CN104966657B - Sample introduction interface device for ionization source, mass spectrometry and liquid phase gas chromatograph-mass spectrometer - Google Patents
Sample introduction interface device for ionization source, mass spectrometry and liquid phase gas chromatograph-mass spectrometer Download PDFInfo
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- CN104966657B CN104966657B CN201510396792.3A CN201510396792A CN104966657B CN 104966657 B CN104966657 B CN 104966657B CN 201510396792 A CN201510396792 A CN 201510396792A CN 104966657 B CN104966657 B CN 104966657B
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Abstract
The invention provides a sample introduction interface device for an ionization source, a mass spectrometry and a liquid phase gas chromatograph-mass spectrometer. The sample introduction interface device for the ionization source includes a liquid phase capillary, a gas-liquid spraying pipe, a sheath gas pipeline, a sheath liquid pipeline and a heating component; the liquid phase capillary is provided with a liquid phase inlet; the gas-liquid spraying pipe can convert a liquid sample at the liquid phase outlet of the liquid phase capillary into mist spray and transmit the mist spray to an ionization zone between the outlet of an ion source and the ion sampling opening of the mass spectrometry; the gas-liquid spraying pipe sleeves the liquid phase capillary, so that the gas-liquid spraying pipe and the liquid phase capillary can form a gas-liquid channel; the gas-liquid spraying pipe is provided with a sheath gas inlet and a sheath liquid inlet; the sheath gas pipeline is used for transmitting sheath gas of preset pressure into the gas-liquid channel; the sheath gas pipeline is communicated with the sheath gas inlet; the sheath liquid pipeline is used for transmitting sheath liquid into the gas-liquid channel and is communicated with the sheath liquid inlet; and the heating component is used for heating the mist spray sprayed from the spraying opening of the gas-liquid spraying pipe and is located at one side of the spraying opening of the gas-liquid spraying pipe, wherein the one side of the spraying opening of the gas-liquid spraying pipe is adjacent to the ionization zone. With the sample introduction interface device for the ionization source, the mass spectrometry and the liquid phase gas chromatograph-mass spectrometer of the invention adopted, the influence of inorganic salt and weak-polar organic solvent on the ionization of the mass spectrometer can be decreased, and the application range of the liquid chromatographic-mass spectrometric method can be expanded.
Description
Technical field
The present invention relates to technical field is tested and analyzed, more particularly, it relates to a kind of ionization source sample introduction interface arrangement, this
Invention further relates to a kind of mass spectrograph with above-mentioned ionization source sample introduction interface arrangement and a kind of with above-mentioned mass spectrometric liquid phase
Chromatograph-mass spectrometer.
Background technology
Mass-spectrometric technique is by physics and chemistry means so that target molecule is ionized, using electromagnetic field by charged molecule according to mass-to-charge ratio
Distinguish the technology of detection.The features such as technology has fast analyze speed, high sensitivity and strong specificity, thus in chemistry and change
The field such as work, biology and life sciences, medical science, pharmacy, material science, environmental protection science is widely used.Liquid phase color
Spectral analysis technology, including capillary electrophoresis, are a kind of separation methods of comparative maturity, high, fast with separation efficiency height, sensitivity
Speed, wide accommodation, it is reproducible and easy to operate the features such as, thus be widely used in the matter of the clinical diagnosises of medical science, medicine
The fields such as amount control, drug metabolite analysis and pharmacokinetic.In recent years, high performance liquid chromatography and mass spectrographic success
Combination, realizes the combination of the strong separating power and mass spectrographic high sensitivity and strong distinguishing ability of liquid chromatograph, can be directly right
The sample of complicated component carries out a point analysis of variance.
Existing LC-ESI/MS (liquid chromatograph-mass spectrometer) is by electron spray ionisation source (ESI) by capillary intraluminal fluid
The liquid sample of phase chromatographic isolation is ionized and imports to mass ions transmission channel and detected.But, when containing in liquid sample
When having fixedness inorganic salt (such as inorganic buffer salt or hydrochlorate etc.), salt can be piled up at shower nozzle, destroy the integrity of spraying,
Mass ions transmission channel can be also blocked, also, salt and the low pole organic reagent in liquid sample can also produce competition electricity
Cause target molecule effectively cannot ionize from the inhibitory action such as matrix effect.Therefore, limit the range of application of LC-MS.
In sum, the impact that inorganic salt and weakly polar organic solvent are ionized to mass spectrograph how is reduced, to expand liquid matter
Associated with range of application, be current those skilled in the art technical problem urgently to be resolved hurrily.
The content of the invention
In view of this, it is an object of the invention to provide a kind of ionization source sample introduction interface arrangement, with reduce inorganic salt and
The impact that weakly polar organic solvent is ionized to mass spectrograph, so as to expand the range of application of LC-MS.
