CN106932524A - Thin layer of liquid chromatograph-mass spectrometer coupling device, purposes and detection method - Google Patents

Thin layer of liquid chromatograph-mass spectrometer coupling device, purposes and detection method Download PDF

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Publication number
CN106932524A
CN106932524A CN201511021226.0A CN201511021226A CN106932524A CN 106932524 A CN106932524 A CN 106932524A CN 201511021226 A CN201511021226 A CN 201511021226A CN 106932524 A CN106932524 A CN 106932524A
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sample
desorption
thin
laser
component
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CN106932524B (en
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聂宗秀
李亚峰
陈素明
熊彩侨
侯剑
张宁
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Institute of Chemistry of CAS
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Institute of Chemistry of CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/90Plate chromatography, e.g. thin layer or paper chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/90Plate chromatography, e.g. thin layer or paper chromatography
    • G01N30/94Development
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/90Plate chromatography, e.g. thin layer or paper chromatography
    • G01N30/95Detectors specially adapted therefor; Signal analysis

Abstract

The present invention proposes thin layer of liquid chromatograph-mass spectrometer coupling device, purposes and detection method, and the device includes:Chromatographic sheet, the thin-layer chromatography plate surface is provided with fixing phase;Desorption chamber, the desorption chamber is arranged on the chromatographic sheet upper surface;Development of Thin-Layer Chromatography unit, the Development of Thin-Layer Chromatography unit is connected with the chromatographic sheet;And mass spectrum unit, the mass spectrum unit with it is described desorption chamber be connected.Thus, it is possible to realize TLC separation process and Mass Spectrometer Method process synchronously carry out, so as to save detection time and simplify detection operating process.

Description

Thin layer of liquid chromatograph-mass spectrometer coupling device, purposes and detection method
Technical field
The present invention relates to analytical chemistry and instrument manufacturing field, in particular it relates to thin layer of liquid chromatograph-mass spectrometer coupling device, Purposes and detection method.
Background technology
Thin-layer chromatography (TLC) is as one of important member in chromatogram family with its convenience, high flux, low cost, solvent Consumption is few etc., and advantage is still widely used so far.Thin-layer chromatography usually using each component Rf value (Rf) qualitative to carry out, But Rf value easily receives external environmental interference, and generally not can determine that the chemical composition of the component still, therefore utilize thin-layer chromatography The analysis qualitative difficulty of sample.And mass spectrum can alleviate above-mentioned asking as a kind of powerful qualitative instrument, and the combination of thin-layer chromatography Topic.In recent years, developing rapidly with mass ions method, various thin-layer chromatography-mass spectrometry (TLC-MS) methods In succession report, such as thin-layer chromatography-substance assistant laser desorpted ionization massspectrum method (TLC/MALDI-MS), thin-layer chromatography- LC-MS spectrometry method (TLC/ESI-MS), thin-layer chromatography-desorption electrospray ionization mass spectrometry method (TLC/DESI-MS), thin-layer chromatography-APCI mass spectrometry method (TLC/APCI-MS) etc..
However, current thin-layer chromatography-mass spectrometry device, using and detection sample method still have much room for improvement.
The content of the invention
The present invention is based on obtained from the following discovery of inventor:
Current thin-layer chromatography-mass spectrometry device, generally existing detection time problem long.Using the thin layer after mass spectrometry Chromatograph-mass spectrometer coupling device carries out sample detection, detection time can even exceed sometimes it is simple using thin-layer chromatography detection when Between.Inventor has found that this is due to when thin-layer chromatography-mass spectrometry, in order to avoid mass spectrum is to sample solution by further investigation Suction/ionization process to thin-layer chromatography sample launch process interference, it usually needs the complete paired samples of thin-layer chromatography separation it Afterwards, it is re-introduced into Mass Spectrometer Method process.And plate chromatography developing solvent relies primarily on capillarity sample is carried out along chromatographic sheet Launch, realize the separation of each component in sample.And this process is time-consuming more long in itself, it usually needs dozens of minutes even Individual hour, and it is mass spectrographic detection need wait Development of Thin-Layer Chromatography process carry out completely after, it is each in the sample that will be separated Individual component is extracted from chromatographic sheet, or each sample on the general plate of thin layer color is ionized respectively, is entered back into The process of mass spectral analysis.Time-consuming for above-mentioned expansion, extraction process, and the introducing of Mass Spectrometer Method will be further increased detection sample The required time.
It is contemplated that at least solving one of technical problem present in prior art to a certain extent.Therefore, of the invention The first purpose is to propose a kind of thin layer of liquid chromatograph-mass spectrometer coupling device that desorption chamber is provided with chromatographic sheet.Should Device is provided with desorption chamber on chromatographic sheet, it is to avoid sample is desorbed and ionization process launched to thin-layer chromatography sample The interference of journey, realize TLC separation process and Mass Spectrometer Method process synchronously carry out, so as to save detection time and letter Detection operating process is changed.
