CN108088809A - Based on thin-layer chromatography-high pressure gas pulse liquid phase component separator associated with bis- spectrum - Google Patents

Based on thin-layer chromatography-high pressure gas pulse liquid phase component separator associated with bis- spectrum Download PDF

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CN108088809A
CN108088809A CN201711475184.7A CN201711475184A CN108088809A CN 108088809 A CN108088809 A CN 108088809A CN 201711475184 A CN201711475184 A CN 201711475184A CN 108088809 A CN108088809 A CN 108088809A
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high pressure
carrier
pellet
spectrum
objective table
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孙诗津
段忆翔
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Sichuan University
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Sichuan University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3577Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08Selective adsorption, e.g. chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Pathology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

The invention discloses one kind based on high pressure gas pulse liquid phase component separator associated with the double spectrum of thin-layer chromatography, including body, high pressure pumping lamp and host, concave mirror is provided on the inside of the body, MCT detectors are provided with above the concave mirror, objective table is provided with above the MCT detectors, the upper surface of the objective table is provided with carrier-pellet, one end of the objective table is provided with carrier-pellet import, the other end of the objective table is provided with carrier-pellet outlet, and detector is provided with above the carrier-pellet;The solute component separation and identification of all kinds of more solute complicated solutions are generally applicable to, application range is extremely wide, especially has significant advantage in terms of the component separation analysis of solution class biomaterial;Solute component is identified by spectroscopic analysis methods, and accuracy is high, full-automatic high speed processing, has high efficiency, can realize the batch processing of relatively large material, and it is integrated with identification to realize substance separation.

