CN109298123A - A kind of novel thin layer chromatogram scanner and the analysis method using the scanner - Google Patents
A kind of novel thin layer chromatogram scanner and the analysis method using the scanner Download PDFInfo
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- CN109298123A CN109298123A CN201810365907.6A CN201810365907A CN109298123A CN 109298123 A CN109298123 A CN 109298123A CN 201810365907 A CN201810365907 A CN 201810365907A CN 109298123 A CN109298123 A CN 109298123A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/90—Plate chromatography, e.g. thin layer or paper chromatography
Abstract
The present invention relates to a kind of novel thin layer chromatogram scanner and utilize the analysis method of the scanner, it is characterized in that reaction ionization tube communicates with argon gas pipeline and guarantees that gas circuit is stablized by mass flow controller, chromato-stick and quartz ampoule tail end vertical alignment, it is wrapped up by copper wire coil in reaction ionization tube middle section, signal generator is of coupled connections with radio frequency amplifier, the radiofrequency signal of signal generator is amplified by signal after radio frequency amplifier to be enhanced and is transferred on copper wire coil, radiofrequency signal field is formed in copper wire coil inside, reaction gas and auxiliary gas are passed through in reaction ionization tube, plasma is generated under the excitation of radiofrequency signal field, plasma tail flame successively scans the chromato-stick at the uniform velocity moved, it is ionized by the component of separator well by plasma and generates ion, ion signal is collected by collector.The present invention can make each chemical component successively quickly be detected, and radio frequency plasma is used for tlc scanning detection for the first time, while realizing the qualitative and quantitative of each ingredient, to provide foundation to quickly understand the chemical composition information of sample.
Description
Technical field
The present invention relates to a kind of new chromatographic quasi-instrument, specifically a kind of novel thin layer chromatogram scanner and utilization should
The analysis method of scanner belongs to Petrochemical Engineering Analysis field, can be used in petroleum and petrochemical industry, medical and health, environmental monitoring with
The fields such as environmental protection.
Background technique
Thin-layer chromatography is a kind of means of very effective tracking chemical reaction, and it is suitable in pillar layer separation to can be also used for
The selection of solvent, the common stationary phase of thin-layer chromatography have aluminium oxide or silica gel, they are that polarity (positive) is either nonpolar
(reverse phase), mobile phase is then a kind of solvent that polarity is to be selected, in the research in most of industrial flows or laboratory, will all be made
Chemical tracing or identification are carried out with such means.
The basic procedure of thin-layer chromatography be by the reaction mixture point in solution on thin plate, then made using capillarity
Solvent (or mixed solvent) is moved up along plate to be unfolded, and according to the polarity of component in mixture, different compounds will be
Mobile different distance, the strong compound of polarity can have very strong suction-operated with polarity silica gel, move on thin plate on thin plate
Distance it is shorter；And nonpolar substance will retain in the solvent phase of flowing longer time to onboard move compared with
Big distance, with advances in technology, thin-layer chromatography derive chromato-stick via original chromatosheet, and chromato-stick is due to material
Intensive solvent expansion is high-efficient increasingly to receive an acclaim, and the chromato-stick being made of different stationary phases is also by more and more scientists
Worker is favored with analysis, and no matter which kind of form thin-layer chromatography is all current industrial manufacture, chemical identification, medication chemistry, ring
The indispensable important technicals of numerous areas such as border protection.
It needs to examine isolated ingredient with the thin-layer chromatogram scanner equipped with specific detectors after the completion of TLC separation
It surveys or identification, the type of Current Scan detection includes ultraviolet spectrophotometry, fluorescence spectrophotometry, hydrogen flameionization detection
Method etc., wherein according to scanning mode, and Single wavelength scanning and double-wavelength scan etc. can be divided into, using thin-layer chromatogram scanner pair
The method that chromatography spot makees scanning quantitation is referred to as thin-layered chromatography.
