CN104258598B - Solid phase extraction column and preparation method thereof as well as chemical sample pretreatment method based on solid phase extraction column - Google Patents
Solid phase extraction column and preparation method thereof as well as chemical sample pretreatment method based on solid phase extraction column Download PDFInfo
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Abstract
The invention relates to a solid phase extraction column and a preparation method thereof as well as a chemical sample pretreatment method based on the solid phase extraction column. The solid phase extraction column comprises a separation column and a solid phase extraction agent, wherein the separation column is filled with the solid phase extraction agent; the solid phase extraction agent is graphene or modified graphene; graphene is single-layered graphene or oligo-layered graphene; modified graphene is selected from at least one of aminated graphene, carboxylated graphene, cyano graphene, nitryl graphene, boric acid based graphene, phosphoric acid based graphene, hydroxylated graphene, sulfhydrylated graphene, methylated graphene, allylated graphene, trifluoromethylated graphene, dodecylated graphene, octadecylated graphene, fluorinated graphene, brominated graphene, chlorinated graphene and iodated graphene. The solid phase extraction column is used for pre-treating a chemical sample and can realize efficient separation effect; and the problem that target components cannot be detected in subsequent detection or a real value cannot be detected to cause data distortion is avoided.
Description
Technical field
The present invention relates to solid phase extraction techniques field, more particularly to a kind of solid-phase extraction column, its preparation method and be based on
The chemical example pre-treating method of solid-phase extraction column.
Background technology
In the detection and analysis work of chemical example, particularly natural sample, modal problem is that the component of sample is big
When many all excessively complicated it is impossible to direct analysis are carried out by chromatograph, or direct analysis effect is bad.Accordingly, it would be desirable to by right
Chemical example carries out pre-treatment to realize the separation of determinand, then carries out chromatography.Locate before chemical example the most frequently used at present
Reason technology is Solid-Phase Extraction (spe) technology, realizes inhaling by the affinity of the special component in component and solid extracting agent
Attached extraction, thus realize the separation of special component.Therefore, solid extracting agent is selected to seem particularly important.Solid extracting agent
Polarity, the characteristic such as solid extracting agent particular functional group, the pore-size distribution on solid extracting agent surface and specific surface area of possessing,
Directly determine extraction efficiency and the selectivity of whole spe process.
Traditionally, the selection of solid extracting agent is generally the silica gel that carbon 18 is chain alkyl modification, ketjenblack EC, gathers
The organic and inorganic material such as phenylethylene micro ball.
Traditional solid extracting agent all has that packing density is larger, consumption is more, make the waste during analysis larger and
Relatively costly the shortcomings of.Topmost problem is, traditional solid extracting agent is many due to consumption, and the micro constitutent in sample is solid
Degree of absorption on phase extractant is larger, thus cannot be measured or cannot detect actual value, therefore in follow-up detection
There is distortion in data.
Content of the invention
Based on this it is necessary to provide a kind of solid-phase extraction column, so that pre-treatment is carried out to chemical example, it is to avoid in follow-up inspection
In survey, target components cannot be measured or cannot detect actual value and the problem of data distortion that exists.
A kind of solid-phase extraction column it is characterised in that including detached dowel and being filled in solid extracting agent in described detached dowel,
Described solid extracting agent is Graphene or the Graphene through modifying；Described Graphene is single-layer graphene or form the few-layer graphene alkene,
The described Graphene through modifying is selected from amination graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boric acid
Base Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene,
Trifluoromethylation Graphene, myristalated Graphene, octadecyl graphite alkene, fluorinated graphene, bromination Graphene, chlorination
At least one in Graphene and iodate Graphene.
Wherein in an embodiment, described detached dowel includes the polypropylene plastics stock column of hollow and is removable installed in institute
State two porous aluminum oxide sieve plates within polypropylene plastics stock column；Described solid extracting agent is filled in described two porous oxygen
Change between aluminum sieve plate.
A kind of preparation method of solid-phase extraction column, comprises the steps:
Select a kind of from multiple solid extracting agents treating selection, the described solid extracting agent treating selection is Graphene or warp
Cross the Graphene modified；Described Graphene is single-layer graphene or form the few-layer graphene alkene, and the described Graphene through modifying is selected from ammonia
Base graphite alkene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxyl
Graphite alkene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, trifluoromethylation Graphene, myristalated
In Graphene, octadecyl graphite alkene, fluorinated graphene, bromination Graphene, chlorination Graphene and iodate Graphene at least
A kind of；
Selected solid extracting agent is loaded in detached dowel, the detached dowel that will be equipped with described solid extracting agent is placed on shaking table
Upper vibration 3min, and it is compacted described solid extracting agent, obtain described solid-phase extraction column.
Wherein in an embodiment, described select a kind of method concrete from multiple solid extracting agents treating selection
For:
Respectively multiple solid extracting agents treating selection are configured to multigroup Solid-Phase Extraction agent dispersing liquid, and are intended to treating test sample
The sterling of the target components detecting in product is configured to multigroup target components dispersion liquid, respectively by multigroup Solid-Phase Extraction agent dispersing liquid
Carry out being mixed to get multigroup mixture with multigroup target components dispersion liquid, and mixture described in every group is carried out ultrasonic disperse, treat
After described mixture sedimentation, select the solid extracting agent in one group of minimum mixture of sedimentation degree；
Described multiple solid extracting agent treating selection is Graphene or the Graphene through modifying, and described Graphene is monolayer
Graphene or form the few-layer graphene alkene, the described Graphene through modifying is selected from amination graphene, carboxylated Graphene, cyano group graphite
Alkene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, methyl graphite
Alkene, allylation Graphene, trifluoromethylation Graphene, myristalated Graphene, octadecyl graphite alkene, fluorographite
Alkene, bromination Graphene, chlorination Graphene and iodate Graphene and amination graphene, carboxylated Graphene, cyano group Graphene, nitre
Base Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, alkene
Propylated Graphene, trifluoromethylation Graphene, myristalated Graphene, octadecyl graphite alkene, fluorinated graphene, bromine
At least one in graphite alkene, chlorination Graphene and iodate Graphene.
A kind of chemical example pre-treating method based on Solid-Phase Extraction, comprises the steps:
Above-mentioned solid phase extraction column is activated；
By in the described solid-phase extraction column after the chemical example injection activation of pre-treatment；
With eluent, drip washing is carried out to described solid-phase extraction column；And
With eluant, eluting is carried out to described solid-phase extraction column, obtain eluent.