Description

Based on thin-layer chromatography-high pressure gas pulse liquid phase component separator associated with bis- spectrum
Technical field
The invention belongs to separator technology fields, and in particular to one kind is based on thin-layer chromatography-high pressure gas associated with bis- spectrum Pulse liquid phase component separator.
Background technology
Separation for different solute components in complicated solution, forefathers, which have explored, such as to be extracted, recrystallizes, semi-permeable membrane Many methods such as method, it is nowadays, accurate, efficient, pervasive to have become the pursued core of new separation equipment research and development with automation Target.Chromatography has been widely adopted as a kind of good separating effect, substance isolation technics applied widely;With gas chromatography phase Than, liquid chromatography is not required to heat, and is conducive to that solute substance is protected not to be destroyed, and with high in terms of Separation of Organic Compounds Resolving power, therefore have a wide range of applications in the experimental studies such as biochemistry, molecular biology field;However liquid chromatography by In there are still cumbersome, speed it is relatively slow, do not fully achieve full-automation the problems such as, be generally only used for the processing of a small amount of sample Analysis, there are still larger limitations on application.
The existing method and apparatus separated for more solute complicated solution solutes with identifying exists and is answered to more solutes Mixture solution carries out solute component separation with can not preferably take into account accuracy, high efficiency and universality during identification and without complete The problem of full-automatic is realized, therefore it is proposed that a kind of be based on thin-layer chromatography-high pressure gas pulse liquid phase group associated with bis- spectrum Divide separator.
The content of the invention
It is an object of the invention to provide one kind based on thin-layer chromatography-high pressure gas pulse liquid phase component associated with bis- spectrum point From device, with solve it is mentioned above in the background art it is existing for more solute complicated solution solutes separate with the method identified and Equipment can not preferably take into account accuracy, high efficiency and general when carrying out solute component separation with identifying to more solute complicated solutions Adaptive and do not fully achieve the problem of full-automation.
To achieve the above object, the present invention provides following technical solution:Based on thin-layer chromatography-high pressure gas associated with bis- spectrum Pulse liquid phase component separator including body, high pressure pumping lamp and host, is provided with concave mirror, institute on the inside of the body It states and MCT detectors is provided with above concave mirror, objective table, the objective table are provided with above the MCT detectors Upper surface be provided with carrier-pellet, one end of the objective table is provided with carrier-pellet import, and the other end of the objective table is set There is carrier-pellet outlet, detector is provided with above the carrier-pellet, and detector is fixedly connected on body, the detector One end be provided with monochromator, one end of the monochromator is provided with the first convex lens, and one end of the high pressure pumping lamp is provided with Laser light source, one end of the laser light source are provided with the second convex lens, are provided with interferometer below the high pressure pumping lamp, institute It states and horizontal glass is provided with below interferometer, one end of the horizontal glass is provided with index glass, and the body is internally provided with module one, The top of the body is connected with module two by gas transmission line, and the one side of the host is connected with small integrate by data cable Device, the small integrator one side is connected with controller by data cable, and is connected between module two and controller by data cable, The opposite side of the host is connected with signal input/output device by data cable.
Preferably, the module one includes the first gas chamber, the second gas chamber, switch control slide block and segmentation sliding block, and described the Segmentation sliding block is provided between one gas chamber and the second gas chamber, first gas chamber is internally provided with switch control slide block.
Preferably, the module two includes valve, accumulator, pressure gauge, cylinder and source of the gas, and the one side of the valve passes through Appendix is provided with accumulator, and the upper surface of the accumulator is provided with pressure gauge, and the one side of the accumulator passes through appendix Air pump is connected with, the one side of the air pump is provided with source of the gas.
Preferably, one end of the switch control slide block is provided with telescopic putter.
Compared with prior art, the beneficial effects of the invention are as follows:
(1)The solute component separation and identification of all kinds of more solute complicated solutions are generally applicable to, application range is extremely wide, especially molten There is significant advantage in terms of the component separation analysis of liquid class biomaterial.
(2)Solute component is identified by spectroscopic analysis methods, and accuracy is high.
(3)Full-automatic high speed processing has high efficiency, can realize the batch processing of relatively large material.
(4)The separation for realizing substance is integrated with identification.When database improves enough, a kind of identification object will be become The shortcut of matter.
(5)Automatization level is high, and being simply provided after parameter just can be automatically performed follow-up work, easy to operate.
(6)Accuracy, high efficiency, universality and simplicity are taken into account.
Description of the drawings
Fig. 1 is the structural diagram of the present invention;
Fig. 2 is one partial enlargement structural representation of module of the present invention;
In figure:1- bodies, 2- concave mirrors, 3-MCT detectors, the first convex lenses of 4-, 5- monochromators, 6- detectors, 7- are carried Body piece, 8- laser light sources, the second convex lenses of 9-, 10- interferometers, the outlet of 11- carrier-pellets, 12- horizontal glass, 13- index glass, 14- high pressures Pumping lamp, 15- modules one, 16- modules two, 17- controllers, the small integrators of 18-, 19- hosts, the import of 20- carrier-pellets, 21- signals Input-output apparatus.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete Whole description, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work Embodiment belongs to the scope of protection of the invention.
