sample pre-treatments
Amount, high sensitivity, and real time on-line monitoring may be implemented, this kind of Ionization Techniques In Mass Spectrometry receives the extensive pass of academia
Note, in chemistry, food analysis, the fields such as bioanalysis and pharmacy are used widely.
But it is above-mentioned based on the Ionization Techniques In Mass Spectrometry of plasma, there is also many defects, such as: pass through high pressure ionization
There are certain risk when gas generates plasma, high voltage may have an impact operator's personal safety；Ion
Makeup, which is set, to be difficult to be miniaturized, and the high pressure generation module volume of ion source is difficult to reduce, and mutually conflicts with present mass spectrum trend toward miniaturization；
Higher cost, such as DART generally use helium as ionized gas, and the cost of helium is very high, this allows for analysis test
Cost is very high, while the experimental provision of DART is very complicated, operates also complex；The compound range of analysis is limited, such as high
Voltage is easy some redox reactions of catalysis, so that the technology detects some substances for being prone to redox reaction
Effect is undesirable；In another example the temperature adjusting range of DART is smaller, usually at 50~550 DEG C, therefore its can detect be mostly
Small molecule, the compound of some macromoleculars are not easy to parse.
In order to overcome drawbacks described above, the applicant Chinese patent CN201520544461.5, CN201520861732.X,
It is individually disclosed in CN201510730846.5 using special plasma flame as the ionization apparatus of ion source.It is above-mentioned to be based on
For the ionization techniques of flame plasma compare traditional ionization techniques based on plasma, there are as follows some
Advantage: simplicity is easy to get, and the generation of flame plasma does not need high voltage, it is only necessary to and some fuel gas produce, and safety is good,
Simultaneously because eliminating bulky high-pressure modular, entire ionization apparatus can be miniaturized；It, can be with by selecting suitable fuel
Keep the temperature adjusting range of flame larger, usually at 50~1500 DEG C, therefore the substance of macromolecular also can parse；Catalytic reaction
A possibility that raw redox reaction, is smaller, does not influence the detection for being prone to the substance of redox reaction.But above-mentioned fire
Still there are some defects for flame ionization apparatus, such as: it is still limited for the detection range of macromolecular substances, it is practically used for
When above-mentioned flame ion device is used for mass spectral analysis, it is difficult the signal for detecting that molecular weight is greater than 1000, in addition, above-mentioned flame
The ionization apparatus ionization apparatus very poor also, current for the Ionization Efficiency of some difficult volatilizations, the substance for being easy to crack
Qualitative analysis can only be done when for mass spectral analysis, can not also carry out quantitative analysis and current ionization apparatus well
Direct-on-line catalysis detection organic reaction is unable to when for mass spectral analysis.These defects affect flame ion technology
Using.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, it is auxiliary using solvent and gas double that the object of the present invention is to provide a kind of
The method and apparatus for helping flame direct ion sample.
To solve the above problems, the present invention adopts the following technical scheme:
A method of flame direct ion sample is assisted using solvent and gas double, is the energy for generating flame
It is pushed under the common push of secondary solvent and auxiliary sheath gas to sample to be tested with active specy, makes sample to be tested ion
Change.
A kind of device using solvent and gas double auxiliary flame direct ion sample, including flame, sample to be tested
With mass spectrum sample intake passage, the flame is located in front of the port of mass spectrum sample intake passage, and the sample to be tested is located at flame and mass spectrum
Between sample intake passage；It further include the secondary solvent channel for introducing secondary solvent and the auxiliary sheath gas for introducing auxiliary sheath gas
Channel, the auxiliary sheath gas channel are sheathed on the outside in secondary solvent channel, the outlet end in the auxiliary sheath gas channel and auxiliary
The outlet end of solvent channel is respectively positioned near flame, and the sample to be tested is located at the outlet end in auxiliary sheath gas channel and assists molten
Between the outlet end and mass spectrum sample intake passage in agent channel.
Preferably, the flame is connected with fuel supply system.
As further preferred scheme, the fuel supply system includes fuel tank and fuel transmission pipe.