Wherein in an embodiment, the operation that above-mentioned solid phase extraction column is activated is particularly as follows: is added activator
In described solid-phase extraction column, the volume of described activator is 1/8 times～1 times of the volume of described detached dowel；Described activator choosing
From methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane, carbon tetrachloride, ether, toluene, benzene, hexamethylene,
Petroleum ether, hexane, pentane, mass fraction be 37% hydrochloric acid and mass fraction be in 40% sodium hydrate aqueous solution at least one
Kind.
Wherein in an embodiment, treat that the volume of the chemical example of pre-treatment is 1/8 times of the volume of described detached dowel
～1 times.
Wherein in an embodiment, the volume of described eluent is 1/8 times～1 times of the volume of described detached dowel；Institute
State eluent be selected from methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane, carbon tetrachloride, ether, toluene,
Benzene, hexamethylene, petroleum ether, hexane, pentane, mass fraction be 37% hydrochloric acid and mass fraction be 40% sodium hydrate aqueous solution
In at least one.
Wherein in an embodiment, the volume of described eluant is 1/8 times～1/2 times of the volume of described detached dowel；
Described eluant is selected from methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane, carbon tetrachloride, ether, first
At least one in benzene, benzene, hexamethylene, petroleum ether, hexane and pentane.
Wherein in an embodiment, also include the step that described eluent is processed, described eluent is carried out
The step processing obtains dried object particularly as follows: drying up described eluent nitrogen, then with described eluant to described dried object
Carry out constant volume.
Above-mentioned solid phase extraction column using Graphene or passes through the Graphene modified as solid extracting agent, utilizes graphite well
Alkene and the selection characterization of adsorption of the Graphene after the Graphene modified is functionalization, the graphite of Graphene and different functionalization
Alkene material has different selectivitys to different elements, polarity and structure, before chemical example being carried out using this solid-phase extraction column
Process, the every component in system to be measured can be fixed effectively, and the stone with Graphene or through modifying with every component
The affine degree of black alkene is different and segmentation is dissociated, thus realizing efficient separating effect, it is to avoid target group in follow-up detection
Point cannot the measured or problem of data distortion that cannot detect actual value and exist.
Brief description
Fig. 1 is the structural representation of the solid-phase extraction column of an embodiment；
Fig. 2 is the flow chart of the chemical example pre-treating method based on Solid-Phase Extraction of an embodiment；
Fig. 3 is the liquid chromatogram of embodiment 1；
Fig. 4 is the liquid chromatogram of embodiment 2；
Fig. 5 is the liquid chromatogram of embodiment 3；
Fig. 6 is the liquid chromatogram of embodiment 4；
Fig. 7 is the liquid chromatogram of embodiment 5；
Fig. 8 is the liquid chromatogram of embodiment 6.
Specific embodiment
Understandable for enabling the above objects, features and advantages of the present invention to become apparent from, below in conjunction with the accompanying drawings to the present invention
Specific embodiment be described in detail.Elaborate a lot of details in order to fully understand this in the following description
Bright.But the present invention can be much to implement different from alternate manner described here, and those skilled in the art can be not
Similar improvement is done, therefore the present invention is not embodied as being limited by following public in the case of running counter to intension of the present invention.
Refer to Fig. 1, the solid-phase extraction column of an embodiment, including detached dowel 10 and be filled in the solid phase in detached dowel 10
Extractant 20.
Detached dowel 10 includes the cylinder 101 of hollow and is removable installed within cylinder 101 two porous of hollow
Property sieve plate 102 (hole of Fig. 1 not shown porous sieve plate 102).Solid extracting agent 20 be filled in two porous sieve plates 102 it
Between.
In present embodiment, the cylinder 101 of hollow is polypropylene plastics cylinder, and porous sieve plate 102 aoxidizes for porous
Aluminum sieve plate.
It is appreciated that in other embodiments, the cylinder 101 of hollow be not limited to polypropylene plastics cylinder or
The cylinder of other materials, such as polypropylene cylinder.Porous sieve plate 102 be also not necessarily limited to porous aluminum oxide sieve plate or its
The porous sieve plate of his material, such as porous polypropylene sieve plate, porous glass fiber sieve plate etc..
One end of the cylinder 101 of hollow is provided with stigma 103.Stigma 103 is the cylindrical shape of both ends open.Stigma 103 with many
Permeability sieve plate 102 connects.
Solid extracting agent 20 is Graphene or the Graphene through modifying.Graphene or the Graphene itself through modifying are made
For carrier and adsorbent, carry or without being filled in detached dowel 10 in cross-linking agent without using other carriers, make
Obtain that preparing of this solid-phase extraction column is relatively simple, preparation cost is relatively low.And, use merely Graphene or the graphite through modifying
Alkene can catch target components effectively as solid extracting agent, need not repair with other kinds of solid extracting agent such as chain alkyl
The combination such as the silica gel of decorations, ketjenblack EC, polystyrene microsphere, can be prevented effectively from silica gel, the graphitization of chain alkyl modification
Traditional solid extracting agent such as carbon black, polystyrene microsphere due to leading to the micro constitutent in largely adsorption sample consumption more
And the problem of the data distortion causing.
Graphene density is extremely low, specific surface area is higher and chemical characteristic is relatively stable, compared with traditional solid extracting agent, such as
The solid extracting agent of silica matrix, can greatly reduce the consumption of extractant using Graphene, and to the ph value of sample no longer
Sensitivity, can effectively open up its range of application wide, realize splendid separating effect.And, Graphene has relatively to nonpolar molecule
Good absorption property, particularly can be interacted by π-π to the molecule having aromatic ring, come further with other nonpolar molecules
Carry out separating.
Graphene is single-layer graphene or form the few-layer graphene alkene.
Certain modification is carried out to Graphene moreover it is possible to obtain more different selections, can be used in different chemical samples
Product carry out pre-treatment.Graphene through modifying is selected from amination graphene, carboxylated Graphene, cyano group Graphene, nitro stone
Black alkene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, pi-allyl
Graphite alkene, trifluoromethylation Graphene, myristalated Graphene, octadecyl graphite alkene, fluorinated graphene, bromination stone
At least one in black alkene, chlorination Graphene and iodate Graphene.
The above-mentioned Graphene referring to functionalization through the Graphene modified, for example, amination graphene refers to draw amino
Enter in Graphene, carboxylated Graphene refers to carboxyl is introduced in Graphene, and fluorinated graphene refers to incorporate fluorine atoms into graphite
In alkene.
The Graphene of functionalization has selection characterization of adsorption, and the grapheme material of different functionalizations is to different elements, pole
Property and structure have different selectivitys, and the Graphene that different target molecules is used with different functionalizations is as adsorbent, energy
Enough obtain preferable separating effect.Such as, amination ink alkene can provide stronger hydrogen bond, so that the polarity containing proton is divided
Son can pass through adsorption by hydrogen bond, and nonpolar molecule then degree of absorption is weaker.