In one aspect of the invention, the present invention proposes a kind of thin layer of liquid chromatograph-mass spectrometer coupling device, and the device includes: Chromatographic sheet, the thin-layer chromatography plate surface is provided with fixing phase;Desorption chamber, the desorption chamber is arranged on described thin Layer chromatography plate upper surface;Development of Thin-Layer Chromatography unit, the Development of Thin-Layer Chromatography unit is connected with the chromatographic sheet;With And mass spectrum unit, the mass spectrum unit with it is described desorption chamber be connected.Thus, it is possible to realize TLC separation process and matter Spectrum detection process is synchronously carried out, so as to save detection time and simplify detection operating process.
Embodiments in accordance with the present invention, the mass spectrum unit includes:Ionization component, the ionization component and the desorption Chamber is connected, and is provided with ion gun in the ionization component, the ion gun be inert gas auxiliary glow discharge from Component, Direct Analysis in Real Time ion gun, low temperature plasma ion gun or dielectric barrier discharge ion gun;Sample desorption group Part, sample desorption component is connected with the desorption chamber and the sample desorbs that component is vertical with the chromatographic sheet to be set Put;And mass spectral analysis component, the mass spectral analysis component with it is described desorption chamber be connected.Thus, it is possible in the sky of closing The interior desorption and ionization for completing sample, such that it is able to improve Ionization Efficiency, improves the sensitivity of analysis.Additionally, The setting of ion gun and sample the desorption component of above-mentioned gas ions assisted class atmospheric pressure ionization method ensure that desorption and ion Change process is not impacted to Development of Thin-Layer Chromatography, and chromatographic sheet will not in above process by laser burnout.
Embodiments in accordance with the present invention, the sample desorption component includes:Diode laser, the diode laser is used In the transmitting continuous light of infrared band;And delay pulse function generator, the delay pulse function generator and two pole Pipe laser is connected, for by the continuous light modulation of the infrared band into pulse type laser.Thus, it is possible to using infrared pulse Formula laser completes the desorption of sample, so as to avoid infringement of the high-energy for chromatographic sheet brought using continuous laser.
Embodiments in accordance with the present invention, the desorption chamber includes:Thin-layer chromatography sample inlet, the thin-layer chromatography sample enters Mouth is arranged on the bottom of the desorption chamber sidewall, and the side wall is near the Development of Thin-Layer Chromatography unit;Ionization entrance, institute State ionization entrance to be arranged on the side wall of the desorption chamber, the ionization entrance is connected with the ionization component;Laser enters Mouthful, the laser entrance is arranged on and be oppositely arranged with the thin-layer chromatography sample inlet and be connected with sample desorption component, The laser entrance capping has quartz glass;Test point, the test point is arranged on the chromatographic sheet upper surface, institute Test point is stated to be oppositely arranged with the laser entrance;And ionized sample outlet, ionized sample outlet with it is described ionize into Mouth is oppositely arranged, and the ionized sample outlet is connected with the mass spectral analysis component.Thus, it is possible to be realized in desorption chamber The desorption and ionization of sample, and Mass Spectrometer Method will be carried out by the sample of desorption and ionization feeding mass spectrum injection port, and then Desorption, the ionizing efficiency in desorption chamber can be improved.
Embodiments in accordance with the present invention, in the desorption chamber, are provided with the chromatographic sheet at the test point For there is substance assistant laser desorpted matrix.Thus, it is possible to the desorption of sample is completed under the conditions of with Matrix-assisted, And then the energy required for desorption can be reduced, further reduce influence of the endothermic desorption process for thin-layer chromatographic analysis.
Embodiments in accordance with the present invention, the matrix contains graphite.Graphite matrix wide material sources, are readily available, such that it is able to The cost that reduction is detected using device of the invention.
Embodiments in accordance with the present invention, the Development of Thin-Layer Chromatography unit includes:Syringe pump, the syringe pump is used for described Chromatographic sheet supplies solvent;And adapter, the adapter respectively with the syringe pump and the chromatographic sheet It is connected, for the solvent to be shunted, and will be supplied to the chromatographic sheet by the solvent of the shunting. Thus, it is possible to improve expansion efficiency of the solvent for sample.
In another aspect of this invention, the present invention proposes previously described thin layer of liquid chromatography-mass spectroscopy and is used in conjunction device in detection sample Purposes in product.Thus, it is possible to the detection of sample is completed using previously described device, such that it is able to improve the efficiency of detection And effect, desorption and the electricity of sample are completed using the ion gun and desorption component that are not impacted to development of chromatogram process From alloing chromatographic process and mass spectral analysis synchronously to carry out, so as to shorten detection time.