As further preferred scheme, it is equipped with flow control valve in fuel tank, it is micro- that flow is equipped on fuel transmission pipe
Adjust valve.
Preferably, the secondary solvent channel is connected with secondary solvent feedway.
As further preferred scheme, the secondary solvent feedway includes that secondary solvent storage tank and secondary solvent pass
Defeated pipe.
As further preferred scheme, flow control valve is equipped on secondary solvent storage tank, in secondary solvent transfer tube
It is equipped with flow rate fine-tuning valve.
Preferably, auxiliary sheath gas channel is connected with auxiliary sheath air feed system.
As further preferred scheme, the auxiliary sheath air feed system includes that auxiliary sheath gas storage tank and auxiliary sheath gas pass
Defeated pipe.
As further preferred scheme, it is equipped with flow control valve on auxiliary sheath gas storage tank, in auxiliary sheath gas transfer tube
It is equipped with flow rate fine-tuning valve.
Preferably, further include sample carrier or sampling device for introducing sample to be tested, sample carrier it is negative
The present position for carrying the outlet ends of sample end or sampling device is the present position of sample to be tested.
As further preferred scheme, the sample carrier includes but is not limited to sample stick or ultrasonic atomizatio piece, it is described into
Sampling device includes but is not limited to liquid chromatography, gas chromatography, syringe pump or Capillary Electrophoresis.
Preferably, the outlet end flush of the outlet end in secondary solvent channel and auxiliary sheath gas channel.
Preferably, the distance between the outlet end in secondary solvent channel and mass spectrum sample intake passage are 20~80mm.
Preferably, the distance between the outlet end in secondary solvent channel and flame are 1~5mm.
Preferably, the angle between the flame core axis of the axis and flame in secondary solvent channel is 0~90 degree.
Preferably, the distance between flame and sample to be tested are 10~40mm.
Preferably, the internal diameter in the secondary solvent channel is 50~300 microns, and outer diameter is 150~500 microns.
Preferably, the secondary solvent channel is capillary, when secondary solvent channel is capillary, capillary
Internal diameter be 50~300 microns, outer diameter be 150~500 microns.
Preferably, the flow velocity of the secondary solvent in secondary solvent channel is 5~70 mul/min.
Preferably, the flow velocity for assisting the auxiliary sheath gas in sheath gas channel is 15~40 ls/h.
Preferably, heat-resisting material, the resistance to height are selected in the secondary solvent channel and auxiliary sheath gas channel
Adiabator includes but is not limited to glass, ceramics or metal material resistant to high temperature.
Preferably, the secondary solvent is selected from least one of water, methanol, ethyl alcohol, acetonitrile.
Preferably, the auxiliary sheath gas is any one in air, carbon dioxide, nitrogen, helium, argon gas
Kind.
Compared to the prior art, the beneficial technical effect of the present invention lies in:
Using the method for the present invention and device, it can not only realize and 1000 are higher than to effective component, molecular weight in actual sample
Macromolecular compound and the ionisation mass spectrometry of difficult volatilization, easily cracking compound, and can be used for quantitative analysis, especially may be used also
Organic reaction is analyzed with direct-on-line, universality is strong, can provide species analysis and study on mechanism for organic chemist
Convenient way is provided, compared with the existing technology, there is conspicuousness progress and practical value.
Detailed description of the invention
Fig. 1 is a kind of device that flame direct ion sample is assisted using solvent and gas double provided by the invention
Structural schematic diagram；
Fig. 2 is the mass spectral analysis figure of Terbinafine hydrochloride emulsifiable paste obtained in inventive embodiments 1；
Fig. 3 is the mass spectral analysis figure of angiotensins obtained in inventive embodiments 2；
Fig. 4 is the TIC figure of muskone obtained in inventive embodiments 3；
Fig. 5 is quantitation curves line chart obtained in inventive embodiments 3；
Fig. 6 is the mass spectral analysis figure of the reaction of Borsche-Drechsel obtained in inventive embodiments 4；
Figure label is schematically as follows: 1, flame；2, sample to be tested；3, mass spectrum sample intake passage；4, secondary solvent channel；5, auxiliary
Help sheath gas channel；6, ionisation region；7, fuel supply system；71, fuel tank；72, fuel transmission pipe；73, fuel supply dress
The flow control valve set；74, the flow rate fine-tuning valve of fuel supply system；8, secondary solvent feedway；81, secondary solvent stores
Tank；82, secondary solvent transfer tube；83, the flow control valve of secondary solvent feedway；84, the stream of secondary solvent feedway
Measure reset valve；9, sheath air feed system is assisted；91, sheath gas storage tank is assisted；92, sheath gas transfer tube is assisted；93, auxiliary sheath gas supplies
To the flow control valve of device；94, the flow rate fine-tuning valve of sheath air feed system is assisted.