When only having a kind of target components in a sample, select a kind of Graphene through modification as Solid-Phase Extraction
Agent.When there are at least two target components in a sample, the property according to two kinds of target components may be selected at least two warps
Cross the Graphene modified as solid extracting agent.In the case of there are at least two target components, can be according to the pole of two kinds of components
Property size to select corresponding different grapheme material from unit structure.
Above-mentioned solid phase extraction column is used Graphene or through the Graphene modified as solid extracting agent, using Graphene or
Strong adsorption through between the Graphene of modification and target components to be detected is so as to have to specifically target components to be detected
Crystallized ability, and there is no absorbability to the detected components of non-targeted, thus effectively capturing trace or a small amount of in sample
Target components to be detected, and the mensure of the concrete content of target components can be obtained in follow-up chromatography, it is to avoid
In follow-up detection, target components cannot be measured or cannot detect actual value and the problem of data distortion that exists.
And, the density of the Graphene due to Graphene or through modifying is less, can efficiently reduce solid-phase extraction column
Middle Graphene or the consumption of the Graphene through modifying, not only enable the microcomponent in system to be measured be detected, simultaneously
Reduce the waste of solid extracting agent, be conducive to cost-effective.
The preparation method of the solid-phase extraction column of one embodiment, for preparing above-mentioned solid phase extraction column.This solid-phase extraction column
Preparation method comprise the steps 110～step 120.
Step 110: select a kind of from multiple solid extracting agents treating selection.
Treat that the solid extracting agent of selection is Graphene or passes through the Graphene modified.Wherein, Graphene is single-layer graphene
Or form the few-layer graphene alkene.Graphene through modifying is selected from amination graphene, carboxylated Graphene, cyano group Graphene, nitro stone
Black alkene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, pi-allyl
Graphite alkene, trifluoromethylation Graphene, myristalated Graphene, octadecyl graphite alkene, fluorinated graphene, bromination stone
At least one in black alkene, chlorination Graphene and iodate Graphene.
In the case of the sterling having target components to be detected, carry out sedimentation experiment to select suitable Solid-Phase Extraction
Agent.
Sedimentation experiment comprises the steps:
Respectively multiple solid extracting agents treating selection are configured to multigroup Solid-Phase Extraction agent dispersing liquid, and are intended to treating test sample
The sterling of the target components detecting in product is configured to multigroup target components dispersion liquid, respectively by multigroup Solid-Phase Extraction agent dispersing liquid
Carry out being mixed to get multigroup mixture with multigroup target components, every group of mixture is carried out ultrasonic disperse, after thing sedimentation to be mixed,
Select the solid extracting agent in one group of minimum mixture of sedimentation degree.
The absorption to target components for the Graphene of the Graphene in one group of minimum mixture of sedimentation degree or process modification
Better performances, therefore select the solid extracting agent in one group of minimum mixture of sedimentation degree.
The solvent of Solid-Phase Extraction agent dispersing liquid and target components dispersion liquid is both preferably deionized water.When target components are being gone
When dissolubility in ionized water is good, from methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane, tetrachloro
Change carbon, ether, toluene, benzene, hexamethylene, petroleum ether, hexane, pentane, mass percent concentration are 37% hydrochloric acid and quality hundred
Divide at least one solvent as dispersion liquid that specific concentration is in 40% aqueous solution of sodium hydroxide.
Due to this dissolubility in water of the Graphene through modifying preferably, in order to truly reflect the graphite through modifying
Alkene is to the absorption situation of target components it is preferable that to treat that the solid extracting agent of selection and above-mentioned solvent are configured to many by multiple respectively
Group Solid-Phase Extraction agent dispersing liquid, concentration is 0.1mg/ml～0.5mg/ml, then is intended to the target components of detection in testing sample
Sterling be also made into 0.5mg/ml as gradient with above-mentioned solvent, concentration be 0.5mg/ml～5mg/ml sequence target components
Dispersion liquid.Respectively multigroup Solid-Phase Extraction agent dispersing liquid and a series of target components dispersion liquid are mixed with the ratio of volume ratio 1:1
Obtain multigroup mixture, every group of mixture takes 1ml～5ml to carry out ultrasonic disperse, after the sedimentation of this mixture, select sedimentation degree
Solid extracting agent in one group of minimum mixture.
Preferably, the method for mixture sedimentation is standing sedimentation 30min～60min or with 3000r/min～4000r/min
Rotating speed centrifugal sedimentation 0.5min～2min.
By sedimentation situation in target components sterling to be detected for the Graphene of above-mentioned Graphene or process modification it is
The calibrating of degree of scatter, to determine the adsorption strength between Graphene or the Graphene through modifying and target components to be detected,
Also the phase of the Graphene quickly and simply judging selection or the Graphene through modification and target components to be detected can be crossed
Mutual relation, is conducive to the selective absorption to target components, improves the vacuum reliability of the data of follow-up chromatography.
In the case of the sterling not having target components to be detected, substantially polarity according to the target components to be detected Lai
Select Graphene or the Graphene through modifying.The bigger molecule of polarity, the Graphene of corresponding selection or through grapheme modified
Just should have bigger polarity, thus playing the effect that target components are produced with strong absorption.
Step 120: solid extracting agent is loaded in detached dowel 10, the detached dowel 10 that will be equipped with solid extracting agent is placed on shaking table
Upper vibration 3min, and it is compacted solid extracting agent, obtain solid-phase extraction column.
Solid extracting agent is loosely loaded in detached dowel 10.Preferably, the volume of solid extracting agent accounts for detached dowel 10
Volume 1/5～1/8.Specifically, put in detached dowel 10 with a porous sieve plate 102, seal one end of detached dowel 10,
It is then charged into solid extracting agent, then another one porous sieve plate 102 is pressed in detached dowel 10, seal the another of detached dowel 10
End, the detached dowel 10 that then will be equipped with solid extracting agent is placed on vibration 3min on shaking table, gentlier presses porous sieve plate 102 to be compacted
Solid extracting agent, obtains solid-phase extraction column.
The preparation method of above-mentioned solid phase extraction column is relatively simple, and preparation is convenient.
Refer to Fig. 2, the chemical example pre-treating method based on Solid-Phase Extraction of an embodiment, comprise the steps
210 to step 240.
Step 210: above-mentioned solid phase extraction column is activated.
The operation of activation is particularly as follows: add activator in solid-phase extraction column.The purpose of activation is to moisten solid extracting agent
Wet, with preferably adsorbed target component.