Petroleum is one of most important resource within the scope of the world today, it can be widely used in chemical industry, pharmacy, agriculture
The various aspects such as industry, space flight, the energy, as the mankind use more and more extensive, environmental hazard caused by petroleum to petroleum resources
Also increasing, but either to petroleum using angle still from the angle of environmental protection, petroleum is carried out detailed
Property Identification and composition analysis (namely Group Component analysis) are all very important work, for example, grinding in organopolysiloxane oil geology
In studying carefully, weight, light organic matter in petroleum can be described by the analysis to petroleum Group Component, this is for oil exploitation scheme
Research play the role of it is vital；In addition, the research of petroleum Group Component can also be ingredient, the evolution, maturation of crude oil
Situation provides evidence.If the biomarker in petroleum can indicate the palaeosedimentary environment of petroleum, for studying geology ring
Border forms and is also very helpful.
Since eighties of last century mid-term, the identification method of petroleum Group Component have passed through a series of differentiation and optimization: 1962
Year American Standard Test and materials association (ASTM) are using carclazyte-silica gel adsorption chromatography method as the standard of analysis mink cell focus race composition
Side (ASTM-D2007), for this method due to the limitation of clay materials, user is less.United States Bureau of Mines (USBM) in 1971 and beauty
The API260 project of institute of Petroleum of state (API) joint funding proposes for mink cell focus to be divided into 5 race's components first: acidic components,
Alkaline constituent, neutral nitrogen compounds, saturated hydrocarbons, aromatic hydrocarbons, this method are known as USBM-API method, are a kind of iteration chromatographies, can be with
Eluting solvent is recycled, but the disadvantage is that very cumbersome and very time-consuming, the only separation of acidic components and alkaline constituent
Just need continuous circulation flushing 6 days, therefore this method only to oil sample acidic components or alkaline constituent specialize in
Or it is just used when carrying out detailed composition research to sample.Jewell etc. proposes mink cell focus being divided into 4 race's components, i.e., saturated hydrocarbons,
Aromatic hydrocarbons, colloid, asphalitine, i.e. SARA method.
At present petroleum Group Component column chromatography for separation frequently with method have SY/T5119-2008 " in rock soluble organic and
Crude oil PONA analysis " method, and method is (referred to as with U.S.EPA 3611 " alumina column purification and separation petroleum waste "
3611 method of EPA).In the Group Component analysis of petroleum, four big components are often classified as, then carry out detailed qualitative analysis；Four big nations
Component is respectively saturated hydrocarbons, aromatic hydrocarbon, colloid and asphalitine.Petroleum Group Component column chromatography for separation is frequently with the People's Republic of China (PRC)
Oil and gas industry standard " soluble organic and crude oil PONA analysis in rock " is standard foundation, standard number: SY/
T5119-2008。
The instrument for being currently used in petroleum Group Component mainly has Single wavelength thin-layer chromatogram scanner, dual-wavelength lamellar scanning instrument, rodlike
Chromatogram scanner etc..
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, are base the present invention is based on rodlike chromatography
Plinth, change tlc scanning detector detection mode, provide it is a kind of by radio frequency plasma excitation novel thin layer chromatography sweep
Instrument is retouched, invention, which solves technical solution used by its technical problem, is: the present invention includes radio-frequency power supply, signal generator, radio frequency
Amplifier, copper wire coil, shading ring, chromato-stick, collector, amplifier, recorder, chromatography rod bracket, is led at reaction ionization tube
Rail, argon gas pipeline, mass flow controller, wherein chromato-stick and mobile platform are fixed by fixing seat and bracket and are put down with mobile
Platform is mobile with setting speed together, it is characterised in that reaction ionization tube is communicated with argon gas pipeline and protected by mass flow controller
It demonstrate,proves gas circuit to stablize, chromato-stick and quartz ampoule tail end vertical alignment, and guarantees 2-3mm distance；Radio frequency reaction ionization part point includes anti-
Ionization tube, copper wire coil, radio frequency amplifier and signal generator are answered, reaction ionization tube middle section is wrapped up by copper wire coil, described
Signal generator is of coupled connections with radio frequency amplifier, and the radiofrequency signal of signal generator is amplified by signal after radio frequency amplifier
Enhance and be transferred on copper wire coil, forms radiofrequency signal field in copper wire coil inside, be passed through reaction gas in reaction ionization tube
With auxiliary gas, plasma is generated under the excitation of radiofrequency signal field, plasma tail flame successively scans the chromatography at the uniform velocity moved
Stick, is ionized by plasma by the component of separator well and generates ion, and ion signal is collected by collector, then put by amplifier
Greatly, the microprocessor such as instrument or computer are finally recorded and Signal acquiring and processing is carried out by special-purpose software.