It please refers to Fig.1 and Fig. 2, the present invention provides a kind of technical solution:Based on thin-layer chromatography-high pressure gas associated with bis- spectrum Pulse liquid phase component separator, including body 1, high pressure pumping lamp 14 and host 19, the inside of body 1 is provided with concave mirror 2, The top of concave mirror 2 is provided with MCT detectors 3, and the top of MCT detectors 3 is provided with objective table, the upper surface of objective table Carrier-pellet 7 is provided with, one end of objective table is provided with carrier-pellet import 20, and the other end of objective table is provided with carrier-pellet outlet 11, the top of carrier-pellet 7 is provided with detector 6, and detector 6 is fixedly connected on body 1, and one end of detector 6 is provided with Monochromator 5, one end of monochromator 5 are provided with the first convex lens 4, and one end of high pressure pumping lamp 14 is provided with laser light source 8, laser light The one end in source 8 is provided with the second convex lens 9, and the lower section of high pressure pumping lamp 14 is provided with interferometer 10, and the lower section of interferometer 10 is set There is a horizontal glass 12, one end of horizontal glass 12 is provided with index glass 13, and body 1 is internally provided with module 1, and the top of body 1 passes through defeated Gas pipeline is connected with module 2 16, and the one side of host 19 is connected with small integrator 18 by data cable, and small 18 one side of integrator leads to It crosses data cable and is connected with controller 17, and connected between module 2 16 and controller 17 by data cable, the opposite side of host 19 Signal input/output device 21 is connected with by data cable.
In the present embodiment, it is preferred that module 1 includes the first gas chamber, the second gas chamber, switch control slide block and segmentation and slides Block, is provided with segmentation sliding block between the first gas chamber and the second gas chamber, the first gas chamber is internally provided with switch control slide block.
In the present embodiment, it is preferred that module 2 16 include valve, accumulator, pressure gauge, cylinder and source of the gas, the one of valve Side is provided with accumulator by appendix, and the upper surface of accumulator is provided with pressure gauge, and the one side of accumulator is connected by appendix Air pump is connected to, the one side of air pump is provided with source of the gas.
In the present embodiment, it is preferred that the one end for switching control slide block is provided with telescopic putter.
The operation principle and process for using of the present invention:The invention is after installation is complete, you can uses.
Operation principle:
【1】Separation principle:It is to be basically separated principle with chromatography.(With the solid of fine dispersion or it is being attached to the liquid of the surface of solids Body is stationary phase, with liquid(It is immiscible with aforesaid liquid)Or in the system that gas is mobile phase, make each group in mixture It is divided to holding to the equilibrium state of two distributed mutuallies and with flowing phase shift, using each component to caused by the difference of stationary phase affinity Translational speed difference, by each component method separated from each other be known as chromatograph, also known as chromatography.According to mobile phase species not Together, chromatography is divided into as liquid chromatography, gas chromatography;Absorbent-type, distribution are divided into according to the difference of affinity between stationary phase and solute Type, ion-exchange type three types (but this is not very stringent, sometimes common to in-between type).The essence of chromatography process is The process of material molecule to be separated partition equilibrium between stationary phase and mobile phase, different substances being assigned between the two phases Institute is different, causes it different with the speed of mobile phase movement, so that with the movement of mobile phase, the different component in mixture It is separated from each other and comes in stationary phase.)It needs to use high pressure gas pulse will since different solute components are separated into after discrete band Solution coating region blowout residing for band where required substance, therefore cannot use traditional glass plate etc. that can not penetrate liquid Holder, use the carrier-pellet 7 being compiled by the coated thin glass fiber of stationary phase film instead, have both permeability and toughness, It ensure that liquid can pass through, and be added significantly to stationary phase and the contact area of solution in 7 length of unit carrier-pellet, So as to shorten the diffusion length needed for solute component separation, make exhibition layer more efficient.
【2】Identification principle:
(1)To non-aqueous solution:Using infrared spectroscopy.(Principle:In material molecule, constitutional chemistry key or functional group Atom is in the state constantly vibrated, and vibration frequency is suitable with the frequency of infrared light.Therefore with Infrared irradiation organic molecule When, if the vibration frequency of some group or rotational frequency are identical with infrared light frequency in material molecule, molecule can just absorb this The energy of the infrared light of frequency shakes and (turns) kinetic energy order transition to the higher kinetic energy grade of shaking and (turn) of energy by original ground state, ripple at this Long infrared light is just subsequently absorbed in the material so as to show absworption peak in infrared spectrum, and different chemical bonds or functional group absorb infrared Light frequency is different, and generated absworption peak is in different position on infrared spectrum, so as to be obtained according to the position of absworption peak Information containing which kind of chemical bond or functional group in molecule carries out structural analysis and identification to material molecule.)It is normal used in this method Rule instrument is Fourier Transform Infrared Spectrometer, and operation principle is:The light that light source is sent is by beam splitter(Semi-transparent semi-reflecting lens)Point A branch of to reach index glass 13 through transmission for two beams, another beam reaches horizontal glass 12 through reflection.Two-beam is respectively through horizontal glass 12 and index glass 13 Reflection returns beam splitter, and index glass 13 is for linear motion with a constant speed, thus the two-beam after beam splitter beam splitting is formed Optical path difference generates interference.Interference light, by sample cell, passes through the interference light containing sample message after sample after beam splitter congregation Detector is reached, is then handled by Fourier transform pairs signal, finally obtains infrared suction of the absorbance with wavelength change Receive spectrogram.
(2)To aqueous solution:Using Raman spectrum analysis method.(In infrared spectroscopy, since the absworption peak of water is larger, Larger interference can be caused to the detection of target substance, therefore needs stringent water removal, therefore this method is not suitable for aqueous solution.And due to The Raman scattering of water is very faint, and Raman spectrum is become as the biological sample and the preferable work of chemical substance in research aqueous solution Tool, therefore use Raman spectrum analysis method instead.)(Raman spectrum analysis method principle:When the monochromatic light exposure that a branch of frequency is v0 to sample After upper, the molecule of sample can scatter incident light.Most of light simply change direction scatter, and the frequency of light still with The frequency of exciting light is identical, and this scattering is known as Rayleigh scattering;And account for dissipating for 10^-6~10^-10 of total scattering luminous intensity It penetrates, not only the direction of propagation of light changes, but also the frequency for scattering light also changes, and this scattering is known as Raman scattering, Raman Scattering is generated due to the change of molecular polarizability.Difference on the frequency between scattering light and incident light is known as Raman shift, draws Graceful displacement depends on the variation of molecular vibration energy level, and unrelated with incident light frequency and only with scattering molecule structure in itself is related, Different chemical bonds or functional group take on a different character molecular vibration, therefore corresponding Raman shift is also feature, draw Size, intensity and the Raman peak shape of graceful displacement are identification chemical bond, the important evidence of functional group.Utilize polarization characteristic, Raman Spectrum is also used as the foundation of molecular isomer judgement, and the covalent bond in inorganic compound between metal ion and ligand is normal With Raman active, thus Raman spectrum can provide the information such as the composition in relation to complex, Structure and stability.