Preferably, the volume of activator is 1/8 times～1 times of the volume of detached dowel 10.The flow velocity of activator is 0.5ml/
Min～2ml/min.
Preferably, activator is selected from deionized water, methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane
Alkane, carbon tetrachloride, ether, toluene, benzene, hexamethylene, petroleum ether, hexane, pentane, mass fraction be 37% hydrochloric acid and quality divide
Number is at least one in 40% sodium hydrate aqueous solution.It is further preferred that activator be selected from methanol, ethyl acetate, ethanol,
Acetonitrile, chloroform, dichloromethane, petroleum ether, mass fraction be 37% hydrochloric acid and mass fraction be the water-soluble of 40% sodium hydroxide
At least one in liquid.
Above-mentioned solid phase extractant employs Graphene or passes through the Graphene modified as solid extracting agent, Graphene or warp
The Graphene crossing modification is insensitive to ph value, and the ph of above-mentioned activator is all applicable in the range of 0～14.
Step 220: by the solid-phase extraction column after the chemical example injection activation of pre-treatment.
Treat that the chemical example of pre-treatment contains target components.When pending chemical example is solution, direct loading.When
When pending chemical example is solid, first it is configured to after solution loading again, solvent is from the solvent being capable of solubilized target component.
Pending chemical example is sent in detached dowel 10, makes pending chemical example slowly flow across Solid-Phase Extraction
Agent, completes loading.Preferably, the volume of pending chemical example is 1/8 times～1 times of the volume of detached dowel 10.Pending
Chemical example flow velocity be 0.1ml/min～1ml/min.
Step 230: drip washing is carried out to solid-phase extraction column with eluent.
After loading, solid extracting agent adsorbed target component.With eluent, drip washing is carried out to solid-phase extraction column, with remove not by
The impurity of solid extracting agent absorption.After drip washing, discard the effluent of drip washing generation.
Preferably, the volume of eluent is 1/8 times～1 times of the volume of detached dowel 10.The flow velocity of eluent is 0.1ml/min
～1ml/min.
The opposite polarity of the polarity of eluent and the solvent of the chemical example treating pre-treatment.Preferably, eluent is selected from and goes
Ionized water, methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane, carbon tetrachloride, ether, toluene, benzene, ring
Hexane, petroleum ether, hexane, pentane, mass fraction are the aqueous solution of 10% sodium carbonate, mass fraction is 37% hydrochloric acid and quality
Fraction is at least one in 40% sodium hydrate aqueous solution.
It is further preferred that eluent is selected from the aqueous solution that deionized water, mass fraction are 10% sodium carbonate, methanol, second
Acetoacetic ester, ethanol, acetonitrile, chloroform, dichloromethane, petroleum ether, mass fraction be 37% hydrochloric acid and mass fraction be 40% hydrogen
At least one in the aqueous solution of sodium oxide.
Step 240: with eluant, eluting is carried out to solid-phase extraction column, obtain eluent.
With eluant, eluting is carried out to solid-phase extraction column, to separate the target components being adsorbed on solid-phase extraction column.
Injected in detached dowel 10 with eluant, make eluant flow slowly into solid extracting agent, realize the desorption of target components,
Obtain eluent.Obtained eluent can be used for chromatography.
Preferably, the volume of eluant is 1/8 times～1/2 times of the volume of detached dowel 10.The flow velocity of eluant is 0.1ml/
Min～1ml/min.
The volume of above-mentioned detached dowel 10 refers to the volume of the cylinder 101 of hollow.
Preferably, after obtaining eluent, then eluent nitrogen is dried up, then obtained to drying up with 1ml～10ml solvent
Dried object carry out constant volume, after constant volume, this solution is sent into subsequent detection equipment, such as chromatograph of liquid etc. is analyzed.
Above-mentioned solvent be selected from deionized water, methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane, four
At least one in chlorination carbon, ether, toluene, benzene, hexamethylene, petroleum ether, hexane and pentane.Preferably, above-mentioned organic solvent
At least one in methanol, ethyl acetate, ethanol, acetonitrile, chloroform, dichloromethane and petroleum ether.
The above-mentioned chemical example pre-treating method based on Solid-Phase Extraction, the Graphene by Graphene or through modifying and mesh
Strong adsorption between mark component is so as to have crystallized ability to specific target components, and does not have energy of adsorption to non-target components
Power, thus effectively capturing trace or micro target components in sample, and can obtain concrete in follow-up chromatography
The mensure of content, thus avoid target components cannot measured actual value and the problem of data distortion that exists.
And, the above-mentioned stone based in the chemical example pre-treating method of Solid-Phase Extraction, using Graphene or through modifying
Black alkene, as solid extracting agent, effectively reduces the usage amount of solid extracting agent, makes the waste minimizing during analysis, cost
Reduce.
The above-mentioned Graphene major part through modifying adopts lomedajr, doylecd, kosynkindv, hwangwf,
In tourj m.j.am.chem.soc., 2008,130:16201 16206, the diazol method of report is functionalized modifying.
As myristalated Graphene is carried out to Graphene as alkylating reagent using to detergent alkylate aryldiazonium salt
Modification obtains, and carboxylated Graphene carries out carboxylated carrying out modification to Graphene and obtaining using hydrolysis after diazo ester reaction.
Amination graphene separately adopts krabbenborg s, naber w j m, velders a h, reinhoudt d
N, wiel w g.chem-eur j., the Azide-reduction of report in 2009,15:8235 8240 carries out amination to graphite
Alkene carries out modification and obtains；Hydroxylating Graphene carries out hydroxylating degree using the method for sodium borohydride selective reduction graphene oxide
Graphene carries out modification and obtains.
It is below specific embodiment.
Embodiment 1
1st, form the few-layer graphene alkene is selected as solid extracting agent according to group polarity.Loose for form the few-layer graphene alkene loading one end is used
In the polypropylene plastics cylinder that porous aluminum oxide sieve plate seals, the volume of solid extracting agent accounts for the volume of polypropylene plastics cylinder
1/5, then seal polypropylene plastics cylinder with another porous aluminum oxide oxidation sieve plate, will be equipped with the poly- of form the few-layer graphene alkene
Acrylic plastic cylinder is placed on vibration 3min on shaking table, gentlier presses porous aluminum oxide sieve plate to be compacted solid extracting agent, consolidate
Phase extraction column.
2nd, α-nitronaphthalene, phenol, the working solution of tetramethylolmethane, benzoic acid and naphthalene are prepared respectively, solvent is dichloromethane,
Concentration is 100ug/l, adds C.I. 13020. as impurity composition, the concentration of C.I. 13020. is 1mg/l.