Specific embodiment
Technical solution of the present invention is described in further detail and completely with reference to the accompanying drawing.
It is provided by the invention a kind of using solvent and gas double auxiliary flame direct ion sample as shown in Figure 1:
Device, including flame 1, sample to be tested 2 and mass spectrum sample intake passage 3, the flame 1 are located in front of the port of mass spectrum sample intake passage 3,
The sample to be tested 2 is between flame 1 and mass spectrum sample intake passage 3；It further include logical for introducing the secondary solvent of secondary solvent
Road 4 and auxiliary sheath gas channel 5 for introducing auxiliary sheath gas, the auxiliary sheath gas channel 5 is sheathed on the outer of secondary solvent channel 4
Portion, the outlet end in the auxiliary sheath gas channel 5 and the outlet end in secondary solvent channel 4 are respectively positioned near flame 1, described to be measured
Sample 2 is located between the outlet end in auxiliary sheath gas channel 5 and the outlet end and mass spectrum sample intake passage 3 in secondary solvent channel 4.
Device of the present invention can with common mass spectrograph (such as: triple quadrupole mass spectrometer, time of-flight mass spectrometer, from
Sub- trap mass spectrograph etc.) mutually it is compatible with, it can also promote the use of in other mass spectral analyses, when being used for mass spectral analysis, with common mass spectrum
Instrument combination, has a wide range of application, practical.
The method for realizing ionization using device of the present invention is the energy for generating flame 1 and active specy auxiliary
It is pushed under the common push of cosolvent and auxiliary sheath gas to sample to be tested 2, ionizes sample to be tested 2.
Shown in Figure 1, in ionization process, flame 1 is pushed under the common push of secondary solvent and auxiliary sheath gas
To sample to be tested 2, and sample to be tested 2 is located in front of the port of mass spectrum sample intake passage 3, therefore, the active specy that flame 1 generates
It is pushed to energy in front of the port of mass spectrum sample intake passage 3, ionization can be generated in front of the port of mass spectrum sample intake passage 3
Region 6, therefore sample to be tested 2 is in ionisation region 6, so the active specy that generates of flame 1 and energy be pushed to from
Can be collided with sample to be tested 2 behind sonization region 6, can make sample to be tested 2 ionize, then ionize after sample through mass spectrum into
Sample channel 3 can carry out subsequent mass spectral analysis into mass spectrograph.Therefore herein described device is compared to traditional fire
Flame ionization apparatus, because sample to be tested 2 and flame 1 are not directly contacted with, thus it is high to can effectively avoid the directly contact of sample to be tested 2
Temperature, and then can effectively avoid sample to be tested 2 and be carbonized by Pintsch process, crack sample to be tested 2 less, therefore even with easy
The compound of cracking also can have good ionising effect.In addition, in the application, flame 1 as novel plasma,
Burned flame 1 can generate a large amount of energy and active specy, the energy for assisting sheath gas and secondary solvent that can generate flame 1
It is pushed at sample to be tested 2 with active specy, while secondary solvent can also assist sample desorption, in ionization process, fire
After the energy and active specy that flame 1 generates are pushed to sample to be tested 2, secondary solvent is first to 2 desorption of sample to be tested, then
The energy and active specy that flame 1 generates assist sample to be tested 2 to ionize again, so that Ionization Efficiency is high, sensitivity is good, generate
Mass spectrogram be easy to parse, miscellaneous peak is less, and spectrogram is more clean.In addition, secondary solvent and auxiliary sheath gas also have certain drop
Temp effect, it is possible to prevente effectively from sample to be tested 2 is destroyed by thermal-flame, so that the present apparatus is to macromolecular compound, (molecular weight is big
In 1000 compound) also there is good ionising effect.