In still another aspect of the invention, the present invention is proposed and is used in conjunction analytical equipment using foregoing thin layer of liquid chromatography-mass spectroscopy The method for detecting sample.Embodiments in accordance with the present invention, the method includes:(1) sample is added to chromatographic sheet On;(2) solvent is supplied to the chromatographic sheet using the Development of Thin-Layer Chromatography unit, carries out the sample Launch;(3) in the desorption chamber, the sample by the expansion is desorbed and is ionized, to obtain Ionization of sample;And (4) supply to the mass spectrum unit ionization of sample, to complete the detection.Thus, The desorption and ionization of sample, Ke Yishi are completed using the ion gun and desorption component that are not impacted to development of chromatogram process Existing TLC separation process and Mass Spectrometer Method process synchronously carry out, operated so as to save detection time and simplify detection Journey.
Embodiments in accordance with the present invention, in step (3), to the sample desorb realizing through the following steps:Profit Pulsed infrared laser is provided with the diode laser and the delay pulse function generator, the pulsed is infrared Laser by the laser entrance be incident to it is described desorption chamber in, so as to make it is described desorption chamber in by the expansion sample There is laser desorption in product.Thus, it is possible to avoid the damage that chromatographic sheet is desorbed and caused using continuous laser.
Brief description of the drawings
Of the invention above-mentioned and/or additional aspect and advantage will be apparent from description of the accompanying drawings below to embodiment is combined Be readily appreciated that, wherein:
Fig. 1 shows thin layer of liquid chromatograph-mass spectrometer coupling apparatus structure schematic diagram according to an embodiment of the invention;
Fig. 2 shows thin layer of liquid chromatograph-mass spectrometer coupling apparatus structure schematic diagram in accordance with another embodiment of the present invention;
Fig. 3 shows the extraction ion flow graph and mass spectrogram of the embodiment of the present invention 1;And
Fig. 4 shows the extraction ion flow graph and mass spectrogram of the embodiment of the present invention 2.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein identical from start to finish Or similar label represents same or similar element or the element with same or like function.Retouched below with reference to accompanying drawing The embodiment stated is exemplary, it is intended to for explaining the present invention, and be not considered as limiting the invention.
In the first aspect of the present invention, the present invention proposes a kind of thin layer of liquid chromatograph-mass spectrometer coupling device.Specifically, refer to Fig. 1, the device includes:Chromatographic sheet 100, desorption chamber 200, development of chromatogram unit 300 and mass spectrum unit 400.
Specifically, embodiments in accordance with the present invention, the surface of chromatographic sheet 100 is provided with fixing phase, so as in fixing phase Complete the Development of Thin-Layer Chromatography of sample.Desorption chamber 200 is arranged on the upper surface of chromatographic sheet 100, in other words, i.e., It is provided with a side surface of fixing phase in chromatographic sheet 100, is provided with desorption chamber 200.For example, according to the present invention One embodiment, desorption chamber 200 can be four sides perforate aluminium alloy housing, be set in chromatographic sheet 100 On upper surface.In operation, desorption chamber 200 is limited outside an isolation on the portion of upper surface of chromatographic sheet 100 The space of portion's environmental disturbances, the inert gas secondary air in the ion gun in mass spectrum unit 400 entirely desorbs chamber 200 excessively, The ionization of sample is completed in above-mentioned space.Development of Thin-Layer Chromatography unit 300 is connected with chromatographic sheet 100, so as to thin The upper surface supply solvent of layer chromatography plate 100, and for the flowing of solvent provides power drive.Mass spectrum unit 400 and solution Inhale chamber 200 to be connected, to complete Mass Spectrometer Method.Thus, it is possible in the environment of relative closure complete sample desorption with And ionization, so as to improve detection efficiency and effect;And the desorption ionization process of sample and thin-layer chromatographic analysis mistake Journey is not interfere with each other, and Development of Thin-Layer Chromatography process can simultaneously be carried out with Mass Spectrometer Method process, such that it is able to significantly save inspection The survey time.
The all parts to thin layer of liquid chromatograph-mass spectrometer coupling device according to embodiments of the present invention are described in detail below.
Embodiments in accordance with the present invention, Development of Thin-Layer Chromatography unit 300 includes syringe pump and adapter.Specifically, inject Pump is used to supply solvent to the chromatographic sheet, and for solvent provides power drive.Adapter respectively with syringe pump with And chromatographic sheet is connected, for solvent to be shunted, and supply to chromatographic sheet.In other words, adapter will be through The solvent for crossing shunting is supplied on the surface for having fixing phase to chromatographic sheet 100, to ensure during sample launches, Solvent abreast flows through the upper surface of chromatographic sheet 100, thereby may be ensured that expansion effect.Additionally, above-mentioned with dynamic The expansion mode that power drives, can accelerate the expansion process of thin-layer chromatography, and then can save detection time.Need explanation It is that the particular type of solvent, the particular type of adapter and Development of Thin-Layer Chromatography unit 300 are in chromatographic sheet 100 The particular location of upper surface is not particularly limited, and those skilled in the art can be designed according to actual conditions.For example, root According to one embodiment of the present of invention, it is possible to use the syringe storage solvent being connected with syringe pump, will be injected using plastic pipe The needle portion of device is connected to adapter, solvent is divided into three strands of liquid streams by adapter, and be supplied to chromatographic sheet 100 On, carry out the expansion of testing sample.It will be appreciated by persons skilled in the art that sample can be added to by conventional method On chromatographic sheet 100, i.e., there is point sample area in one end of chromatographic sheet 100, point sample is carried out using capillary.Also, Point sample area need to be arranged on the downstream direction of the solvent that Development of Thin-Layer Chromatography unit 300 is provided, i.e. solvent flow to first it is thin The upper surface of layer chromatography plate 100, and advanced along chromatographic sheet 100, then by point sample area, solvent is touched and is located at The testing sample in point sample area, and testing sample is launched.