3rd, methanol is added in solid-phase extraction column and solid-phase extraction column is activated, the flow velocity of methanol is 1ml/min, methanol
Volume be 1/8 times of volume of polypropylene plastics cylinder.
4th, take respectively in the above-mentioned solid phase extraction column after the injection activation of 100ml above-mentioned working solution, carry out loading.Above-mentioned work
The volume of liquid is 1/8 times of the volume of polypropylene plastics cylinder, and flow velocity is 1ml/min.
5th, with ethanol, above-mentioned solid phase extractant is carried out with drip washing, the volume of ethanol is the 1/ of the volume of polypropylene plastics cylinder
8 times, flow velocity is 1ml/min.
6th, carry out affording eluent for the mixed solution 0.5ml of 1:1 mixing by volume with acetonitrile and petroleum ether again,
The volume of mixed solution is 1/8 times of the volume of polypropylene plastics cylinder, and the flow velocity of mixed solution is 0.5ml/min.
7th, above-mentioned eluent nitrogen is dried up and obtain dried object, then carry out constant volume with 1ml ethanol, take 20ul sample introduction to carry out
(using Agilent 1100 high performance liquid chromatography work station, mobile phase is acetonitrile and water 1:1 mixing by volume to liquid-phase chromatographic analysis
Mixed solvent, flow velocity be 0.5ml/min), the spectrogram obtaining is as shown in Figure 3.
As seen from Figure 3, above-mentioned it is used form the few-layer graphene alkene as the solid-phase extraction column of solid extracting agent to above-mentioned projects
Mark component can be good at selectivity and catches and dissociate, and can preferably remove impurity C.I. 13020..
Embodiment 2
1st, hydroxylating Graphene is selected as solid extracting agent according to group polarity.Load one by loose for hydroxylating Graphene
In the polypropylene plastics cylinder that end porous aluminum oxide sieve plate seals, the volume of solid extracting agent accounts for polypropylene plastics cylinder
The 1/8 of volume, then seals polypropylene plastics cylinder with another porous aluminum oxide sieve plate, will be equipped with hydroxylating Graphene
Polypropylene plastics cylinder is placed on vibration 3min on shaking table, gentlier pressure porous aluminum oxide sieve plate, to be compacted solid extracting agent, obtains
Solid-phase extraction column.
2nd, chloropropene, the working solution of acrylamide, acrylic acid and propenyl are prepared respectively, solvent is methanol, and concentration is equal
For 100ug/l, add that green b strong as impurity composition, the concentration being good for that green b is 1mg/l.
3rd, the mixed solvent of ethyl acetate and ethanol 1:1 mixing by volume is added in solid-phase extraction column to Solid-Phase Extraction
Post is activated, and the flow velocity of mixed solvent is 1.5ml/min, and the volume of mixed solvent is the 1/ of the volume of polypropylene plastics cylinder
8 times.
4th, take respectively in the above-mentioned solid phase extraction column after the injection activation of 100ml above-mentioned working solution, carry out loading.Above-mentioned work
The volume of liquid is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 1ml/min.
5th, with isopropanol, above-mentioned solid phase extractant is carried out with drip washing, the volume of isopropanol is the volume of polypropylene plastics cylinder
1 times, flow velocity be 0.5ml/min.
6th, carry out affording eluent with ethyl acetate and methylene chloride volume than the mixed solution 0.5ml for 2:1 again,
The volume of mixed solution is 1/8 times of the volume of polypropylene plastics cylinder, and the flow velocity of mixed solution is 1ml/min.
7th, above-mentioned eluent nitrogen is dried up and obtain dried object, then carry out constant volume with 1ml acetonitrile, take 20ul sample introduction to carry out
(using Agilent 1100 high performance liquid chromatography work station, mobile phase is the 4:1 mixing by volume of first alcohol and water to liquid-phase chromatographic analysis
Mixed solvent, flow velocity be 0.5ml/min), the spectrogram obtaining is as shown in Figure 4.
As seen from Figure 4, above-mentioned it is used hydroxylating Graphene as the solid-phase extraction column of solid extracting agent to above-mentioned items
Target components can be good at selectivity and catch and dissociate, and can preferably remove impurity and be good for that green b.
Embodiment 3
1st, respectively multiple solid extracting agents treating selection are added in ethanol and be configured to multigroup Solid-Phase Extraction agent dispersing liquid, dense
Spend for 0.1mg/ml, then be intended to the sterling of the target components of detection in testing sample and be also made into 0.5mg/ml with above-mentioned solvent
For gradient, concentration is a sequence target components dispersion liquid of 0.5mg/ml～5mg/ml, and wherein, the sterling of target components is respectively
Naphthalene acetic acid, indolebutyric acid, salicylic acid and benzenesulfonic acid.Respectively by Solid-Phase Extraction agent dispersing liquid and target components dispersion liquid with volume ratio
The ratio of 1:1 is mixed to get many parts of mixture, and every part of mixture takes 1ml to carry out ultrasonic disperse, treats this mixture quiescent settling
After 30min, the sedimentation degree of the mixture containing amination graphene is minimum, selects amination graphene as Solid-Phase Extraction
Agent.
2nd, select amination graphene as solid extracting agent.By loose for amination graphene loading one end porous oxygen
Change in the polypropylene plastics cylinder that aluminum sieve plate seals, the volume of solid extracting agent accounts for the 1/6 of the volume of polypropylene plastics cylinder, so
Seal polypropylene plastics cylinder with another porous aluminum oxide sieve plate afterwards, will be equipped with the polypropylene plastics stock column of amination graphene
Body is placed on vibration 3min on shaking table, gentlier pressure porous aluminum oxide sieve plate, to be compacted solid extracting agent, obtains solid-phase extraction column.
3rd, naphthalene acetic acid, the working solution of indolebutyric acid, salicylic acid and benzenesulfonic acid are prepared respectively, solvent is ethanol, and concentration is equal
For 100ug/l, add dimethylbenzene green grass or young crops as impurity composition, the blue or green concentration of dimethylbenzene is 1mg/l.
4th, acetonitrile is added in solid-phase extraction column and solid-phase extraction column is activated, the flow velocity of acetonitrile is 1ml/min, acetonitrile
Volume be 1 times of volume of polypropylene plastics cylinder.
5th, take respectively in the above-mentioned solid phase extraction column after the injection activation of 100ml above-mentioned working solution, carry out loading.Above-mentioned work
The volume of liquid is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 0.1ml/min.
6th, with isopropanol, above-mentioned solid phase extractant is carried out with drip washing, the volume of isopropanol is the volume of polypropylene plastics cylinder
1 times, flow velocity be 0.8ml/min.