The side of the chromato-stick is provided with chromatography rod bracket, and chromatography rod bracket is connected on guide rail.
Preferably, the reaction ionization tube is made of high temperature resistant quartz ampoule.The radio frequency range of the signal generator
Between 10-1000MHz, power is between 1-500W after radio frequency amplifier amplifies.Preferably, the reaction gas is argon gas,
Range of flow is 1.0-50.0mL/min, and the supplement reaction gas is helium, range of flow 1.0-100.0mL/min.
The second object of the present invention is that a kind of this instrument of use progress petroleum is provided by taking the detection of petroleum Group component separation as an example
The method of Group Component analysis, method separate petroleum hydrocarbon by rodlike thin-layer chromatography, are swept by radio frequency discharge thin-layer chromatography
It retouches instrument to be detected, sample, which is put, to be passed sequentially through different organic solvents in the bottom of chromato-stick and be unfolded, and chromato-stick is moving
It is at the uniform velocity successively ionized by isolated component, the signal of ionization is collected and puts by ionization source tail end under the drive of moving platform
Greatly, it is finally calculated by special-purpose software.
The present invention is added the moving guide rail optimized using the detector innovated and designed so that a whole set of instrument simplicity lightly, is adsorbed
Chemical constituent on chromato-stick can be desorbed and ionize simultaneously, and chromato-stick moves along sliding rail at the uniform velocity driven by the motor
By plasma wake flame, so that the separation for realizing chemical component and desorption ionization simultaneously, pass through the signal of collector and amplifier
Collect and amplification, each chemical component can be made successively quickly to be detected, this patent it is a technical advantage that for the first time by radio frequency etc.
Gas ions are detected for tlc scanning, while realizing the qualitative and quantitative of each ingredient, thus to quickly understand sample
Chemical composition information provides foundation.
Detailed description of the invention
Fig. 1: structural schematic diagram of the embodiment of the present invention.
In figure: radio-frequency power supply 101, signal generator 102, radio frequency amplifier 103, reaction ionization tube 104, copper wire coil
105, shading ring 106, chromato-stick 107, collector 108, amplifier 109, recorder 110, chromatography rod bracket 111, guide rail 112,
Argon gas pipeline 113, mass flow controller 114.
Specific embodiment
It is described with reference to make the present invention detailed description in detail below.As shown in the picture, the present invention includes radio frequency electrical
Source 101, signal generator 102, radio frequency amplifier 103, reaction ionization tube 104, copper wire coil 105, shading ring 106, chromato-stick
107, collector 108, amplifier 109, recorder 110, chromatography rod bracket 111, guide rail 112, argon gas pipeline 113, mass flow
Controller 114, wherein chromato-stick 107 is fixed with bracket by fixing seat with mobile platform and sets speed together with mobile platform
Degree movement, it is characterised in that reaction ionization tube 104 communicates with argon gas pipeline 113 and guarantees gas by mass flow controller 100
Road is stablized, chromato-stick 107 and quartz ampoule tail end vertical alignment, and guarantees 2-3mm distance；Radio frequency reaction ionization part point includes reaction
Ionization tube 104, copper wire coil 105, radio frequency amplifier 103 and signal generator 102 react 104 middle section of ionization tube by copper wire line
Circle 105 is wrapped up, and the signal generator 102 is of coupled connections with radio frequency amplifier 103, the radiofrequency signal of signal generator 102
Being amplified by signal after radio frequency amplifier 103 enhances and is transferred on copper wire coil 105, is formed inside copper wire coil 105
Radiofrequency signal field is passed through reaction gas and auxiliary gas in reaction ionization tube 104, generates plasma under the excitation of radiofrequency signal field
Body, plasma tail flame successively scan the chromato-stick 107 at the uniform velocity moved, by the component of separator well by plasma ionization generate from
Son, ion signal are collected by collector 108, are then amplified by amplifier 109, and micro- place such as instrument 110 or computer is finally recorded
Reason machine carries out Signal acquiring and processing by special-purpose software.