Shown in Figure 1, the flame 1 is connected with fuel supply system 7.The fuel supply system 7 includes fuel tank
71 and fuel transmission pipe 72.In addition, being equipped with flow control valve 73 in fuel tank 71, it is micro- that flow is equipped on fuel transmission pipe 72
Adjust valve 74.When being analyzed by mass spectrometry, 7 output gas fuel of fuel supply system is opened, gaseous fuel is then made to be ignited generation
Flame 1 in gaseous fuel transmission process, can pass through the stream of 74 regulating gas fuel of flow control valve 73 and flow rate fine-tuning valve
Amount, and then size, height, the temperature of flame 1 are adjusted, so that flame 1 is adapted with sample to be tested 2, to guarantee ionising effect.
Fuel used is inorganic fuel or organic-fuel, and inorganic fuel includes but is not limited to hydrogen, and organic-fuel includes but is not limited to
HC fuel, Aalcohols fuel, ketone fuel, ethers fuel or esters fuel, HC fuel include but is not limited to saturated alkane class,
Unsaturated alkanes or the mixture being made of a variety of hydrocarbons, preferably hydrogen.
The secondary solvent channel 4 is connected with secondary solvent feedway 8.The secondary solvent feedway 8 includes auxiliary
Cosolvent storage tank 81 and secondary solvent transfer tube 82.It is equipped with flow control valve 83 on secondary solvent storage tank 81, is assisting
Solvent delivery pipe 82 is equipped with flow rate fine-tuning valve 84.Correspondingly, auxiliary sheath gas channel 5 is connected with auxiliary sheath air feed system
9.The auxiliary sheath air feed system 9 includes auxiliary sheath gas storage tank 91 and auxiliary sheath gas transfer tube 92.In auxiliary sheath gas storage
Tank 91 is equipped with flow control valve 93, is equipped with flow rate fine-tuning valve 94 on auxiliary sheath gas transfer tube 92.When being analyzed by mass spectrometry, beat
Secondary solvent feedway 8 and auxiliary sheath air feed system 9 are opened, keeps secondary solvent and auxiliary sheath gas logical by secondary solvent respectively
Road 4 and auxiliary sheath gas channel 5 are introduced near flame 1, during introducing secondary solvent and auxiliary sheath gas, can be passed through
It adjusts flow control valve 83, flow rate fine-tuning valve 84, flow control valve 93, flow rate fine-tuning valve 94 and adjusts secondary solvent and auxiliary sheath gas
Flow velocity, for example, in the application, the flow velocity of the secondary solvent in secondary solvent channel 4 is 5~70 mul/min, assists sheath gas
The flow velocity of auxiliary sheath gas in channel 5 is 15~40 ls/h, in order to which secondary solvent and auxiliary sheath gas push to flame 1
At sample to be tested 2, sample to be tested 2 is ionized, while being also convenient for the temperature by secondary solvent and auxiliary sheath controlled atmosphere section flame 1
Degree adjusts the desorption effect to sample to be tested 2, and then guarantees the ionising effect of sample to be tested 2.
Above-mentioned apparatus can also include the sample carrier or sampling device (not shown) for introducing sample to be tested 2, sample
The present position of the outlet ends at the load sample end or sampling device of carrier is the present position of sample to be tested 2.Sample carries
Body or sampling device use universal support or device, as long as sample to be tested 2 can be introduced to the port of mass spectrum sample intake passage 3
Front, for example, the sample carrier includes but is not limited to sample stick, ultrasonic atomizatio piece, the sampling device includes but not
It is limited to the continuous sample introductions device such as liquid chromatography, gas chromatography, syringe pump, Capillary Electrophoresis.In the application, due to flame 1 with to
Sample 2 is not directly contacted with, therefore does not do excessive requirement to the heat-resisting quantity of sample carrier or sampling device, for example, working as sample
When carrier is sample stick, not requiring sample stick is high temperature resistant sample stick, save the cost.Meanwhile when sampling device be liquid chromatogram,
When the continuous sample introductions device such as gas-chromatography, syringe pump, when so that the present apparatus being used for mass spectral analysis, it can be ensure that with continuous sample introduction
The stability of signal.