Embodiments in accordance with the present invention, with reference to Fig. 2, by the sample of expansion under the propulsion of solvent, into desorption chamber 200.Mass spectrum unit 400 is connected with desorption chamber 200, to complete the Mass Spectrometer Method part by the sample for launching.Thus, The whole samples such as do not need to complete whole thin layer of liquid chromatography, then carry out Mass Spectrometer Method, such that it is able to significantly save detection Time.
Specifically, mass spectrum unit 400 includes:Ionization component 410, sample desorption component 420 and mass spectral analysis component 430.Specifically, ionization component 410 is connected with chamber 200 is desorbed, and ionizes in component 410 and be provided with ion gun, To complete the ionization of sample in chamber is desorbed.Embodiments in accordance with the present invention, ion gun can be aided in for inert gas Glow discharge ion source, Direct Analysis in Real Time ion gun, low temperature plasma ion gun or dielectric barrier discharge ion gun. The ionization process of above-mentioned ion gun need not introduce extra liquid stream, such that it is able to avoid ionization process to thin-layer chromatography Sample launches to interfere.It should be noted that those skilled in the art can select ion gun according to actual conditions, as long as Sample can be ionized by gas ions assisted class atmospheric pressure ionization method, and development of chromatogram process is not impacted, Do not damage chromatographic sheet.Sample desorption component 420 is provided with laser desorption device, to complete the laser of testing sample Heating desorption.Specifically, sample desorption component 420 can include:Diode laser and delay pulse function generator, Diode laser is used to launch the continuous light of infrared band, and delay pulse function generator is connected with diode laser, by two The continuous light modulation of infrared band that pole pipe laser sends is into pulse type laser.Thus, it is possible to complete using infrared pulse formula laser Into the desorption of sample, so as to avoid infringement of the high-energy for chromatographic sheet brought using continuous laser.Sample desorption group Part 420 is vertically arranged with chromatographic sheet 100.It will be appreciated by persons skilled in the art that because laser is along straightline propagation, Therefore sample desorption component 420 is vertically arranged with chromatographic sheet 100 and is conducive to making being moved along the place plane of chromatographic sheet 100 Dynamic sample is desorbed in the presence of laser.Thus, using above-mentioned ion gun and sample desorption component, sample is completed Normal pressure desorption ionization in situ, it is to avoid the influence due to pressure, vacuum or additional extractant to development of chromatogram process, It is synchronous with mass spectral analysis such that it is able to realize chromatography process.
Mass spectral analysis component 430 is connected with desorption chamber 200.Complete what is desorbed and ionize in chamber 200 is desorbed Sample carries out mass spectral analysis into mass spectral analysis component 430.Thus, it is possible to realize mass spectral analysis and thin-layer chromatographic analysis Synchronously carry out, without waiting specimen in use to complete expansion process on chromatographic sheet 100, then desorbed, ion Change and mass spectral analysis, and then sample detection time can be greatly reduced.It should be noted that mass spectral analysis component 430 with The connected concrete mode of desorption chamber 200 is not particularly limited, and those skilled in the art can be configured according to actual conditions, As long as disclosure satisfy that the sample supply that will have passed through desorption, ionization process, to the injection port of mass spectral analysis component 430, is gone forward side by side Row Mass Spectrometer Method.
Embodiments in accordance with the present invention, desorb chamber 200 and are attached with miscellaneous part for convenience, and desorption chamber 200 is also Can have:Thin-layer chromatography sample inlet, laser entrance, ionization entrance, test point and ionized sample outlet.