Another object of the present invention is to provide a kind of mass spectrograph and with above-mentioned ionization source sample introduction interface arrangement
Plant with above-mentioned mass spectrometric liquid chromatography mass combined instrument.
In order to achieve the above object, the present invention provides following technical scheme：
A kind of ionization source sample introduction interface arrangement, including：
Liquid phase capillary tube, the liquid phase capillary tube have the fluid inlet entered for liquid sample；
The liquid sample of the liquid-phase outlet of the liquid phase capillary tube can be converted into spraying and be transported to ionogenic outlet
And the gas-liquid jet pipe of the ionized region between the ion thief hatch of mass analyzer, the gas-liquid jet pipe are coated at the liquid phase capillary
Gas-liquid channel is formed described in Guan Bingyu between liquid phase capillary tube, the import of sheath gas and sheath fluid import on the gas-liquid jet pipe, is provided with；
The sheath air pipe of the sheath gas for conveying preset pressure into the gas-liquid channel, the sheath air pipe and the sheath
Gas inlet communication；
For the sheath liquid pipeline for conveying sheath fluid into the gas-liquid channel, the sheath liquid pipeline is connected with the sheath fluid import
It is logical；
For the heating member heated to the spraying that the ejiction opening from the gas-liquid jet pipe sprays, the heating member is located at
The ejiction opening of the gas-liquid jet pipe is near the side of the ionized region.
Preferably, above-mentioned ionization source is with sample introduction interface arrangement, and the liquid-phase outlet of the liquid phase capillary tube protrudes from described
The ejiction opening of gas-liquid jet pipe.
Preferably, with sample introduction interface arrangement, the port of export of the gas-liquid jet pipe is from away from the ionization for above-mentioned ionization source
Tapered at one end of the one end in area to the close ionized region, and a diameter of 0.8mm-1.2mm of ejiction opening of the gas-liquid jet pipe；
The distance of ejiction opening of the liquid-phase outlet of the liquid phase capillary tube away from the gas-liquid jet pipe is 0.3mm-0.5mm.
Preferably, above-mentioned ionization source is with sample introduction interface arrangement, and the port of export of the gas-liquid jet pipe is taper ejiction opening, institute
The straight length that taper ejiction opening is stated with the gas-liquid jet pipe is detachably connected.
Preferably, with sample introduction interface arrangement, the heating member is the circle for being coated at the gas-liquid jet pipe to above-mentioned ionization source
Column sleeve cylinder, the cylindrical sleeves have heating part near the side of the ionized region；
Ionization source sample introduction interface arrangement also includes base, and the cylindrical sleeves are arranged on the base and pass through
Bolt is fixedly connected with the gas-liquid jet pipe, and the tapped through hole passed through for the bolt is provided with the cylindrical sleeves, described
The outer wall of gas-liquid jet pipe is offseted with the bolt, and with along its axially arranged a plurality of fixed mark on the gas-liquid jet pipe outer wall
Timberline.
Preferably, above-mentioned ionization source is with sample introduction interface arrangement, the cylindrical sleeves by the first micrometer, the 2000th point
Chi and the 3rd micrometer are arranged on the base, the micrometric screw of first micrometer along X to setting, the described 2000th
The micrometric screw of chi is divided to arrange along Y-direction, the micrometric screw of the 3rd micrometer is arranged along Z-direction, the frame of second micrometer
Frame is fixed on the micrometric screw of first micrometer, and the framework of the 3rd micrometer is fixed on second micrometer
On micrometric screw, the cylindrical sleeves are fixedly installed on the micrometric screw of the 3rd micrometer；Wherein, X to, Y-direction, Z-direction
It is vertical two-by-two.
Preferably, above-mentioned ionization source is with ceramic cylinder in sample introduction interface arrangement, is also arranged with outside the cylindrical sleeves, described
Ceramic cylinder is connected away from the threaded one end of the one end with the cylindrical sleeves away from the ionized region of the ionized region.
Preferably, above-mentioned ionization source is also included with sample introduction interface arrangement：
Control the control chamber of the running voltage and temperature of the heating member；
The diaphragm valve of the sheath atmospheric pressure that the sheath air pipe is transported in the gas-liquid jet pipe is adjusted, the diaphragm valve is arranged
On the sheath air pipe.
It can be seen from above-mentioned technical scheme that, the ionization source sample introduction interface arrangement that the present invention is provided includes liquid phase capillary
Pipe, gas-liquid jet pipe, sheath air pipe, sheath liquid pipeline and heating member；Wherein, liquid phase capillary tube has the liquid phase entered for liquid sample
Import；The liquid sample of the liquid-phase outlet of liquid phase capillary tube can be converted into spraying and be transported to ionogenic outlet by gas-liquid jet pipe
And the ionized region between the ion thief hatch of mass analyzer, gas-liquid jet pipe be coated at liquid phase capillary tube and with liquid phase capillary tube it
Between form gas-liquid channel, the import of sheath gas and sheath fluid import are provided with gas-liquid jet pipe；Sheath air pipe is for defeated in gas-liquid channel
Send the sheath gas of preset pressure, sheath air pipe and sheath gas inlet communication；Sheath liquid pipeline is for conveying sheath fluid, sheath fluid into gas-liquid channel
Pipeline and sheath fluid inlet communication；Heating member for from gas-liquid jet pipe ejiction opening spray spraying heat, heating member position
In gas-liquid jet pipe ejiction opening near the side of ionized region.