In the application, the outlet end in secondary solvent channel 4 and the outlet end flush in auxiliary sheath gas channel 5 are auxiliary to guarantee
The synchronism of cosolvent and auxiliary sheath gas.
In the application, flame 1, sample to be tested 2, mass spectrum sample intake passage 3, secondary solvent channel 4 and auxiliary sheath gas channel 5 it
Between be discrete state, and flame 1, sample to be tested 2, mass spectrum sample intake passage 3 and secondary solvent channel 4 and auxiliary sheath gas channel 5 it
Between mutual alignment it is adjustable.
For example, in the application, the outlet end (outlet end for also corresponding to auxiliary sheath gas channel 5) in secondary solvent channel 4 with
The distance between mass spectrum sample intake passage 3 d1 is 20~80mm.Further, the outlet end in secondary solvent channel 4 (also corresponds to auxiliary
Help the outlet end in sheath gas channel 5) it with the distance between flame 1 d2 is 1~5mm, in order to pass through secondary solvent and auxiliary sheath gas
Flame 1 is pushed at sample to be tested 2, at the same compared to traditional flame ion device for, the application Flame 1 and matter
It is larger to compose the distance between sample intake passage 3, it is small to mass spectrum sample intake passage 3 and the pollution of corresponding mass spectrograph, while the generation of flame 1
High temperature on mass spectrum sample intake passage 3 and it is corresponding it is mass spectrometric influence also smaller, ensure that mass spectral analysis effect and mass spectrometric make
Use the service life.
Angle between the axis in secondary solvent channel 4 (also corresponding to auxiliary sheath gas channel 5) and the flame core axis of flame 1
α is 0~90 degree.The axis in secondary solvent channel 4 is parallel with the auxiliary axis in sheath gas channel 5.Flame 1 and sample to be tested 2 it
Between distance d3 be 5~40mm.The internal diameter in the secondary solvent channel 4 is 50~300 microns, and outer diameter is 150~500 microns.
In the application, the secondary solvent channel 4 is capillary, when secondary solvent channel 4 is capillary, correspondingly, capillary
Internal diameter is 50~300 microns, and outer diameter is 150~500 microns.
In the application, heat-resisting material, the high temperature resistant are selected in the secondary solvent channel 4 and auxiliary sheath gas channel 5
Material includes but is not limited to glass, ceramics or metal material resistant to high temperature.In the application, auxiliary sheath gas channel 5 is sheath tracheae.
In the application, the secondary solvent be selected from least one of water, methanol, ethyl alcohol, acetonitrile, be mainly used for auxiliary to
2 desorption of sample.
In the application, auxiliary sheath gas is mainly used for pushing to flame 1 at sample to be tested 2, therefore, to auxiliary sheath gas
Of less demanding, the auxiliary sheath gas can select valence selected from any one in air, oxygen, nitrogen, helium, argon gas
Helium, the argon gas of lattice valuableness, can also select cheap air, carbon dioxide, oxygen, nitrogen, compared to common in DART
Expensive helium for, analysis cost can be substantially reduced to a certain extent.
Technical effect achieved by the present invention is further illustrated below with reference to concrete application embodiment.
Embodiment 1
Use device of the present invention and mass spectrograph (mass analyzer is triple quadrupole bar) to actual sample hydrochloric acid spy's ratio
Naphthalene sweet smell emulsifiable paste is analyzed by mass spectrometry:
Gaseous fuel is hydrogen, and secondary solvent is methanol, and the flow velocity of secondary solvent is 20 mul/min, and auxiliary sheath gas is
Nitrogen, the flow velocity of auxiliary sheath gas are 25 ls/h.