7th, the mixed solution 0.5ml being 1:1 with acetonitrile and water volume ratio again carries out affording eluent, mixed solution
Volume is 1/2 times of the volume of polypropylene plastics stock column, and the flow velocity of mixed solution is 0.1ml/min.
8th, above-mentioned eluent nitrogen is dried up and obtain dried object, then carry out constant volume with 1ml ethyl acetate, take 20ul sample introduction
(using Agilent 1100 high performance liquid chromatography work station, mobile phase is acetonitrile and water 1:1 by volume to carry out liquid-phase chromatographic analysis
The mixed solvent of mixing, flow velocity is 0.5ml/min), the spectrogram obtaining is as shown in Figure 5.
As seen from Figure 5, above-mentioned it is used amination graphene as the solid-phase extraction column of solid extracting agent to above-mentioned items
Target components can be good at selectivity and catch and dissociate, and can preferably remove removal xylene blue or green.
Embodiment 4
1st, respectively multiple solid extracting agents treating selection are added and in dichloromethane, be configured to multigroup solid extracting agent dispersion
Liquid, concentration is 0.5mg/ml, then be intended in testing sample the target components of detection sterling be also made into above-mentioned solvent with
0.5mg/ml be gradient, concentration be 0.5mg/ml～5mg/ml a sequence target components dispersion liquid, wherein, target components pure
Product are respectively phylloxanthin, chlorophyll b, chlorophyll a and alkene.Respectively by Solid-Phase Extraction agent dispersing liquid and target components dispersion liquid with body
The long-pending ratio than 1:1 is mixed to get many parts of mixture, and every part of mixture takes 5ml to carry out ultrasonic disperse, treats that this mixture is static heavy
After fall 60min, the sedimentation degree of the mixture containing myristalated Graphene is minimum, selects myristalated Graphene conduct
Solid extracting agent.
2nd, select myristalated Graphene as solid extracting agent.Loose for myristalated Graphene loading one end is used
In the polypropylene plastics cylinder that porous aluminum oxide sieve plate seals, the volume of solid extracting agent accounts for the volume of polypropylene plastics cylinder
1/6, then seal polypropylene plastics cylinder with another porous aluminum oxide sieve plate, will be equipped with myristalated Graphene
Polypropylene plastics cylinder is placed on vibration 3min on shaking table, gentlier pressure porous aluminum oxide sieve plate, to be compacted solid extracting agent, obtains
Solid-phase extraction column.
3rd, phylloxanthin, the working solution of chlorophyll b, chlorophyll a and alkene are prepared respectively, solvent is ethyl acetate, and concentration is equal
For 100ug/l, add Congo red as impurity composition, the concentration of Congo red is 1mg/l.
4th, the mixed solvent of dichloromethane and petroleum ether 1:2 mixing by volume is added in solid-phase extraction column and solid phase is extracted
Post is taken to be activated, the flow velocity of mixed solvent is 2ml/min, the volume of mixed solvent is the 1 of the volume of polypropylene plastics cylinder
Times.
5th, take respectively in the above-mentioned solid phase extraction column after the injection activation of 100ml above-mentioned working solution, carry out loading.Above-mentioned work
Liquid amasss 1 times of the volume for polypropylene plastics cylinder, and flow velocity is 0.5ml/min.
6th, carry out drip washing with the mixed solvent above-mentioned solid phase extractant of chloroform and dichloromethane 1:2 mixing by volume, mix
The volume of bonding solvent is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 0.1ml/min.
7th, carry out affording for the mixed solution 0.5ml of 2:1 mixing by volume with ethyl acetate and petroleum ether again
De- liquid, the volume of mixed solution is 1/4 times of the volume of polypropylene plastics stock column, and the flow velocity of mixed solution is 0.8ml/min.
8th, above-mentioned eluent nitrogen is dried up and obtain dried object, then carry out constant volume with 1ml chloroform, take 20ul sample introduction to carry out
(using Agilent 1100 high performance liquid chromatography work station, mobile phase is the 4:1 mixing by volume of first alcohol and water to liquid-phase chromatographic analysis
Mixed solvent, flow velocity be 0.5ml/min), the spectrogram obtaining is as shown in Figure 6.
As seen from Figure 6, above-mentioned it is used myristalated Graphene as the solid-phase extraction column of solid extracting agent to above-mentioned
The objectives component can be good at selectivity and catches and dissociate, and can preferably remove Congo red.
Embodiment 5
1st, respectively multiple solid extracting agents treating selection are added and in dichloromethane, be configured to multigroup solid extracting agent dispersion
Liquid, concentration is 0.5mg/ml, then be intended in testing sample the target components of detection sterling be also made into above-mentioned solvent with
0.5mg/ml be gradient, concentration be 0.5mg/ml～5mg/ml a sequence target components dispersion liquid, wherein, target components pure
Product are α-Gamma Hexaochlorocyclohexane.Respectively Solid-Phase Extraction agent dispersing liquid and target components dispersion liquid are mixed to get with the ratio of volume ratio 1:1
Many parts of mixture, every part of mixture takes 5ml to carry out ultrasonic disperse, after this mixture quiescent settling 60min, containing dodecyl
The sedimentation degree of the mixture of graphite alkene is minimum, selects myristalated Graphene as solid extracting agent.
2nd, select myristalated Graphene as solid extracting agent.Loose for myristalated Graphene loading one end is used
In the polypropylene plastics cylinder that porous aluminum oxide sieve plate seals, the volume of solid extracting agent accounts for the volume of polypropylene plastics cylinder
1/6, then seal polypropylene plastics cylinder with another porous aluminum oxide sieve plate, will be equipped with myristalated Graphene
Polypropylene plastics cylinder is placed on vibration 3min on shaking table, gentlier pressure porous aluminum oxide sieve plate, to be compacted solid extracting agent, obtains
Solid-phase extraction column.
3rd, obtain Folium Camelliae sinensis powder by crossing 50 mesh sieves after the Tea Samples being polluted by α-Gamma Hexaochlorocyclohexane pulverizing, take 2.5g Folium Camelliae sinensis powder to add
Extract in the mixed liquor of 20ml normal hexane-acetone (volume ratio of normal hexane and acetone is 97.5:2.5), be placed in 45 DEG C of shaking table
40min is extracted in middle concussion, obtains extracting solution.
4th, the hydrochloric acid that mass fraction is 37% is added in solid-phase extraction column and solid-phase extraction column is activated, the stream of hydrochloric acid
Speed is 0.5ml/min, and the volume of mixed solvent is 1 times of the volume of polypropylene plastics cylinder.