Using when, first by liquid sample from fluid inlet import liquid phase capillary tube；Pass through sheath trachea road direction gas-liquid simultaneously
In passage, conveying sheath gas, conveys sheath fluid by sheath liquid pipeline into gas-liquid channel, so that preset pressure is full of in gas-liquid channel
The gas-liquid mixture fluid of (typically in 5kPa to 10kPa), can drive during gas-liquid mixture fluid is flowed out to ejiction opening
The liquid sample that the liquid-phase outlet of liquid phase capillary tube flows out is converted into spraying together；Then heating member carries out adding to whole spraying
Heat, enables the gas-liquid mixture from ejiction opening transmitting fully to heat, and then makes determinand molecule gasify, and inorganic salt molecule cluster gathers
Into solid-state crystallite, such that it is able to efficiently separate determinand molecule and inorganic salt in liquid sample, such as phosphate, carbonate,
Borate, hydrochlorate etc.；By determinand molecular jet between ionogenic outlet and the ion thief hatch of mass analyzer
In ionized region, the ionizing efficiency of ionization source can be improved in the solvent such as protonated solvent such as water, methanol of this process volatilization, and it is weak
Polar organic solvent is difficult to generation quasi-molecular ion is combined with proton, hardly ionizes with determinand competition.
In summary, ionization source sample introduction interface arrangement of the invention can reduce inorganic salt and weakly polar organic solvent pair
The impact of mass spectrograph ionization, so as to expand the range of application of LC-MS.
Present invention also offers a kind of mass spectrograph, including mass ion source and mass analyzer, the mass ion source is
DART ionization sources, the mass spectrograph also include for liquid sample to be transported to the sample introduction interface arrangement of the DART ionization sources,
The sample introduction interface arrangement is any of the above-described kind of ionization source sample introduction interface arrangement, due to above-mentioned ionization source sample introduction interface arrangement
With the effect above, the mass spectrograph with above-mentioned ionization source sample introduction interface arrangement has same effect, therefore no longer goes to live in the household of one's in-laws on getting married herein
State.
Present invention also offers a kind of liquid chromatography mass combined instrument, including chromatograph and with the chromatographic liquid-like
The mass spectrograph of product outlet connection, the mass spectrograph is any of the above-described kind of mass spectrograph, as above-mentioned mass spectrograph has the effect above, tool
There is above-mentioned mass spectrometric liquid chromatography mass combined instrument that there is same effect, therefore repeat no more herein.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can be with basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the partial structural diagram of ionization source sample introduction interface arrangement provided in an embodiment of the present invention；
Fig. 2 is another partial structural diagram of ionization source sample introduction interface arrangement provided in an embodiment of the present invention.
Specific embodiment
A kind of ionization source sample introduction interface arrangement is embodiments provided, inorganic salt can be reduced and low pole is organic
The impact that solvent is ionized to mass spectrograph, so as to expand the range of application of LC-MS.
To make purpose, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
The a part of embodiment of the present invention, rather than the embodiment of whole.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
Refer to accompanying drawing 1-2, ionization source sample introduction interface arrangement provided in an embodiment of the present invention include liquid phase capillary tube 1,
Gas-liquid jet pipe 2, sheath air pipe 4, sheath liquid pipeline 5 and heating member；Wherein, liquid phase capillary tube 1 has the liquid entered for liquid sample
Phase import；Gas-liquid jet pipe 2 can by the liquid sample of the liquid-phase outlet of liquid phase capillary tube 1 be converted into spraying be transported to it is ionogenic
Outlet and the ion thief hatch of mass analyzer between ionized region, gas-liquid jet pipe 2 be coated at liquid phase capillary tube 1 and with liquid phase hair
Gas-liquid channel is formed between tubule 1, the import of sheath gas and sheath fluid import on gas-liquid jet pipe 2, is provided with；Sheath air pipe 4 is for gas-liquid
The sheath gas of conveying preset pressure, sheath air pipe 4 and sheath gas inlet communication in passage；Sheath liquid pipeline 5 is for defeated in gas-liquid channel
Send sheath fluid, sheath liquid pipeline 5 and sheath fluid inlet communication；Heating member for from gas-liquid jet pipe 2 ejiction opening spray spraying carry out
Heating, heating member are located at the ejiction opening of gas-liquid jet pipe 2 near the side of ionized region.