The side of the chromato-stick 107 is provided with chromatography rod bracket 111, and chromatography rod bracket 111 is connected to guide rail 112
On.
Preferably, the reaction ionization tube 104 is made of high temperature resistant quartz ampoule.The radio frequency frequency of the signal generator 102
Rate range is between 10-1000MHz, and power is between 1-500W after the amplification of radio frequency amplifier 103.Preferably, the reaction
Gas is argon gas, and range of flow 1.0-50.0mL/min, the supplement reaction gas is helium, range of flow 1.0-100.0mL/
min。
Embodiment one: petroleum Group Component measures in pedotheque soluble organic matter
Measurement key instrument used is the device of the invention developed, and corollary apparatus has 1, centrifuge, chromatography cylinder 3,
Constant humidity cabinet 1, electronic balance 1, micro syringe and reagent etc. are several.
Experimental procedure:
One, 5g pedotheque is weighed, after chloroform extraction centrifugation, takes supernatant 5-10mg in sample bottle, use is micro
500 μ L methylene chloride are added in syringe, and covering tightly bottle cap jog dissolves sample sufficiently；
Two, prepare chromatographic solution, normal hexane, toluene, methylene chloride: methanol 95:5 are separately added into three chromatography cylinders, respectively
Solvent liquid level height about 10mm in cylinder covers cylinder cap closed 30 minutes；
Three, point sample:
1,1 μ L sample liquid is extracted from sample bottle with micro syringe, divides 3-5 point to the silica gel chromatograph stick 107 activated
On, control sample spot height is less than 2mm, is placed in chromato-stick 107 in draught cupboard solvent flashing 5-8 minutes after point sample；
2, chromato-stick 107 is placed in constant humidity cabinet after keeping 10min, chromato-stick 107 is put into the first chromatography cylinder, with just
30min is unfolded in hexane, rises to solvent front away from taking out after point of sample 85-90mm, at room temperature in placing in draught cupboard
3min；
3, it is replaced in after keeping 10min in constant humidity cabinet, is put into the second chromatography cylinder and 10min is unfolded with toluene, until solvent
Forward position reach point of sample top 45-50mm at after, take out and in draught cupboard in open placement 3min at room temperature；
4, it is again placed in constant humidity cabinet and keeps 10min, be put into third chromatography cylinder, with methylene chloride: methanol (95:5)
5min is unfolded in mixed solvent, until taking out the room temperature decentralization in draught cupboard after solvent front reaches at the 15-20mm of point of sample top and setting
5min, volatilize solvent to the greatest extent；
Four, Group Component measures
1, it opens radio-frequency power supply 101 to switch, adjusting frequency is 650MHz；Argon gas switch is opened, argon gas is from argon gas pipeline 113
Interior entrance is adjusted by mass flow controller 114, and argon gas flow velocity is 500mL/min, the radiofrequency signal of signal generator 102
Being amplified by signal after radio frequency amplifier 103 enhances and is transferred on copper wire coil 105, is formed inside copper wire coil 105
Helium switch is opened in radiofrequency signal field, and adjusting flow velocity is 55mL/min, and igniting makes plasma stability；
2, open moving guide rail 112 motor, set moving distance be 160mm, movement speed 5.0mm/s, wait from
Daughter wake flame successively scans the chromato-stick 107 at the uniform velocity moved；
3, computer and software systems are opened；
4, start 112 motor of moving guide rail and analysis acquisition system simultaneously, ionized by the component of separator well by plasma
Ion is generated, ion signal is collected by collector 108, then amplified by amplifier 109, and instrument 110 or computer are finally recorded
Equal microprocessor carry out Signal acquiring and processing by special-purpose software, record simultaneously output test result, including chromatogram and each chromatography
Each each chromatographic peak area is successively recorded as A1, A2, A3, A4 by scanning sequency, clicks to enter every group of peak by the peak area at peak
Check the mass number situation of corresponding molecule.