Specifically, thin-layer chromatography sample inlet is arranged in desorption chamber 200, near the one of Development of Thin-Layer Chromatography unit 300 The bottom of the side wall of side, so that the sample supply that will be launched under being acted in solvent is into desorbing chamber 200.Need Bright, the concrete shape of thin-layer chromatography sample inlet is not particularly limited, for example, thin-layer chromatography sample inlet can be narrow Seam, as long as the sample under solvent effect can be entered in desorption chamber 200 by thin-layer chromatography sample inlet.Laser Entrance is connected with sample desorption component 420.Thus, it is possible to make to enter desorption chamber 200 using sample desorption component 420 Sample is desorbed.Furthermore, it is possible to cover quartz glass in laser entrance, thus, chamber is desorbed ensureing that laser can be incident to On the premise of room 200, the seal of desorption chamber 200 can be improved.Ionization entrance is arranged on the side wall of desorption chamber 200 On, ionization entrance is connected with ionization component 410.Thus, it is possible to realize carrying out ion to the sample in desorption chamber 200 Change.Test point can be arranged in desorption chamber 200 on chromatographic sheet 100, and laser entrance is arranged on just going up for test point Side.It should be noted that test point is not particularly limited relative to the particular location of chromatographic sheet 100, art technology Personnel can be designed according to the actual conditions of testing sample, the particular location to test point.For example, when detection sample is When being difficult to separate sample, it is slightly long that air line distance of the test point apart from the point sample area of chromatographic sheet 100 can be set, with Just sample can move sufficiently long range, to improve thin-layer chromatography in the presence of solvent on chromatographic sheet 100 Separating effect.It will be appreciated to those of skill in the art that laser entrance is arranged on the surface of test point, so as to test point The sample at place is desorbed in the presence of sample desorption component 420.Because laser is along straightline propagation, laser entrance is arranged on Laser vertical is conducive to be had an effect with sample in the direction that sample is moved on chromatographic sheet 100 directly over test point, And then sample analyzing efficiency can be improved, and can prevent sample from just being sent out in advance without enough Development of Thin-Layer Chromatography processes Raw desorption.Ionized sample outlet is arranged on the side wall of desorption chamber 200, and is oppositely arranged with ionization entrance, to incite somebody to action By in desorption, the sample feeding mass spectral analysis component 430 of ionization.For example, according to one embodiment of present invention, electricity Can just to the mass spectrum injection port of mass spectral analysis component 430 from sample export.
It should be noted that sample desorption component 420 is used for not disturbing on chromatographic sheet on the premise of the expansion of sample, Desorb testing sample.Based on above-mentioned purpose, the related improvement carried out to device proposed by the present invention falls within the present invention Protection domain.For example, embodiments in accordance with the present invention, in order to reduce the energy required for sample is desorbed, it is to avoid by The energy provided in desorption component 420 is too high and cause chromatographic sheet to damage or impact to development of chromatogram process, in inspection At measuring point, i.e., in desorption chamber 200 on the position relative with laser desorption device of the upper surface of chromatographic sheet 100, can add Matrix, it is substance assistant laser desorpted to complete, improve the heat absorption efficiency at test point, it is to avoid chromatographic sheet the last 100 Desorption laser damage.Embodiments in accordance with the present invention, matrix can be the material composition that can be absorbed heat.Specifically, according to Embodiments of the invention, can contain graphite in matrix.It is for instance possible to use addition pencil matrix easy, difficult for drop-off, That is pencil trace is used as matrix.
People in the art is appreciated that in actual applications the specific set-up mode of said apparatus is not particularly limited.That is, In the application, chromatographic sheet 100 be able to can be disposed vertically with horizontal positioned, it is also possible to be placed horizontal by acute angle. Those skilled in the art can according to actual needs, and the specific set-up mode to said apparatus is configured, as long as the device Previously described relative position relation is met between all parts.In other words, as long as sample can be along chromatographic sheet 100 are sufficiently spread out, and are then desorbed and are ionized in desorption chamber 200, by the sample energy for desorbing and ionize Enough into carrying out simple analysis process in mass spectral analysis component 430.
In sum, thin layer of liquid chromatograph-mass spectrometer coupling device of the invention, using Development of Thin-Layer Chromatography unit 300 pairs The sample for being added in the upper surface of chromatographic sheet 100 is launched, and in chamber 200 is desorbed, the sample by launching is carried out Desorption and ionization.Wherein, the ionization of sample is the ion gun reality by not introducing liquid stream, not influenceing Development of Thin-Layer Chromatography Existing;The desorption of sample desorbs the LASER HEATING desorption realization that component 420 is provided by sample, in order to avoid LASER HEATING Damage to chromatographic sheet 100 and the influence for sample expansion, the present invention use the pulsed laser heating of Matrix-assisted Desorption.By the sample that desorbs and ionize into carrying out mass spectral analysis in mass spectral analysis component 430.Thus, the combination Device can realize the development of chromatogram process of sample and the Mass Spectrometer Method process of sample while carrying out, without waiting all samples Product are completed after Development of Thin-Layer Chromatography process, then the ionization and mass spectral analysis for carrying out sample.
Thus, thin layer of liquid chromatograph-mass spectrometer coupling (LTLC-MS) device of the invention has advantages below:
1st, the present invention uses normal pressure desorption ionization method and power drive thin layer of liquid development of chromatogram technology, simplifies and analyzed Journey, substantially reduces analysis time, and whole analysis took time within 15 minutes.
2nd, the present invention improves sample desorption efficiency using pencil vestige as matrix, reduces required laser energy, it is ensured that Thin layer of liquid chromatosheet is not desorbed laser damage in whole process.