It should be noted that above-mentioned sheath air pipe 4 is transported to axial direction stream of the sheath gas in gas-liquid channel along liquid phase capillary tube 1
It is dynamic, the liquid sample uniformly continuous spraying flowed out is driven from liquid phase capillary tube 1 together with sheath fluid.Specifically, in order to reduce gravity
Affect, gas-liquid jet pipe 2 is vertically arranged, ionogenic outlet is located at same level with the ion thief hatch of mass analyzer
On line, ionized region is formed between the two, gas-liquid jet pipe 2 is arranged above ionized region；Heating member is located at the ejiction opening of gas-liquid jet pipe 2
It is located at immediately below the ejiction opening of gas-liquid jet pipe 2 near the side of ionized region, i.e. heating member, whole spraying is heated, is had
Preferable signal effect.
Above-mentioned liquid sample can be fluid sample direct injected and the liquid sample through chromatographic isolation.
Using when, liquid sample is imported into liquid phase capillary tube 1 from fluid inlet first；Simultaneously by sheath air pipe 4 to gas
In liquid passage, conveying sheath gas, conveys sheath fluid by sheath liquid pipeline 5 into gas-liquid channel, so that full of default pressure in gas-liquid channel
The gas-liquid mixture fluid of power (typically in 5kPa to 10kPa), being capable of band during gas-liquid mixture fluid is flowed out to ejiction opening
The liquid sample that the liquid-phase outlet of hydrodynamic phase capillary tube 1 flows out is converted into spraying together；Then heating member is carried out to whole spraying
Heating, enables the gas-liquid mixture from ejiction opening transmitting fully to heat, and then makes determinand molecule gasify, inorganic salt molecule cluster
Solid-state crystallite is polymerized to, such that it is able to efficiently separate determinand molecule and inorganic salt in liquid sample, such as phosphate, carbonic acid
Salt, borate, hydrochlorate etc.；By determinand molecular jet between ionogenic outlet and the ion thief hatch of mass analyzer
Ionized region in, the ionizing efficiency of ionization source can be improved in the solvent such as protonated solvent such as water, methanol of this process volatilization, and
Weakly polar organic solvent is difficult to generation quasi-molecular ion is combined with proton, hardly ionizes with determinand competition.
In summary, ionization source sample introduction interface arrangement of the invention can reduce inorganic salt and weakly polar organic solvent pair
The impact of mass spectrograph ionization, so as to expand the range of application of LC-MS.
In specific embodiment, the determinand molecule that gasification separation is gone out by the ionization source sample introduction interface arrangement of the present invention sprays
It is mapped to outlet and the mass spectrum point of DART (abbreviation of Direct Analysis in Real Time, Direct Analysis in Real Time) ionization source
In ionized region between the ion thief hatch of parser, introduce in mass spectrographic mass analyzer after DART is ionized, it is adaptable to liquid
The Mass Spectrometer Method of body sample direct injected and the liquid sample through chromatographic isolation.
In order to reach preferable spray effect, the ionization source that above-described embodiment is provided with sample introduction interface arrangement, liquid phase hair
The liquid-phase outlet of tubule 1 protrudes from the ejiction opening of gas-liquid jet pipe 2.Now, the liquid-phase outlet of liquid phase capillary tube 1 is located at gas-liquid jet pipe
I.e. near the side of ionized region on the outside of 2 ejiction opening, it is easy to drive liquid sample to form spraying.Certainly, above-mentioned liquid phase capillary tube 1
Liquid-phase outlet can also be arranged on the inside of the ejiction opening of gas-liquid jet pipe 2.
Further, as shown in Figure 1-2, the port of export of gas-liquid jet pipe 2 is from the one end away from ionization source near ionization source
Tapered at one end, and a diameter of 0.8mm-1.2mm of ejiction opening of gas-liquid jet pipe 2, preferably 1mm；The liquid phase of liquid phase capillary tube 1 goes out
Ejiction opening mouthful away from gas-liquid jet pipe 2 apart from 0.3mm-0.5mm, preferably 0.5mm.So, gas-liquid jet pipe 2 has less
Ejiction opening, accelerate flow velocity of the sheath fluid sheath gas fluid-mixing at ejiction opening, coordinate sheath gas and sheath liquid energy in gas-liquid channel
Enough drive the liquid sample of liquid-phase outlet to obtain good gas-liquid blending spraying state so that determinand molecule and inorganic salt it
Between have preferable separating effect.The ejiction opening of above-mentioned diminution simultaneously can also limit liquid phase capillary tube 1 to a certain extent and put
It is dynamic.It is understood that above-mentioned gas-liquid jet pipe 2 can also be straight tube shape, as long as can realize driving liquid sample to reach spraying
The shape of state.