Each mass fraction calculates according to the following formula in sample:
In formula:
I S, A, N and B are replaced, then:
Xi--- the mass fraction for respectively indicating saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt is expressed as a percentage；
Ai--- respectively indicate the peak area of saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt；
Fi--- respectively indicate the mass calibration coefficient of saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt；
AS, AA, ANAnd AB--- saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt peak area；
FS, FA, FNAnd FB--- saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt mass calibration coefficient.
The measuring method of sample each component mass calibration coefficient positive coefficient is as follows:
When saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt identical in quality, and the mass calibration coefficient F of saturated hydrocarbonsS=1
When, then:
The mass calibration coefficient of aromatic hydrocarbon:
The mass calibration coefficient of colloid:
The mass calibration coefficient of asphalitine:
Embodiment two: petroleum Group Component measures in crude oil sample
Measurement key instrument used is the device of the invention developed, and corollary apparatus has chromatography cylinder 3, constant humidity cabinet 1,
Electronic balance 1, micro syringe and reagent etc. are several.
Experimental procedure:
One, by crude oil sample with 0.22 μm of organic filtering with microporous membrane into sample bottle, then added with micro syringe
Enter 500 μ L methylene chloride, covering tightly bottle cap jog dissolves sample sufficiently；
Two, prepare chromatographic solution, be separately added into normal hexane, normal hexane in three chromatography cylinders: methylene chloride (1:1V:V), just
Hexane: isoamyl alcohol (9:1V:V).Solvent liquid level height about 10mm in each cylinder.Cover cylinder cap closed 30 minutes；
Three, point sample:
1,1 μ L sample liquid is extracted from sample bottle with micro syringe, divides 3-5 point to the silica gel chromatograph stick 107 activated
On.It controls sample spot height and is less than 2mm.Chromato-stick 107 is placed in draught cupboard solvent flashing 5-8 minutes after point sample；
2, chromato-stick 107 is placed in constant humidity cabinet after keeping 10min, chromato-stick 107 is put into the first chromatography cylinder, with just
30min is unfolded in hexane, rises to solvent front away from taking out after point of sample 85-90mm, at room temperature in placing in draught cupboard
3min；
3, it is replaced in after keeping 10min in constant humidity cabinet, is put into the second chromatography cylinder and is mixed with normal hexane with methylene chloride
Solvent (1:1V:V) be unfolded 10min, until solvent front reach point of sample top 45-50mm at after, take out and in draught cupboard
Open placement 3min at room temperature；
4, it is again placed in constant humidity cabinet and keeps 10min, be put into third chromatography cylinder, with normal hexane: isoamyl alcohol (9:1V:
V) 5min is unfolded in mixed solvent, until taking out the room temperature in draught cupboard after solvent front reaches at the 15-20mm of point of sample top and transferring
5min is set, volatilize solvent to the greatest extent；
Four, Group Component measures
1, radio-frequency signal generator power switch is opened, adjusting frequency is 650MHz；Argon gas switch is opened, argon gas is from argon gas pipeline
Entering in 113, is adjusted by mass flow controller 114, argon gas flow velocity is 500mL/min, the radio frequency of signal generator 102
Signal is amplified by signal after radio frequency amplifier 103 to be enhanced and is transferred on copper wire coil 105, inside copper wire coil 105
Radiofrequency signal field is formed, helium switch is opened, adjusting flow velocity is 55mL/min, and igniting makes plasma stability；
2, open moving guide rail 112 motor, set moving distance be 160mm, movement speed 5.0mm/s, wait from
Daughter wake flame successively scans the chromato-stick 107 at the uniform velocity moved；
3, computer and software systems are opened；
4, start the motor and spectrometer analysis acquisition system of moving guide rail 112 simultaneously, by the component of separator well by it is equal from
Daughter ionization generates ion, and ion signal is collected by collector 108, then amplified by amplifier 109, is finally recorded instrument 110
Or the microprocessor such as computer carry out Signal acquiring and processing by special-purpose software, record simultaneously output test result, including chromatogram
And the peak area of each chromatographic peak, each each chromatographic peak area is successively recorded as A1, A2, A3, A4 by scanning sequency, click into
Enter the mass number situation that corresponding molecule is checked at every group of peak.