3rd, present invention employs sample desorption chamber so that the desorption ionization process of sample occurs one on thin layer of liquid chromatosheet In the environment of individual relative closure, Ionization Efficiency and sensitivity for analysis are improve.Additionally, the addition of matrix, pulse laser Using and plasmaassisted class atmospheric pressure ionization method use, also ensure that liquid chromatogram separation process is not examined by mass spectrum The influence of survey process, thin layer of liquid chromatosheet is not destroyed during analysis by laser burns.
4th, present invention employs pulsed infrared diode laser heating desorption, pulse laser is used so that sample desorption ionization Process without interference with the normal separation process of thin layer of liquid chromatogram, so as to ensure that thin layer of liquid chromatographic isolation and Mass Spectrometer Method process While carry out.
5th, the cumbersome time-consuming analysis process of conventional liquid phase thin-layer chromatography-mass spectrum is converted into similar gas chromatography-mass spectrometry by the present invention With (GC-MS) or liquid chromatograph mass spectrography (LC-MS) process, entirely analyzing only needs two steps:Point sample, beginning liquid phase Thin-layer chromatography-mass spectrometry process, then only needs to wait for more than ten minutes, you can take analysis result.It is square in itself with reference to TLC Just, low cost, without as the cylinder of GC or LC need complex maintenance the advantages of, thin layer of liquid chromatography-mass spectroscopy (LTLC-MS) There to be very wide application prospect.
In another aspect of this invention, the present invention proposes previously described thin layer of liquid chromatograph-mass spectrometer coupling device in detection sample Purposes in product.Thus, it is possible to carry out sample detection using the device with above-mentioned advantage, the sample for making EI-MS process desorbs, Ionization process is not impacted to Development of Thin-Layer Chromatography process, therefore can realize that thin-layer chromatographic analysis are same with mass spectral analysis Step is carried out, and such that it is able to save detection time, simplifies detecting step.The feature of sample detection and excellent is carried out using the device Point is above having been carried out description in detail, will not be repeated here.
In still another aspect of the invention, the present invention is proposed using the detection of previously described thin layer of liquid chromatograph-mass spectrometer coupling device The method of sample.Embodiments in accordance with the present invention, the method includes:
(1) point sample
Embodiments in accordance with the present invention, in this step, sample are added on chromatographic sheet.For example, it is possible to use hair Tubule, by sample added to the point sample area of chromatographic sheet.
(2) Development of Thin-Layer Chromatography is carried out
Embodiments in accordance with the present invention, in this step, using Development of Thin-Layer Chromatography unit, solvent are supplied to thin layer color On spectrum plate, sample is launched.In this step, Development of Thin-Layer Chromatography unit provides power drive for solvent, and will Solvent is shunted, and can abreast flow through the surface of chromatographic sheet as far as possible so as to solvent.
(3) sample desorption/ionization
Embodiments in accordance with the present invention, in this step, desorb chamber in, to through expansion sample desorbed and Ionization, to obtain ionization of sample.Specifically, in this step, using the ionization component pair being connected with desorption chamber Sample is ionized, and is desorbed using the sample desorption component being connected with desorption chamber.
Specifically, sample desorb realizing through the following steps:Using diode laser and delay pulse letter Number generator provides pulsed infrared laser, and pulsed infrared laser is incident to solution by the laser entrance desorbed in chamber sidewall In suction chamber, to make that laser desorption occurs by the sample of expansion in desorption chamber.
Additionally, in order to reduce the energy required for desorption, it is to avoid laser energy is too high to Development of Thin-Layer Chromatography process or thin layer color Spectrum plate impact, can in advance desorb chamber in relevant position, i.e., at test point add matrix, by mechanism auxiliary Laser desorption process completes the desorption of sample, such that it is able to reduce the energy required for desorption.Specific species on matrix, The position of addition, before have been carried out in detail description, will not be repeated here.
(4) Mass Spectrometer Method
Embodiments in accordance with the present invention, in this step, ionization of sample are supplied to mass spectrum unit, to complete detection.
It should be noted that because this method is realized using previously described thin layer of liquid chromatograph-mass spectrometer coupling device, because This method has the whole features and advantage that previously described device has during sample detection, no longer goes to live in the household of one's in-laws on getting married herein State.
In sum, method provided by the present invention has advantages below:
1st, the present invention uses normal pressure desorption ionization method and power drive thin layer of liquid development of chromatogram technology, simplifies and analyzed Journey, substantially reduces analysis time, and whole analysis took time within 15 minutes.
2nd, the present invention improves sample desorption efficiency using pencil vestige as matrix, reduces required laser energy, it is ensured that Thin layer of liquid chromatosheet is not desorbed laser damage in whole process.
3rd, present invention employs sample desorption chamber so that the desorption ionization process of sample occurs one on thin layer of liquid chromatosheet In the environment of individual relative closure, Ionization Efficiency and sensitivity for analysis are improve.Additionally, the addition of matrix, pulse laser Using and plasmaassisted class atmospheric pressure ionization method use, also ensure that liquid chromatogram separation process is not examined by mass spectrum The influence of survey process, thin layer of liquid chromatosheet is not destroyed during analysis by laser burns.