In order to optimize above-mentioned technical proposal, the port of export of gas-liquid jet pipe 2 is taper ejiction opening, taper ejiction opening and gas-liquid spray
The straight length of pipe 2 is detachably connected.Now, the surface of gas-liquid jet pipe 2 is taper seat, is easy to processing.Specifically, the taper sprays
Mouthful using threaded connection realize detachably, when taper ejiction opening wear and tear it is more serious when can only change ejiction opening, saved into
This, while being easy to dismounting.The port of export of the gas-liquid jet pipe 2 can also be multiple planes constitute, or curved surface formed tapered shape
In order that spraying is heated evenly, it is preferred that heating member is the cylindrical sleeves 3 for being coated at gas-liquid jet pipe 2, cylindrical sleeves
3 have heating part 31 near the side of ionized region；In order to reduce gravity impact, gas-liquid jet pipe 2 is vertically arranged, DART's
Outlet is located in same horizontal line with the ion thief hatch of mass spectrographic mass analyzer, forms ionized region, gas-liquid spray between the two
Pipe 2 is arranged above ionized region, and the top of cylindrical sleeves 3 is set on the outside of gas-liquid jet pipe 2, and bottom is provided with heating part 31, is located at
The lower section of gas-liquid jet pipe 2 is heated to whole spraying, and signal effect is more preferable.Interchangeable, above-mentioned heating member can also be edge
Circumferentially disposed multiple heating plates.
For the ease of installing, ionization source sample introduction interface arrangement also includes base (not shown), and cylindrical sleeves 3 are arranged
It is fixedly connected with gas-liquid jet pipe 2 on base and by bolt, on cylindrical sleeves 3, is provided with the tapped through hole passed through for bolt,
The outer wall of gas-liquid jet pipe 2 is offseted with bolt, and with along its axially arranged a plurality of fixed marking line on 2 outer wall of gas-liquid jet pipe.
By the present invention in that bolt is offseted through the tapped through hole on cylindrical sleeves 3 and with the outer wall of gas-liquid jet pipe 2, oppressed using bolt
2 outer wall of gas-liquid jet pipe produces trickle Metal Deformation banding cylindrical sleeves 3 and gas-liquid jet pipe 2.According to detection liquid sample not
Together, the present invention is made bolt be locked at corresponding fixation of gas-liquid jet pipe 2 and represents line also by the height and position of adjustment gas-liquid jet pipe 2
Position, so as to pass through to change the height of gas-liquid jet pipe 2, realize the phase between heating part 31 and the ejiction opening of gas-liquid jet pipe 2
It is adjustable to position, so as to make liquid sample reach preferable released state by regulation, improve ionization effect.Certainly, cylindrical sleeve
Cylinder 3 can also be achieved a fixed connection by other structures with gas-liquid jet pipe 2, connecting pole being such as weldingly connected with both respectively etc..
In order to further optimize above-mentioned technical proposal, above-mentioned cylindrical sleeves 3 by the first micrometer, the second micrometer and
3rd micrometer is arranged on base, and, along X to setting, the micrometric screw of the second micrometer is along Y for the micrometric screw of the first micrometer
To setting, the micrometric screw of the 3rd micrometer is arranged along Z-direction, and the framework of the second micrometer is fixed on the micrometer spiral shell of the first micrometer
On bar, the framework of the 3rd micrometer is fixed on the micrometric screw of the second micrometer, and cylindrical sleeves 3 are fixedly installed on the 3000th point
On the micrometric screw of chi；Wherein, X is vertical two-by-two to, Y-direction, Z-direction.The present invention causes cylindrical sleeves 3 relative by three micrometers
Can be three-dimensional adjustable in base, so as to pass through to adjust gas in the different buffer salt systems of analysis and different organic solvents system
The ejiction opening of liquid jet pipe 2 obtains stable detection signal relative to DART and the three-dimensional position of mass spectrographic mass analyzer.
The ionization source sample introduction interface arrangement can be with efficiently/Ultra Performance Liquid Chromatography/capillary electrophoresis-DART ionization
Source-mass analyzer is integrated and is used, and carries out open type to the liquid sample of sample or direct injected through liquid phase separation big
Air pressure is ionized and introduces mass spectrum and is analyzed detection, and this device improves requirement of the LC-MS to liquid phase buffer salt, and strengthens
The signal intensity and stability of DART detections.
Certainly, by other devices, the present invention can also realize that cylindrical sleeves 3 can be three-dimensional adjustable relative to base, such as
The X being made up of line slide rail, ball-screw and servomotor is to, the motion of Y-direction, Z-direction.
Cylindrical sleeves 3 are outer to be also arranged with ceramic cylinder (not shown), one end and circle of the ceramic cylinder away from ionized region
Column sleeve cylinder 3 connects away from the threaded one end of ionized region.Above-mentioned ceramic cylinder can be incubated to heating part 31, realize thermal-arrest and
Air-flow is limited, makes liquid sample reach more preferable separating effect.
