CN104258598A - 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, particularly relate to a kind of solid-phase extraction column, its preparation method and the chemical example pre-treating method based on solid-phase extraction column.
Background technology
In the detection analytical work of chemical example, particularly natural sample, modal problem is, the component Many times of sample is all too complicated, cannot carry out Direct Analysis, or Direct Analysis effect is bad by chromatogram.Therefore, need by carrying out to chemical example the separation that pre-treatment realizes determinand, then carry out chromatography.Chemical example pretreatment technology the most frequently used is at present SPE (SPE) technology, namely realizes sorption extraction by the affinity of the special component in component and solid extracting agent, thus realizes the separation of special component.Therefore, solid extracting agent is selected to seem very important.The characteristics such as the pore-size distribution on the particular functional group that the polarity of solid extracting agent, solid extracting agent possess, solid extracting agent surface and specific area, directly determine the extraction efficiency of whole SPE process and selective.
Traditionally, the selection of solid extracting agent is generally the organic and inorganic material of the carbon 18 i.e. silica gel, ketjenblack EC, polystyrene microsphere etc. of chain alkyl modification.
Traditional solid extracting agent all exists that packing density is comparatively large, consumption is more, make the shortcomings such as the comparatively large and cost of the waste in analytic process is higher.Topmost problem is, traditional solid extracting agent due to consumption many, the degree of absorption of the micro constitutent in sample on solid extracting agent is comparatively large, and thus measuredly maybe cannot cannot detect actual value in follow-up detection, therefore data exist distortion.
Summary of the invention
Based on this, be necessary to provide a kind of solid-phase extraction column, to carry out pre-treatment to chemical example, avoid target components in follow-up detection measuredly maybe cannot cannot detect actual value and problem, the problem includes: the problem of data distortion.
A kind of solid-phase extraction column, is characterized in that, comprise splitter and be filled in the solid extracting agent in described splitter, and described solid extracting agent is Graphene or the Graphene through modifying; Described Graphene is single-layer graphene or few layer graphene, and the described Graphene through modifying is selected from least one in amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, fluorinated graphene, bromination Graphene, chlorination Graphene and iodate Graphene.
Wherein in an embodiment, described splitter comprises the polypropylene plastics stock column of hollow and is removable installed in two porous aluminum oxide sieve plates of described polypropylene plastics stock column inside; Described solid extracting agent is filled between described two porous aluminum oxide sieve plates.
A preparation method for solid-phase extraction column, comprises the steps:
Select a kind of from solid extracting agent multiple to be selected, described in solid extracting agent to be selected be Graphene or the Graphene through modifying; Described Graphene is single-layer graphene or few layer graphene, and the described Graphene through modifying is selected from least one in amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, fluorinated graphene, bromination Graphene, chlorination Graphene and iodate Graphene;
Selected solid extracting agent is loaded in splitter, the splitter that described solid extracting agent is housed is placed on shaking table and vibrates 3min, and solid extracting agent described in compacting, obtain described solid-phase extraction column.
Wherein in an embodiment, describedly from solid extracting agent multiple to be selected, a kind of method is selected to be specially:
Respectively solid extracting agent multiple to be selected is mixed with many group SPE agent dispersing liquids, and the sterling of the target components for detecting in testing sample is mixed with many group target components dispersion liquids, undertaken being mixed to get organizing mixture by organizing SPE agent dispersing liquid more and organizing target components dispersion liquid more respectively more, and carry out ultrasonic disperse by often organizing described mixture, after described mixture sedimentation, select the solid extracting agent in one group of mixture that sedimentation degree is minimum;
Described multiple solid extracting agent to be selected is Graphene or the Graphene through modifying, and described Graphene is single-layer graphene or few layer graphene, and the described Graphene through modifying is selected from amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, methylate Graphene, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, 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, methylate Graphene, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, fluorinated graphene, bromination Graphene, at least one in chlorination Graphene and iodate Graphene.
Based on a chemical example pre-treating method for SPE, comprise the steps:
Above-mentioned solid phase extraction column is activated;
Chemical example until pre-treatment is injected the described solid-phase extraction column after activation;
With eluent, drip washing is carried out to described solid-phase extraction column; And
With eluant, eluent, wash-out is carried out to described solid-phase extraction column, obtain eluent.
Wherein in an embodiment, be specially the operation that above-mentioned solid phase extraction column activates: added by activator in described solid-phase extraction column, the volume of described activator is 1/8 times ~ 1 times of the volume of described splitter; Described activator is selected from methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane, pentane, mass fraction be 37% hydrochloric acid and mass fraction be at least one in 40% sodium hydrate aqueous solution.
Wherein in an embodiment, treat that the volume of the chemical example of pre-treatment is 1/8 times ~ 1 times of the volume of described splitter.
Wherein in an embodiment, the volume of described eluent is 1/8 times ~ 1 times of the volume of described splitter; Described eluent is selected from methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane, pentane, mass fraction be 37% hydrochloric acid and mass fraction be at least one in 40% sodium hydrate aqueous solution.
Wherein in an embodiment, the volume of described eluant, eluent is 1/8 times ~ 1/2 times of the volume of described splitter; Described eluant, eluent is selected from least one in methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane and pentane.
Wherein in an embodiment, also comprise the step that described eluent is processed, described the step that eluent processes to be specially: described eluent nitrogen is dried up and obtains dry thing, then with described eluant, eluent, constant volume is carried out to described dry thing.