5th, loading, the body of said extracted liquid will be carried out in the above-mentioned solid phase extraction column after the injection activation of 5ml said extracted liquid
Amass the volume for polypropylene plastics cylinder 1/8 times, flow velocity is 1ml/min.
6th, with acetonitrile, above-mentioned solid phase extractant is carried out with drip washing, the volume of acetonitrile is the 1 of the volume of polypropylene plastics cylinder
Times, flow velocity is 1ml/min.
7th, carry out affording eluting for the mixed solution 25ml of 1:9 mixing by volume with ethyl acetate and petroleum ether again
Liquid, retains the pigment in Folium Camelliae sinensis in eluent, remove pesticide residues with other compositions in Folium Camelliae sinensis, the volume of wherein mixed solution is
1/4 times of the volume of polypropylene plastics stock column, the flow velocity of mixed solution is 1ml/min.
8th, use 1ml normal hexane constant volume after above-mentioned eluent nitrogen being dried up, the solution after constant volume is taken 20ul sample introduction to enter
(using Agilent 1100 high performance liquid chromatography work station, mobile phase is that 1:1 mixes by volume for acetonitrile and water to row liquid-phase chromatographic analysis
The mixed solvent closing, flow velocity is 0.5ml/min).Separately take α-Gamma Hexaochlorocyclohexane to be made into the pesticide sample solution of 100ng/ml, take sample molten
Liquid 20ul sample introduction, for demarcating the α-Gamma Hexaochlorocyclohexane in Tea Samples.Finally demarcate the spectrogram completing such as Fig. 7, non-pigment miscellaneous peak is done
Disturb, and so that α-Gamma Hexaochlorocyclohexane is eluted it was demonstrated that Graphene solid-phase extraction column has effectively completed its remove impurity pigment
Function.
Embodiment 6
1st, respectively multiple solid extracting agents treating selection are added and in dichloromethane, be configured to multigroup solid extracting agent dispersion
Liquid, concentration is 0.5mg/ml, then be intended in testing sample the target components of detection sterling be also made into above-mentioned solvent with
0.5mg/ml be gradient, concentration be 0.5mg/ml～5mg/ml a sequence target components dispersion liquid, wherein, target components pure
Product are respectively phylloxanthin, chlorophyll b, chlorophyll a and alkene.Respectively by Solid-Phase Extraction agent dispersing liquid and target components dispersion liquid with body
The long-pending ratio than 1:1 is mixed to get many parts of mixture, and every part of mixture takes 5ml to carry out ultrasonic disperse, treats that this mixture is static heavy
After fall 60min, the sedimentation degree of the mixture containing myristalated Graphene is minimum, selects myristalated Graphene conduct
Solid extracting agent.
2nd, select myristalated Graphene as solid extracting agent.Loose for myristalated Graphene loading one end is used
In the polypropylene plastics cylinder that porous aluminum oxide sieve plate seals, the volume of solid extracting agent accounts for the volume of polypropylene plastics cylinder
1/6, then seal polypropylene plastics cylinder with another porous aluminum oxide sieve plate, will be equipped with myristalated Graphene
Polypropylene plastics cylinder is placed on vibration 3min on shaking table, gentlier pressure porous aluminum oxide sieve plate, to be compacted solid extracting agent, obtains
Solid-phase extraction column.
3rd, it is polished into homogenate by sending into pulverizer after Fructus Lycopersici esculenti sample stripping and slicing, then take 0.5g strained tomatoes to add 10ml acetone,
Extracted under 120w is ultrasonic, leach Fructus Lycopersici esculenti residue after 10min, obtain extracting solution.
4th, the mixed solvent of dichloromethane and chloroform 1:2 mixing by volume is added in solid-phase extraction column to Solid-Phase Extraction
Post is activated, and the flow velocity of mixed solvent is 0.8ml/min, and the volume of mixed solvent is the 1 of the volume of polypropylene plastics cylinder
Times.
5th, loading, the body of said extracted liquid will be carried out in the above-mentioned solid phase extraction column after the injection activation of 2ml said extracted liquid
Amass the volume for polypropylene plastics cylinder 1/9 times, flow velocity 1ml/min.
6th, use the 10% sodium carbonate liquor drip washing of 5ml again, then use the 37% of 5ml hydrochloric acid drip washing, contain miscellaneous after washing
The waste liquid of matter discards, and wherein, the cumulative volume of sodium carbonate liquor and hydrochloric acid is 1 times of the volume of polypropylene plastics cylinder, sodium carbonate
The flow velocity of solution is 0.5ml/min, and the flow velocity of hydrochloric acid is 0.5ml/min.
7th, finally use normal hexane 15ml eluting pigment, obtain eluent.The volume of normal hexane is the appearance of polypropylene plastics stock column
Long-pending 1/6 times, the flow velocity of normal hexane is 0.3ml/min.
8th, use the normal hexane constant volume of 1ml after above-mentioned eluent nitrogen being dried up, the solution after constant volume is removed 20ul sample introduction
(using Agilent 1100 high performance liquid chromatography work station, mobile phase is acetonitrile and water 1:1 by volume to carry out liquid-phase chromatographic analysis
The mixed solvent of mixing, flow velocity is 0.5ml/min), obtain spectrogram such as Fig. 8 it was demonstrated that Graphene solid-phase extraction column can be effectively
Lycopene in Fructus Lycopersici esculenti and beta-carotene are retained, and are effectively passed through the organic acid in drip washing eluting tamato fruit,
It is made not disturbed in follow-up chromatograph.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the guarantor of the present invention
Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (9)
1. a kind of solid-phase extraction column is it is characterised in that including detached dowel and being filled in solid extracting agent in described detached dowel, institute
Stating solid extracting agent is Graphene or the Graphene through modifying；Described Graphene is single-layer graphene or form the few-layer graphene alkene, institute
State and be selected from amination graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate through the Graphene modified
Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, three
Fluoromethylation Graphene, myristalated Graphene, octadecyl graphite alkene, fluorinated graphene, bromination Graphene, chlorination stone
At least one in black alkene and iodate Graphene, described detached dowel includes the polypropylene plastics stock column of hollow and is removable installed in
Two porous aluminum oxide sieve plates within described polypropylene plastics stock column；Described solid extracting agent is filled in described two porous
Between aluminium oxide sieve plate, one end of the cylinder of hollow is provided with stigma, and stigma is the cylindrical shape of both ends open, and stigma is sieved with porous
Plate connects.