Preferably, ionization source sample introduction interface arrangement also includes the control of the running voltage and temperature of control heating member
Case；The diaphragm valve that sheath air pipe 4 is transported to the sheath atmospheric pressure in gas-liquid jet pipe 2 is adjusted, diaphragm valve is arranged on sheath air pipe 4.
In specific work process, heating member running voltage is 24V, by the temp controlled meter control temperature of control chamber.The pressure of sheath air-flow can be with
As desired by barrier film valve regulation.Can also pass through when this device analysis difference buffer salt system and different organic solvents system
The stable detection signal of the control gain of parameter such as heating-up temperature and sheath gas.
For the ease of assembling, above-mentioned liquid phase capillary tube 1 is fixed on gas-liquid jet pipe 2 away from the one of ionization source by graphite gasket
End is top, and graphite gasket is arranged and is sealed between liquid phase capillary tube 1 and gas-liquid jet pipe 2, the import of sheath gas and sheath fluid import position
In graphite gasket near the side of ionization source.Now can as needed, by the phase for adjusting graphite gasket and liquid phase capillary tube 1
To position, the relative position of the liquid-phase outlet of liquid phase capillary tube 1 and the ejiction opening of gas-liquid jet pipe 2 is adjusted.
Further, the internal diameter of liquid phase capillary tube 1 is 75 μm -150 μm.Liquid phase capillary tube 1 is metal capillary or table
Layer has the quartz capillary of polyimide coating, so that liquid phase capillary tube 1 is bent, is conveniently adjusted its position, while drop
Because of the damage of bending generation in the low course of work.Above-mentioned polyimides, with preferable resistant of high or low temperature, electric insulating quality, glue
Knot property, radiation resistance, resistance to medium, chemical stability and anti-flammability, improve the service life of liquid phase capillary tube 1.
The present invention also sets up waste collecting device below ionized region, is easy to collect the waste liquid for spraying.
The embodiment of the present invention additionally provides a kind of mass spectrograph, including mass ion source and mass analyzer, mass ion source
For DART ionization sources, mass spectrograph is also included for liquid sample to be transported to the sample introduction interface arrangement of DART ionization sources, and sample introduction connects
The ionization source sample introduction interface arrangement that mouth device is provided for any of the above-described embodiment, can reduce inorganic salt and low pole is organic
The impact that solvent is ionized to mass spectrograph, so as to expand the range of application of LC-MS；Its advantage is by ionization source sample introduction interface
What device brought, the part of correlation in above-described embodiment is specifically refer to, here is just repeated no more.
In an embodiment of concrete practice：
Ionization source sample introduction interface arrangement parameter setting：Heating-up temperature be 250 DEG C, sheath gas air pressure be 5kPa, DART temperature
For 350 DEG C, DART is 10mm with mass analyzer distance, and ejiction opening is above DART with mass analyzer line apart from mass spectrum
Analyzer 7mm.
Liquid sample to be measured is Reserpine, and 5 μ g/mL of concentration are dissolved in water/acetonitrile for 1:In 1 solution, solution system contains
137mM NaCl, 2.7mM KCl, 10mM Na2HPO4, 2mM KH2PO4。
The sample enters this device with the flow velocity of 200 μ L/min by peristaltic pump, eliminates the interference of inorganic salinity, obtains
Good ionization effect.
In another embodiment of concrete practice：
Ionization source sample introduction interface arrangement parameter setting：Device heating-up temperature is 260 DEG C, and sheath gas air pressure is 10kPa, DART
Temperature is 350 DEG C, and DART is 15mm with mass analyzer distance, and ejiction opening is positioned at distance above DART with mass analyzer line
Mass spectrum 10mm.
Testing sample is reached for lorazepam, clonazepam, diazepam, oxazepam, nitrazepam, chlordiazepoxide and maleic acid miaow
Seven kinds of benzodiazepines such as azoles logical sequence, after dissolving in methyl alcohol, are diluted to phosphoric acid-potassium dihydrogen phosphate that pH is 2.5
Concentration is respectively 30-150 μ g/mL.
Biased sample is separated in the way of gradient elution, and introduces this device by liquid chromatograph, is obtained after DART ionization
LC-MS spectrogram there is no notable difference with the separating degree of simple liquid phase separation, seven kinds of materials can well be ionized and not received
To phosphatic impact.
The DART ionization sources that the present invention is adopted have good tolerance to inorganic salt and aprotic solvents, weak polar solvent
Property.DART (Direct Analysis in Real Time technology) ionization source is a kind of new open type atmospheric pressure ionization techniques.DART technologies are bases
Develop in Atmosphere Pressure Chemical Ionization (APCI) (APCI) principle, ionization is carried out by way of this molecule-ionic reaction can be with
Target molecule is ionized in the case of sample contains higher salinity and stronger matrix effect.Its main ionization process master
To include that the water in excited state gas (such as nitrogen, helium or argon) atom and surrounding air that electric discharge is produced reacts, by shape
Into water cluster from
The mode of son and then the quasi-molecular ion for generating determinand with sample molecule reaction carries out ionization and excited state gas
The mode that atom generates molecular ion with determinand molecule direct reaction in gas phase is ionized i.e. Penning ionization (Penning
Ionization) two kinds of principles.