4th, present invention employs pulsed infrared diode laser heating desorption, pulse laser is used so that sample desorption ionization Process without interference with the normal separation process of thin layer of liquid chromatogram, so as to ensure that thin layer of liquid chromatographic isolation and Mass Spectrometer Method process While carry out.
5th, the cumbersome time-consuming analysis process of conventional liquid phase thin-layer chromatography-mass spectrum is converted into similar gas chromatography-mass spectrometry by the present invention With (GC-MS) or liquid chromatograph mass spectrography (LC-MS) process, entirely analyzing only needs two steps:Point sample, beginning liquid phase Thin-layer chromatography-mass spectrometry process, then only needs to wait for more than ten minutes, you can take analysis result.It is square in itself with reference to TLC Just, low cost, without as the cylinder of GC or LC need complex maintenance the advantages of, thin layer of liquid chromatography-mass spectroscopy (LTLC-MS) There to be very wide application prospect.
The solution of the present invention is explained below in conjunction with embodiment.It will be understood to those of skill in the art that following implementation Example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.In the following embodiments, unless otherwise specified, Mass spectrum model Thermo the LTQ XL, USA for being used.Unreceipted particular technique or condition in embodiment, according to this Technology described by document or condition in field are carried out according to product description.Agents useful for same or the unreceipted production of instrument Manufacturer person, be can by city available from conventional products.In the following embodiments, unless otherwise specified, term " phase To intensity " refer to the intensity at each peak in actual spectrogram and the ratio of the peak intensity of highest peak in spectrogram.
The aminopyrine standard sample of embodiment 1 is detected
Using thin layer of liquid chromatograph-mass spectrometer coupling device of the invention to aminopyrine (being purchased from Sigma companies) standard sample Product are measured.
Aminopyrine ethanol as solvent is made into 10-3The solution of mol/L.The μ L points of matched somebody with somebody solution about 0.5 are taken to completing in advance On the TLC plates of pencil matrix (uniformly being coated at test point using conventional Pencil with 2B hardness).Then by TLC plates upper end with turn Joint is close to fix, and is oppositely arranged with laser entrance at middle pencil substrate application.Solvent used herein is mixed solvent, That is carbon tetrachloride:Ethyl acetate:Methyl alcohol volume ratio is 3:3:1 mixed solvent.After 500mL solvents being drawn with syringe Connection respective line, is fixed on syringe pump.After everything in readiness, argon gas auxiliary gas (flow velocity about 60 is opened successively ML/min), glow discharge ion source voltage (- 3000V), syringe pump (solvent flow velocity is 85 μ L/min herein), mass spectrum Instrument, diode laser laser (1.1A, pulse length 0.05s, frequency 0.04Hz), it is to obtain that 10min is waited afterwards The chromatographic mass spectrometry figure of aminopyrine.
In the present embodiment, TLC plates are disposed vertically, and solvent launches to sample from top to bottom.
Fig. 3 a are the extraction ion flow graph of resulting aminopyrine signal.Because laser used is pulse laser, thus color Spectral peak is made up of corresponding sub- peak.It can be seen that launch peak type be essentially normal distribution, illustrate TLC separation processes and Do not interfered between Mass Spectrometer Method process, realize separation synchronous with detection.Fig. 3 b are signal most strength in Fig. 3 a Corresponding mass spectrogram (after background correction).Aminopyrine mass signal (m/z 232) the intensity signal to noise ratio is very good.
Embodiment 2, aminopyrine and 6-Methylcoumarin biased sample are detected
Aminopyrine is measured with the isometric biased sample of the equimolar concentration of 6-Methylcoumarin.
By aminopyrine 10-3The solution of mol/L and 6-Methylcoumarin 10-3Mol/L ethanol solutions 1:1 mixing, takes 0.5 μ L Put onto the TLC plates for completing pencil matrix in advance.Remaining step is with embodiment 1.
Fig. 4 a are the superposition that mixture extracts ion flow graph.It can be seen that two chromatographic peaks have reached baseline separation, Further demonstrate the actual application ability of the method.Matter of Fig. 4 b corresponding to signal most strength in No. 1 peak in Fig. 4 a Spectrogram, mass spectrograms of Fig. 4 c corresponding to signal most strength in Fig. 4 a (after background correction).
In the description of the invention, it is to be understood that term " on ", D score, " level ", " vertical ", " level ", " hang down Directly " etc. the orientation or position relationship of instruction are, based on orientation shown in the drawings or position relationship, to be for only for ease of description this hair Bright and simplified description, must be with specific orientation, with specific orientation rather than the device or element for indicating or imply meaning Construction and operation, therefore be not considered as limiting the invention.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature " on " or D score can be One and second feature directly contact, or the first and second features pass through intermediary mediate contact.And, fisrt feature is Two features " top " can be fisrt feature directly over second feature or oblique upper, or be merely representative of fisrt feature level height Higher than second feature.