The Raman spectrum of general material molecule is very faint, in order to obtain the signal of enhancing, using doing for electrode surface roughening Method obtains the Surface Enhanced Raman Scattering Spectrum of high 10^4-10^7 times of intensity, when the Molecular Adsorption with resonance Raman effect exists During the electrode surface of roughening, what is obtained is serrs spectrum, and intensity can enhance 10^2-10^3 again.)
【3】Device systems run control principle:
The functions such as Fourier Transform Infrared Spectrometer module, Raman spectrometer module, high pressure draught generator, mechanical driving device Module accesses same computer, is central host 19(Hereinafter referred to as host 19), all parameter settings are in host It is completed on 19, database is also stored in host 19.Host 19 installs Fourier Transform Infrared Spectrometer and Raman spectrometer Driving and control program(Or its modified version), high pressure draught generator and mechanical driving device control program and will be each Program, which is bound up, makes the master control program of system coordination running, and master control program can call the resource of database simultaneously can be i.e. When the data that two spectrometers measure are saved in database.Master control program first opens basic parameter in each run Interface is set, inputs the essential information of this operation(The mark spectrum for the target substance that non-aqueous solution/aqueous solution, needs are isolated Line/by whole solutes respectively are isolated by coming, Yes/No preserves this data measured), click on START button after the completion of typing and set It is standby to start to work according to preset program.
Working-flow:
(1)Non-aqueous solution separates predetermined component workflow:IR data → the Fourier transformation for transferring target substance is red External spectrum analyzer module starts;High pressure draught generator preparation → mechanical driving device starts, by carrier-pellet 7 slowly to Forward The dynamic infrared spectrum by detecting band → measure is in real time compared with standard spectrum, once similarity reaches preset value, high pressure draught Generator is discharged from high speed nitrogen stream and blows out area's liquid, is collected into container;After one zone is blown off, lower section is collected Transmission one lattice of tape travel change a new collection vessel and accept, until entire carrier-pellet 7 is completely by detecting band, work of system It completes, and new data is stored in database.
(2)The whole components of non-aqueous solution separation or identification chemical composition workflow:Ftir analysis Instrument module starts;High pressure draught generator preparation → mechanical driving device starts, and carrier-pellet 7 is slowly advanced through detection Band, after detecting the infrared spectrum that short distance is stablized, high pressure draught generator sprays high speed nitrogen stream by area's liquid blowout, collection Into container, when a zone blow off end detect it is new(With upper spectrum similarity less than preset value)Infrared spectrum When, mechanical driving device pause, lower section collects transmission one lattice of tape travel and changes a new collection vessel undertaking, mechanical driving device It reruns, and so on, until entire carrier-pellet 7 is completely by detecting band, system one action is completed, new data is stored in Database, and each spectrum detected standard spectrum corresponding with data bank is compared, if similarity reaches preset value, Then identify the chemical composition of the component.
(3)Aqueous solution separates predetermined component workflow:Transfer Raman spectrum data → Raman spectrometer of target substance Module starts;High pressure draught generator preparation → mechanical driving device starts, and carrier-pellet 7 is slowly advanced through detection band → the Raman spectrum measured is in real time compared with standard spectrum, once similarity reaches preset value, high pressure draught generator is discharged from High speed nitrogen stream blows out area's liquid, is collected into container;After one zone is blown off, transmission tape travel one is collected in lower section Lattice change a new collection vessel and accept, and until entire carrier-pellet 7 is completely by detecting band, system one action is completed, and will New data is stored in database.
(4)The whole components of aqueous solution separation or identification chemical composition workflow:Raman spectrometer module starts;High pressure gas Flow-generator preparation → mechanical driving device starts, and carrier-pellet 7 is slowly advanced through detection band, detects that short distance is stablized Raman spectrum after, high pressure draught generator sprays high speed nitrogen stream by the blowout of area liquid, is collected into container, when an area Band blow off end detect it is new(With upper spectrum similarity less than preset value)During Raman spectrum, mechanical driving device is temporary Stop, lower section collects transmission one lattice of tape travel and changes a new collection vessel undertaking, and mechanical driving device reruns, so past Multiple, until entire carrier-pellet 7 is completely by detecting band, system one action is completed, and new data is stored in database, and will detection To each spectrum standard spectrum corresponding with data bank compared, if similarity reaches preset value, identify the component Chemical composition.
(5)Aqueous solution or non-aqueous solution specific components separate spare flow workflow:Target substance is transferred current real Test environment(The conditions such as corresponding solvent, stationary phase, temperature)Under Rf values(Rf value, before distance/solvent of Rf=component movement Along the distance moved)Front wheel in 7 front end alignment detection band of data → carrier-pellet → and mechanical driving device(Two, respectively Positioned at objective table both sides)The counter to connect【Survey the number of turns that shaft turns over(Numerical value consecutive variations can get fractional part)】It opens It is dynamic, high pressure gas generator prepares → when sovent diffusion is to the measure standard Rf value sovent diffusion apart from when, idler wheel is fast Speed, which starts, makes carrier-pellet 7 proceed to the position that target substance should reach(Distance is by counter controls), high pressure draught generator It sprays high speed nitrogen stream to blow out solution at this, separation is completed.(This method is easily disturbed, and accuracy is general, only makees spare selection. Also due to accuracy is general, substance is identified without Rf value method.)
As a result, this system complete basic parameter set after, only need to assign " beginnings " order, system can be automatically performed separation, The tasks such as identification realize the full-automation of equipment operation.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace And modification, the scope of the present invention is defined by the appended.