Each mass fraction calculates according to the following formula in sample:
In formula:
I S, A, N and B are replaced, then:
Xi--- the mass fraction for respectively indicating saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt is expressed as a percentage；
Ai--- respectively indicate the peak area of saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt；
Fi--- respectively indicate the mass calibration coefficient of saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt；
AS, AA, ANAnd AB--- saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt peak area；
FS, FA, FNAnd FB--- saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt mass calibration coefficient.
The measuring method of sample each component mass calibration coefficient positive coefficient is as follows:
When saturated hydrocarbons, aromatic hydrocarbon, resin and asphalt identical in quality, and the mass calibration coefficient F of saturated hydrocarbonsS=1
When, then:
The mass calibration coefficient of aromatic hydrocarbon:
The mass calibration coefficient of colloid:
The mass calibration coefficient of asphalitine:
The above-described embodiments are merely illustrative of preferred embodiments of the present invention, not to structure of the invention
Think and range is defined, without departing from the design concept of the invention, ordinary engineering and technical personnel is to this in this field
The all variations and modifications that the technical solution of invention is made, should all fall into protection scope of the present invention, and the present invention is claimed
Technology contents are all described in the claims.
Claims (3)
1. a kind of novel thin layer chromatogram scanner and the analysis method using the scanner, including radio-frequency power supply (101), signal hair
Raw device (102), radio frequency amplifier (103), reaction ionization tube (104), copper wire coil (105), shading ring (106), chromato-stick
(107), collector (108), amplifier (109), recorder (110), chromatography rod bracket (111), guide rail (112), argon gas pipeline
(113), mass flow controller (114), wherein chromato-stick (107) and mobile platform fixed by fixing seat with bracket and with shifting
Moving platform is mobile with setting speed together, it is characterised in that reaction ionization tube (104) communicates with argon gas pipeline (113) and passes through matter
Measure flow controller (100) and guarantee that gas circuit is stablized, chromato-stick (107) and quartz ampoule tail end vertical alignment, and guarantee 2-3mm away from
From radio frequency reaction ionization part point includes reaction ionization tube (104), copper wire coil (105), radio frequency amplifier (103) and signal hair
Raw device (102), reaction ionization tube (104) middle section are wrapped up by copper wire coil (105), the signal generator (102) and radio frequency
Amplifier (103) is of coupled connections, and by radio frequency amplifier (103), signal is amplified the radiofrequency signal of signal generator (102) afterwards
Enhance and be transferred on copper wire coil (105), form radiofrequency signal field inside copper wire coil (105), in reaction ionization tube
(104) it is passed through reaction gas and auxiliary gas in, plasma is generated under the excitation of radiofrequency signal field, plasma tail flame is successively swept
The chromato-stick (107) at the uniform velocity moved is retouched, is ionized by the component of separator well by plasma and generates ion, ion signal is by collector
(108) it collects, is then amplified by amplifier (109), be finally recorded the microprocessor such as instrument (110) or computer by special-purpose software
Carry out Signal acquiring and processing.
2. a kind of novel thin layer chromatogram scanner according to claim 1 and the analysis method using the scanner, special
Sign is that the side of chromato-stick (107) is provided with chromatography rod bracket (111), and chromatography rod bracket (111) is connected to guide rail (112)
On.
3. a kind of novel thin layer chromatogram scanner according to claim 1 and the analysis method using the scanner, special
Sign is that react ionization tube (104) is made of high temperature resistant quartz ampoule, and the radio frequency range of the signal generator (102) exists
Between 10-1000MHz, power is between 1-500W after the amplification of radio frequency amplifier 103, it is preferred that and the reaction gas is argon gas,
Range of flow is 1.0-50.0mL/min, and the supplement reaction gas is helium, range of flow 1.0-100.0mL/min.
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| CN201810365907.6A CN109298123A (en) | 2018-04-23 | 2018-04-23 | A kind of novel thin layer chromatogram scanner and the analysis method using the scanner |
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Cited By (1)
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| CN114513890A (en) * | 2022-04-19 | 2022-05-17 | 北京大学第三医院（北京大学第三临床医学院） | Plasma sterilization device with high energy utilization rate and application |
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