2. a kind of preparation method of solid-phase extraction column, comprises the steps:
Select a kind of from multiple solid extracting agents treating selection, the described solid extracting agent treating selection is for Graphene or through repairing
The Graphene of decorations；Described Graphene is single-layer graphene or form the few-layer graphene alkene, and the described Graphene through modifying is selected from amination
Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxyl fossil
Black alkene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, trifluoromethylation Graphene, dodecyl graphite
At least one in alkene, octadecyl graphite alkene, fluorinated graphene, bromination Graphene, chlorination Graphene and iodate Graphene；
The detached dowel that in selected solid extracting agent loading detached dowel, will be equipped with described solid extracting agent is placed on and shakes on shaking table
Dynamic 3min, and it is compacted described solid extracting agent, obtain described solid-phase extraction column；
Described detached dowel includes the polypropylene plastics stock column of hollow and is removable installed within described polypropylene plastics stock column two
Individual porous aluminum oxide sieve plate；Described solid extracting agent is filled between described two porous aluminum oxide sieve plates, the post of hollow
One end of body is provided with stigma, and stigma is the cylindrical shape of both ends open, and stigma is connected with porous sieve plate.
3. the preparation method of solid-phase extraction column according to claim 2 is it is characterised in that described treat consolidating of selection from multiple
Select a kind of method in phase extractant particularly as follows:
Respectively multiple solid extracting agents treating selection are configured to multigroup Solid-Phase Extraction agent dispersing liquid, and are intended in testing sample
The sterling of the target components detecting is configured to multigroup target components dispersion liquid, respectively by multigroup Solid-Phase Extraction agent dispersing liquid with many
Group target components dispersion liquid carries out being mixed to get multigroup mixture, and mixture described in every group is carried out ultrasonic disperse, treats described mixed
After compound sedimentation, select the solid extracting agent in one group of minimum mixture of sedimentation degree；
Described multiple solid extracting agent treating selection is Graphene or the Graphene through modifying, and described Graphene is mono-layer graphite
Alkene or form the few-layer graphene alkene, described through modification Graphene be selected from amination graphene, carboxylated Graphene, cyano group Graphene,
Nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates,
Allylation Graphene, trifluoromethylation Graphene, myristalated Graphene, octadecyl graphite alkene, fluorinated graphene,
Bromination Graphene, chlorination Graphene and iodate Graphene and amination graphene, carboxylated Graphene, cyano group Graphene, nitro
Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allyl
Base graphite alkene, trifluoromethylation Graphene, myristalated Graphene, octadecyl graphite alkene, fluorinated graphene, bromination
At least one in Graphene, chlorination Graphene and iodate Graphene.
4. a kind of chemical example pre-treating method based on Solid-Phase Extraction is it is characterised in that comprise the steps:
Solid-phase extraction column described in claim 1 is activated；
By in the described solid-phase extraction column after the chemical example injection activation of pre-treatment；
With eluent, drip washing is carried out to described solid-phase extraction column；And
With eluant, eluting is carried out to described solid-phase extraction column, obtain eluent.
5. the chemical example pre-treating method based on Solid-Phase Extraction according to claim 4 is it is characterised in that want to right
Ask the operation that the solid-phase extraction column described in 1 is activated particularly as follows: adding in described solid-phase extraction column activator, described activation
The volume of agent is 1/8 times～1 times of the volume of described detached dowel；Described activator is selected from methanol, ethanol, isopropanol, acetonitrile, second
Acetoacetic ester, chloroform, dichloromethane, carbon tetrachloride, ether, toluene, benzene, hexamethylene, petroleum ether, hexane, pentane, mass fraction are
37% hydrochloric acid and mass fraction are at least one in 40% sodium hydrate aqueous solution.
6. the chemical example pre-treating method based on Solid-Phase Extraction according to claim 4 is it is characterised in that treat pre-treatment
The volume of chemical example be 1/8 times～1 times of volume of described detached dowel.
7. the chemical example pre-treating method based on Solid-Phase Extraction according to claim 4 is it is characterised in that described drip washing
The volume of agent is 1/8 times～1 times of the volume of described detached dowel；Described eluent is selected from methanol, ethanol, isopropanol, acetonitrile, second
Acetoacetic ester, chloroform, dichloromethane, carbon tetrachloride, ether, toluene, benzene, hexamethylene, petroleum ether, hexane, pentane, mass fraction are
37% hydrochloric acid and mass fraction are at least one in 40% sodium hydrate aqueous solution.
8. the chemical example pre-treating method based on Solid-Phase Extraction according to claim 4 is it is characterised in that described eluting
The volume of agent is 1/8 times～1/2 times of the volume of described detached dowel；Described eluant be selected from methanol, ethanol, isopropanol, acetonitrile,
In ethyl acetate, chloroform, dichloromethane, carbon tetrachloride, ether, toluene, benzene, hexamethylene, petroleum ether, hexane and pentane at least
A kind of.
9. the chemical example pre-treating method based on Solid-Phase Extraction according to claim 4 it is characterised in that also include right
The step that described eluent is processed, the described step that eluent is processed is particularly as follows: by described eluent nitrogen
Dry up and obtain dried object, then with described eluant, constant volume is carried out to described dried object.
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| CN105717249A (en) * | 2016-03-29 | 2016-06-29 | 中华人民共和国济宁出入境检验检疫局 | Method for detecting aldicarb and aldicarb metabolites through graphene solid-phase extraction |
| CN106018585A (en) * | 2016-05-14 | 2016-10-12 | 中华人民共和国济宁出入境检验检疫局 | Method for detecting residual sulfa drugs on basis of graphene oxide solid phase extraction technology |
| CN106035938B (en) * | 2016-06-21 | 2020-06-26 | 华北制药集团新药研究开发有限责任公司 | Lutein ester tablet candy and preparation method thereof |
| CN107831229A (en) * | 2017-10-30 | 2018-03-23 | 诺安实力可商品检验（青岛）有限公司 | The assay method that a kind of Pesticides in Tea medicine remains more |
| CN108499549B (en) * | 2018-03-30 | 2021-12-14 | 广州质量监督检测研究院 | Solid phase micro-extraction head for enriching perfluoro compounds and preparation method thereof |
| CN108888998A (en) * | 2018-05-11 | 2018-11-27 | 上海市农业科学院 | A kind of solid-phase extraction column and preparation method thereof for enrichment purification mycotoxin |
| CN110961078A (en) * | 2019-11-28 | 2020-04-07 | 河海大学 | Application of fluorinated graphene material, solid-phase micro-extraction probe and adsorption extraction stirring rod based on fluorinated graphene extraction coating |
| CN111389372B (en) * | 2020-05-15 | 2023-03-24 | 安阳工学院 | Special graphene oxide aerogel solid-phase extraction column for perfluorinated acid compounds and preparation method thereof |
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