In the present invention, term " upper surface " is refered in particular to during sample analysis, and the side of sample is added on chromatographic sheet.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specific example ", Or the description of " some examples " etc. means to combine specific features, structure, material or feature bag that the embodiment or example are described It is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term necessarily It is directed to identical embodiment or example.And, the specific features of description, structure, material or feature can be any Combined in an appropriate manner in individual or multiple embodiments or example.Additionally, in the case of not conflicting, the skill of this area Can be combined for the feature of the different embodiments or example described in this specification and different embodiments or example by art personnel And combination.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment be it is exemplary, It is not considered as limiting the invention, one of ordinary skill in the art within the scope of the invention can be to above-described embodiment It is changed, changes, replacing and modification.

Claims (10)

1. a kind of thin layer of liquid chromatograph-mass spectrometer coupling device, it is characterised in that including:
Chromatographic sheet, the thin-layer chromatography plate surface is provided with fixing phase;
Desorption chamber, the desorption chamber is arranged on the chromatographic sheet upper surface;
Development of Thin-Layer Chromatography unit, the Development of Thin-Layer Chromatography unit is connected with the chromatographic sheet;And
Mass spectrum unit, the mass spectrum unit is connected with the desorption chamber.
2. device according to claim 1, it is characterised in that the mass spectrum unit includes:
Ionization component, the ionization component with it is described desorption chamber be connected, and it is described ionize component in be provided with from Component, the ion gun is inert gas auxiliary glow discharge ion gun, Direct Analysis in Real Time ion gun, low temperature plasma Ion gun or dielectric barrier discharge ion gun;
Sample desorbs component, and the sample desorption component is connected with the desorption chamber and sample desorption component is thin with described Layer chromatography plate is vertically arranged;And
Mass spectral analysis component, the mass spectral analysis component is connected with the desorption chamber.
3. device according to claim 2, it is characterised in that the sample desorption component includes:
Diode laser, the diode laser is used to launch the continuous light of infrared band;And
Delay pulse function generator, the delay pulse function generator is connected with the diode laser, for by institute State the continuous light modulation of infrared band into pulse type laser.
4. device according to claim 3, it is characterised in that the desorption chamber includes:
Thin-layer chromatography sample inlet, the thin-layer chromatography sample inlet is arranged on the bottom of the desorption chamber sidewall, the side Wall is near the Development of Thin-Layer Chromatography unit;
Ionization entrance, the ionization entrance is arranged on the side wall of the desorption chamber, ionization entrance and the ionization Component is connected;
Laser entrance, the laser entrance is connected with sample desorption component, and the laser entrance capping has quartz glass;
Test point, the test point is arranged on the chromatographic sheet upper surface, and the test point is relative with the laser entrance Set;And
Ionized sample is exported, and the ionized sample outlet is oppositely arranged with the ionization entrance, and the ionized sample is exported and institute Mass spectral analysis component is stated to be connected.
5. device according to claim 4, it is characterised in that in the desorption chamber, the institute at the test point State and be provided with chromatographic sheet for there is substance assistant laser desorpted matrix.
6. device according to claim 5, it is characterised in that the matrix contains graphite.
7. device according to claim 1, it is characterised in that the Development of Thin-Layer Chromatography unit includes:
Syringe pump, the syringe pump is used to supply solvent to the chromatographic sheet;And
Adapter, the adapter is connected with the syringe pump and the chromatographic sheet respectively, for by the solvent Shunting, and will be supplied to the chromatographic sheet by the solvent of the shunting.
8. the thin layer of liquid chromatography-mass spectroscopy described in any one of claim 1~7 is used in conjunction purposes of the analytical equipment in sample is detected.
9. the method that sample is detected using the thin layer of liquid chromatograph-mass spectrometer coupling device described in any one of claim 1~7, its It is characterised by, including:
(1) sample is added on chromatographic sheet;
(2) solvent is supplied to the chromatographic sheet using the Development of Thin-Layer Chromatography unit, carries out the sample Launch;
(3) it is described desorption chamber in, the sample by the expansion is desorbed and ionized, so as to obtain from Sonization sample;
(4) ionization of sample is supplied to the mass spectrum unit, to complete the detection.
10. method according to claim 9, it is characterised in that in step (3), carrying out desorption to the sample is Realize through the following steps:It is red pulsed to be provided using the diode laser and the delay pulse function generator Outer laser, the pulsed infrared laser is incident in the desorption chamber by the laser entrance, to make the desorption There is laser desorption in the sample in chamber by the expansion.
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CN111103388A (en) * 2018-10-29 2020-05-05 中山大学 Method for integrating thin layer chromatography and mass spectrometry detection
CN109142610A (en) * 2018-11-13 2019-01-04 吕梁学院 The method with assay is examined in the extraction of triterpene compound in a kind of shiny-leaved yellowhorn
CN110954645A (en) * 2019-09-09 2020-04-03 山东琪康生物技术有限公司 Detection method of high-quality Sihuang dysentery stopping granules
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