The ionizing efficiency of DART can be improved in the solvent such as protonated solvent such as water, methanol of this process volatilization.DART is electric
The LC-MS spectrogram obtained after does not have notable difference with the separating degree of simple liquid phase separation, and seven kinds of materials can be well electric
From and be subject to phosphatic impact.
The embodiment of the present invention additionally provides a kind of liquid chromatography mass combined instrument, including chromatograph and with chromatographic liquid
The mass spectrograph of sample export connection, mass spectrograph is above-mentioned mass spectrograph, as above-mentioned mass spectrograph has the effect above, with above-mentioned matter
The liquid chromatography mass combined instrument of spectrometer has same effect, therefore repeats no more herein.
The present invention realizes liquid chromatograph and DART-MS combination analysis.And by optimizing liquid phase effluent with mass spectrum entrance
The related parameters of position, the species of secondary solvent, ionization, realize the qualitative and quantitative analysis to heterogeneity compound, and
And can be set up including the LC-DART-MS analysis methods suitable for traditional Chinese medicine complex system and biological sample according to result of study.
The present invention is expanded applications of the DART in association area significantly, and requirement of the LC-MS to liquid phase buffer salt is further put
It is wide.
In this specification, each embodiment is described by the way of progressive, and what each embodiment was stressed is and other
The difference of embodiment, between each embodiment identical similar portion mutually referring to.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope for causing.
Claims (8)
1. a kind of ionization source sample introduction interface arrangement, it is characterised in that include：
Liquid phase capillary tube (1), the liquid phase capillary tube (1) is with the fluid inlet entered for liquid sample；
Can by the liquid sample of the liquid-phase outlet of the liquid phase capillary tube (1) be converted into spraying be transported to it is ionogenic outlet with
The gas-liquid jet pipe (2) of the ionized region between the ion thief hatch of mass analyzer, the gas-liquid jet pipe (2) are coated at the liquid phase
Capillary tube (1) simultaneously forms gas-liquid channel between the liquid phase capillary tube (1), is provided with sheath gas and enters on the gas-liquid jet pipe (2)
Mouth and sheath fluid import；
For into the gas-liquid channel convey preset pressure sheath gas sheath air pipe (4), the sheath air pipe (4) with it is described
Sheath gas inlet communication；
For the sheath liquid pipeline (5) for conveying sheath fluid into the gas-liquid channel, the sheath liquid pipeline (5) is connected with the sheath fluid import
It is logical；
For the heating member heated to the spraying that the ejiction opening from the gas-liquid jet pipe (2) sprays, the heating member is located at
The ejiction opening of the gas-liquid jet pipe (2) is near the side of the ionized region；
The heating member is to be coated at the cylindrical sleeves (3) of the gas-liquid jet pipe (2), the cylindrical sleeves (3) near it is described from
The side of component has heating part (31)；
Ionization source sample introduction interface arrangement also includes base, and the cylindrical sleeves (3) are arranged on the base and pass through
Bolt is fixedly connected with the gas-liquid jet pipe (2), is provided with and leads to for the screw thread that the bolt is passed through on the cylindrical sleeves (3)
Hole, the outer wall of the gas-liquid jet pipe (2) are offseted with the bolt, and with setting along its axial direction on the gas-liquid jet pipe (2) outer wall
The a plurality of fixed marking line put；
The cylindrical sleeves (3) are arranged on the base by the first micrometer, the second micrometer and the 3rd micrometer, institute
The micrometric screw of the first micrometer is stated along X to setting, the micrometric screw of second micrometer is arranged along Y-direction, the described 3000th
The micrometric screw of chi is divided to arrange along Z-direction, the framework of second micrometer is fixed on the micrometric screw of first micrometer,
The framework of the 3rd micrometer is fixed on the micrometric screw of second micrometer, and the cylindrical sleeves (3) are fixedly installed
On the micrometric screw of the 3rd micrometer；Wherein, X is vertical two-by-two to, Y-direction, Z-direction.
2. ionization source as claimed in claim 1 sample introduction interface arrangement, it is characterised in that the liquid of the liquid phase capillary tube (1)
Mutually outlet protrudes from the ejiction opening of the gas-liquid jet pipe (2).
3. ionization source as claimed in claim 2 sample introduction interface arrangement, it is characterised in that the outlet of the gas-liquid jet pipe (2)
End is from the one end away from the ionized region to the tapered at one end near the ionized region, and the ejiction opening of the gas-liquid jet pipe (2)
A diameter of 0.8mm-1.2mm；
The distance of ejiction opening of the liquid-phase outlet of the liquid phase capillary tube (1) away from the gas-liquid jet pipe (2) is 0.3mm-0.5mm.