A small amount of Terbinafine hydrochloride emulsifiable paste is directly dipped using sample stick, then by load sample end (the i.e. salt of sample stick
Sour terbinafine emulsifiable paste) it is fixed in front of the port of mass spectrum sample intake passage 3；It lights gas burning and generates flame 1, flame 1 and sample
The distance at the load sample end of product stick is 30mm；Secondary solvent methanol and auxiliary sheath are introduced respectively by capillary and sheath tracheae
Gas, secondary solvent and auxiliary sheath gas spray along the axis direction of capillary and flame 1 are pushed to Terbinafine hydrochloride emulsifiable paste
Place, ionizes Terbinafine hydrochloride emulsifiable paste, and mass analyzer is made to be constantly in acquisition state.
The mass spectral analysis figure for the Terbinafine hydrochloride emulsifiable paste that Fig. 2 is occurs in Terbinafine hydrochloride emulsifiable paste in figure
Main chemical compositions Terbinafine relevant ions peak (m/z) 292, and without other foreign ion peaks interfere, illustrate to use
Device of the present invention can realize good ionising effect to active chemical in actual sample.
Embodiment 2
Device of the present invention and mass spectrograph (mass analyzer is triple quadrupole bar) is used to crack to hardly possible volatilization, easily, is big
The angiotensins of molecular weight is analyzed by mass spectrometry:
Gaseous fuel is hydrogen, and secondary solvent is methanol, and the flow velocity of secondary solvent is 20 mul/min, and auxiliary sheath gas is
Nitrogen, the flow velocity of auxiliary sheath gas are 20 ls/h.
Using methanol as solvent, the angiotensins sample solution of 10ppm is configured, by liquid chromatogram by angiotensins sample
Product solution is led in front of the port of mass spectrum sample intake passage 3；It lights gas burning and generates flame 1, flame 1 and angiotensins sample
The distance of solution is 30mm；By capillary and sheath tracheae introduce respectively secondary solvent methanol and auxiliary sheath gas, secondary solvent and
Auxiliary sheath gas sprays along the axis direction of capillary and pushes to flame 1 at angiotensins sample solution, keeps blood vessel tight
Plain sample solution ionization is opened, and mass analyzer is made to be constantly in acquisition state.
There is the relevant ions peak (m/ of angiotensins in figure in the mass spectral analysis figure for the angiotensins that Fig. 3 is
Z) 1046,1068, and interfered without other foreign ion peaks, illustrate to use device of the present invention that can volatilize to hardly possible, is easy to crack
The good ionising effect of compound realization of solution, macromolecule.
Embodiment 3
Device of the present invention is used quantitatively to be divided with mass spectrograph (mass analyzer is triple quadrupole bar) muskone
Analysis:
Draw muskone standard solution standard curve: respectively by muskone be configured to concentration be 0.1ppm, 0.2ppm,
The standard solution of 0.5ppm, 1ppm, 2ppm, 5ppm, 10ppm, 20ppm, 50ppm, 100ppm take the Moschus of various concentration respectively
10 μ L of ketone standard solution is analyzed by mass spectrometry according to analysis condition described in embodiment 1, respectively under mass spectrographic SRM mode, is taken
239- > 95 m/z are detection ion pair, and collision energy is the TIC ion flow graph of 28eV, draw the standard of muskone standard solution
Curve, then the muskone sample by actual needs test is configured to certain density sample solution, in identical test condition
Under be analyzed by mass spectrometry, the content of muskone in actual sample can be measured, realize the quantitative analysis of muskone.
The TIC ion flow graph for the muskone standard solution (1ppm) that Fig. 4 is, SN indicates that signal-to-noise ratio, RT indicate in figure
Time, AA indicate peak area；From fig. 4, it can be seen that TIC ion flow graph shows that peak shape is good, illustrate the mass spectral analysis side of the present embodiment
Method is stablized, favorable reproducibility.
The standard curve for the muskone standard solution that Fig. 5 is, as seen from Figure 5, obtained standard curve is linearly good,
Illustrate to realize good quantitative analysis to sample using device of the present invention.