Claims (4)

1. based on thin-layer chromatography-high pressure gas pulse liquid phase component separator associated with bis- spectrum, including body(1), high pressure pumping lamp (14)And host(19), it is characterised in that:The body(1)Inside be provided with concave mirror(2), the concave mirror (2)Top be provided with MCT detectors(3), the MCT detectors(3)Top be provided with objective table, the objective table it is upper Surface is provided with carrier-pellet(7), one end of the objective table is provided with carrier-pellet import(20), the other end of the objective table sets It is equipped with carrier-pellet outlet(11), the carrier-pellet(7)Top be provided with detector(6), and detector(6)It is fixedly connected on machine Body(1)On, the detector(6)One end be provided with monochromator(5), the monochromator(5)One end be provided with the first convex lens Mirror(4), the high pressure pumping lamp(14)One end be provided with laser light source(8), the laser light source(8)One end be provided with second Convex lens(9), the high pressure pumping lamp(14)Lower section be provided with interferometer(10), the interferometer(10)Lower section be provided with it is fixed Mirror(12), the horizontal glass(12)One end be provided with index glass(13), the body(1)Be internally provided with module one(15), institute State body(1)Top module two is connected with by gas transmission line(16), the host(19)One side connected by data cable There is small integrator(18), the small integrator(18)One side is connected with controller by data cable(17), and module two(16)With Controller(17)Between connected by data cable, the host(19)Opposite side by data cable be connected with signal input/it is defeated Go out equipment(21).
2. according to claim 1 be based on thin-layer chromatography-high pressure gas pulse liquid phase component separator associated with bis- spectrum, It is characterized in that:The module one(15)Including the first gas chamber, the second gas chamber, switch control slide block and split sliding block, described first Segmentation sliding block is provided between gas chamber and the second gas chamber, first gas chamber is internally provided with switch control slide block.
3. according to claim 1 be based on thin-layer chromatography-high pressure gas pulse liquid phase component separator associated with bis- spectrum, It is characterized in that:The module two(16)Including valve, accumulator, pressure gauge, cylinder and source of the gas, the one side of the valve passes through defeated Tracheae is provided with accumulator, and the upper surface of the accumulator is provided with pressure gauge, and the one side of the accumulator is connected by appendix Air pump is connected to, the one side of the air pump is provided with source of the gas.
4. according to claim 1 be based on thin-layer chromatography-high pressure gas pulse liquid phase component separator associated with bis- spectrum, It is characterized in that:One end of the switch control slide block is provided with telescopic putter.
CN201711475184.7A 2017-12-29 2017-12-29 Based on thin-layer chromatography-high pressure gas pulse liquid phase component separator associated with bis- spectrum Pending CN108088809A (en)

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CN117046388A (en) * 2023-10-12 2023-11-14 四川大学华西医院 Device for high-pressure oxidation experiment of protein crystal

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