4. ionization source as claimed in claim 3 sample introduction interface arrangement, it is characterised in that the outlet of the gas-liquid jet pipe (2)
Hold as taper ejiction opening, the taper ejiction opening is detachably connected with the straight length of the gas-liquid jet pipe (2).
5. ionization source as claimed in claim 1 sample introduction interface arrangement, it is characterised in that the cylindrical sleeves (3) also cover outward
Be provided with ceramic cylinder, the ceramic cylinder away from the ionized region one end with the cylindrical sleeves (3) away from the ionized region
Threaded one end connection.
6. ionization source as claimed in claim 1 sample introduction interface arrangement, it is characterised in that also include：
Control the control chamber of the running voltage and temperature of the heating member；
The diaphragm valve of the sheath atmospheric pressure that the sheath air pipe (4) is transported in the gas-liquid jet pipe (2) is adjusted, the diaphragm valve sets
Put on the sheath air pipe (4).
7. a kind of mass spectrograph, including mass ion source and mass analyzer, it is characterised in that the mass ion source is that DART is electric
From source, the mass spectrograph is also included for liquid sample to be transported to the sample introduction interface arrangement of the DART ionization sources, it is described enter
Sample interface arrangement is the ionization source sample introduction interface arrangement as described in any one of claim 1-6.
8. a kind of liquid chromatography mass combined instrument, including chromatograph and the mass spectrum being connected with the chromatographic liquid sample outlet
Instrument, it is characterised in that the mass spectrograph is mass spectrograph as claimed in claim 7.
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| CN106841459A (en) * | 2017-03-31 | 2017-06-13 | 北京雪迪龙科技股份有限公司 | A kind of gas chromatography combined with mass spectrometry interface, system and flow matches method |
| IT201700115527A1 (en) * | 2017-10-13 | 2019-04-13 | Univ Degli Studi Di Urbino Carlo Bo | MACHINE FOR CHEMICAL ANALYSIS INCLUDING THE COMBINATION OF MASS SPECTROMETRY WITH ELECTRONIC IONIZATION WITH LIQUID CHROMATOGRAPHY |
| CN109841485B (en) * | 2017-11-27 | 2020-05-08 | 中国科学院大连化学物理研究所 | Device for improving ion transmission efficiency by aerodynamic assistance method |
| CN110085506A (en) * | 2018-01-26 | 2019-08-02 | 广州禾信仪器股份有限公司 | Sample introduction assembly, open type ion source system and mass spectrometer |
| CN110085507B (en) * | 2018-01-26 | 2024-03-26 | 广州禾信仪器股份有限公司 | Open ion source system and mass spectrometer |
| CN108831819A (en) * | 2018-04-20 | 2018-11-16 | 中国药科大学 | A kind of equipment and its application in ortho states-denaturation conversion ions source |
| CN109473336B (en) * | 2018-12-19 | 2024-03-12 | 中国科学院长春应用化学研究所 | High-efficiency ionization probe electrospray mass spectrum ion source device and probe suitable for same |
| CN110400740A (en) * | 2019-07-23 | 2019-11-01 | 中国科学院上海有机化学研究所 | A kind of method and apparatus using solvent and gas double auxiliary flame direct ion sample |
| CN111024804A (en) * | 2019-12-19 | 2020-04-17 | 北京工业大学 | Chip-based sheath gas-assisted nanoliter electrospray ionization mass spectrometry ion source system and method |
| CN115097057B (en) * | 2022-06-02 | 2023-07-21 | 浙江大学 | Liquid chromatography-mass spectrometry detection method capable of directly analyzing salt-containing sample based on heat-assisted neutral double-spray rapid evaporation |
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| US5170053A (en) * | 1990-08-30 | 1992-12-08 | Finnigan Corporation | Electrospray ion source and interface apparatus and method |
| US5122670A (en) * | 1991-05-17 | 1992-06-16 | Finnigan Corporation | Multilayer flow electrospray ion source using improved sheath liquid |
| US6511850B1 (en) * | 1999-07-13 | 2003-01-28 | The Texas A&M University System | Pneumatic nebulizing interface to convert an analyte-containing fluid stream into an aerosol, method for using same and instruments including same |
| WO2007029431A1 (en) * | 2005-09-07 | 2007-03-15 | Human Metabolome Technologies, Inc. | Method of calibrating mass detected by mass spectrograph |
| CN204189766U (en) * | 2014-10-09 | 2015-03-04 | 东华理工大学 | Overhead polar coordinates adjusting device |
| CN204927235U (en) * | 2015-07-08 | 2015-12-30 | 中国科学院长春应用化学研究所 | Ionization source is with advancing a kind interface arrangement , mass spectrograph and liquid chromatograph/mass spectrometer |
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