Embodiment 4
Use device of the present invention and mass spectrograph (mass analyzer is triple quadrupole bar) to Borsche-Drechsel
Reaction is analyzed by mass spectrometry:
Borsche-Drechsel reaction is as follows:
Compound 1 and 2 is dissolved in the sample solution that methanol is made into compound 1 and compound 2 respectively, then by two kinds of samples
Solution is mixed to form mixing sample solution, is then analyzed by mass spectrometry according to condition described in embodiment 2.
The mass spectral analysis figure for the Borsche-Drechsel reaction that Fig. 6 is；In addition to the phase of compound 1 and 2 in spectrogram
It closes outside quasi-molecular ions (m/z) 99,109, has also appeared reaction intermediate compound 3 and the relevant quasi-molecular ions of reaction product compound 4
(m/z) 172,189, and interfered without other foreign ion peaks, illustrate that device of the present invention can accelerate Borsche-
Drechsel reaction can analyze organic reaction with direct-on-line, provide convenient way for study on mechanism.
It is visible in summary: after device of the present invention and mass spectrometry, to be remarkably improved the sensitive of mass spectral analysis
Degree and universality, macromolecular compound and difficult volatilization, easily cracking compound to actual sample, molecular weight higher than 1000 all have
Good ionising effect, has a wide range of application, and universality is strong, cannot be only used for the qualitative analysis of compound, it may also be used for sample
Quantitative analysis, especially can with direct-on-line analyze organic reaction, provide species analysis and reaction for organic chemist
Mechanism study provides convenient way, compared with the existing technology, has conspicuousness progress and practical value.
It is last it is necessarily pointed out that: the foregoing is merely the preferable specific embodiment of the present invention, but the present invention
Protection scope be not limited thereto, anyone skilled in the art in the technical scope disclosed by the present invention,
Any changes or substitutions that can be easily thought of, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of method using solvent and gas double auxiliary flame direct ion sample, it is characterised in that: produce flame
Raw energy and active specy is pushed under the common push of secondary solvent and auxiliary sheath gas to sample to be tested, is made to test sample
Product ionization.
2. it is a kind of using solvent and gas double auxiliary flame direct ion sample device, including flame, sample to be tested and
Mass spectrum sample intake passage, it is characterised in that: the flame is located in front of the port of mass spectrum sample intake passage, and the sample to be tested is located at fire
Between flame and mass spectrum sample intake passage；It further include secondary solvent channel for introducing secondary solvent and for introducing auxiliary sheath gas
Sheath gas channel is assisted, the auxiliary sheath gas channel is sheathed on the outside in secondary solvent channel, the outlet in the auxiliary sheath gas channel
The outlet end in end and secondary solvent channel is respectively positioned near flame, and the sample to be tested is located at the outlet end in auxiliary sheath gas channel
Between the outlet end and mass spectrum sample intake passage in secondary solvent channel.
3. the apparatus of claim 2, it is characterised in that: the flame is connected with fuel supply system.
4. the apparatus of claim 2, it is characterised in that: the secondary solvent channel is connected with secondary solvent supply dress
It sets.
5. the apparatus of claim 2, it is characterised in that: auxiliary sheath gas channel is connected with auxiliary sheath gas supply dress
It sets.
6. the apparatus of claim 2, it is characterised in that: the outlet end in secondary solvent channel and mass spectrum sample intake passage it
Between distance be 20~80mm.
7. the apparatus of claim 2, it is characterised in that: the distance between the outlet end in secondary solvent channel and flame
For 1~5mm.
8. the apparatus of claim 2, it is characterised in that: the internal diameter in the secondary solvent channel is 50~300 microns.
9. the apparatus of claim 2, it is characterised in that: the flow velocity of the secondary solvent in secondary solvent channel be 5~
70 mul/min, assisting the flow velocity of the auxiliary sheath gas in sheath gas channel is 15~40 ls/h.
10. the apparatus of claim 2, it is characterised in that: the auxiliary sheath gas be selected from air, carbon dioxide, nitrogen,
Any one in helium, argon gas.
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