Above-mentioned solid phase extraction column using Graphene or through modification Graphene as solid extracting agent, utilize well Graphene and through the Graphene modification and functionalized after the adsorption selection characteristic of Graphene, Graphene and different functionalized grapheme material are to different elements, polarity and structure have different selective, this solid-phase extraction column is used to carry out pre-treatment to chemical example, every component in system to be measured can be fixed effectively, and with every component is different from the affine degree of the Graphene that Graphene or process are modified, segmentation is dissociated, thus realize efficient separating effect, avoid target components in follow-up detection measuredly maybe cannot cannot detect actual value and problem, the problem includes: the problem of data distortion.
Accompanying drawing explanation
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 SPE 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.
Detailed description of the invention
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the solid-phase extraction column of an embodiment, comprise splitter 10 and be filled in the solid extracting agent 20 in splitter 10.
Splitter 10 comprises the cylinder 101 of hollow and is removable installed in two porous sieve plates 102 (hole of the not shown porous sieve plate 102 of Fig. 1) of cylinder 101 inside of hollow.Solid extracting agent 20 is filled between two porous sieve plates 102.
In present embodiment, the cylinder 101 of hollow is polypropylene plastics cylinder, and porous sieve plate 102 is porous aluminum oxide sieve plate.
Be appreciated that in other embodiments, the cylinder 101 of hollow is not limited to polypropylene plastics cylinder, also can be the cylinder of other materials, as polypropylene cylinder.Porous sieve plate 102 is also not limited to porous aluminum oxide sieve plate, also can be the porous sieve plate of other materials, as porous polypropylene sieve plate, porous glass fiber sieve plate etc.
One end of the cylinder 101 of hollow is provided with column cap 103.Column cap 103 is the cylindrical shape of both ends open.Column cap 103 is communicated with porous sieve plate 102.
Solid extracting agent 20 is Graphene or the Graphene through modifying.Graphene or through the Graphene itself modified as carrier and adsorbent, to carry without the need to using other carriers or without the need to being filled in splitter 10 by means of crosslinking agent, comparatively simply, preparation cost is lower in the preparation making this solid-phase extraction column.And, simple use Graphene or can captured target component effectively as solid extracting agent through the Graphene modified, without the need to the coupling such as silica gel, ketjenblack EC, polystyrene microsphere of modifying as chain alkyl with the solid extracting agent of other types, the traditional solid extracting agent of the silica gel, ketjenblack EC, polystyrene microsphere etc. that can effectively avoid chain alkyl to modify causes micro constitutent in adsorption sample largely and the problem of the data distortion caused due to consumption more.
Graphene density is extremely low, specific area is higher and chemical characteristic is comparatively stable, compared with traditional solid extracting agent, as the solid extracting agent of silica matrix, use Graphene can reduce the consumption of extractant greatly, and it is no longer responsive to the pH value of sample, effectively can open up its range of application wide, realize splendid separating effect.Further, Graphene has good absorption property to nonpolar molecule, particularly to there being the molecule of aromatic ring can be interacted by π-π, comes to be separated with other nonpolar molecules further.
Graphene is single-layer graphene or few layer graphene.
Certain modification is carried out to Graphene, more how different selections can also be obtained, can be used in carrying out pre-treatment to different chemical examples.Graphene through modifying is selected from least one in amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, fluorinated graphene, bromination Graphene, chlorination Graphene and iodate Graphene.
The above-mentioned Graphene through modifying refers to functionalized Graphene, and such as, amination Graphene refers to be introduced in Graphene by amino, and carboxylated Graphene refers to be introduced in Graphene by carboxyl, and fluorinated graphene refers to be introduced fluorine atom in Graphene.
Functionalized Graphene has adsorption selection characteristic, different functionalized grapheme material has different selective to different elements, polarity and structure, use different functionalized Graphenes as adsorbent to different target molecules, good separating effect can be obtained.Such as, amination ink alkene can provide stronger hydrogen bond, thus makes the polar molecule containing proton can by Hydrogen Binding Adsorption, and nonpolar molecule then degree of absorption is more weak.
When only having a kind of target components in a sample, select a kind of Graphene through modifying as solid extracting agent.When there is at least two kinds of target components in a sample, at least two kinds can be selected through the Graphene of modification as solid extracting agent according to the character of two kinds of target components.When there is at least two kinds of target components, corresponding different grapheme materials can be selected according to the polarity size of two kinds of components and unit structure.
The Graphene that above-mentioned solid phase extraction column uses Graphene or process to modify is as solid extracting agent, utilize Graphene or the strong suction-operated through between the Graphene and target components to be detected of modification, it is made to have crystallized ability to specific target components to be detected, and adsorption capacity is not had to the detected components of non-targeted, thus effectively capture trace or a small amount of target components to be detected in sample, and the mensuration of the concrete content of target components can be obtained in follow-up chromatography, avoid target components in follow-up detection and measuredly maybe cannot cannot detect actual value and the problem of the data distortion existed.
And, due to Graphene or the density of Graphene through modifying less, effectively can reduce the consumption of Graphene or the Graphene through modification in solid-phase extraction column, the microcomponent in system to be measured is not only enable to be detected, reduce the waste of solid extracting agent simultaneously, be conducive to saving cost.
The preparation method of the solid-phase extraction column of one embodiment, for the preparation of above-mentioned solid phase extraction column.The preparation method of this solid-phase extraction column comprises the steps 110 ~ step 120.
Step 110: select a kind of from solid extracting agent multiple to be selected.
Solid extracting agent to be selected is Graphene or the Graphene through modifying.Wherein, Graphene is single-layer graphene or few layer graphene.Graphene through modifying is selected from least one in amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, fluorinated graphene, bromination Graphene, chlorination Graphene and iodate Graphene.
When there being the sterling of target components to be detected, carry out sedimentation experiment to select suitable solid extracting agent.
Sedimentation experiment comprises the steps:
Respectively solid extracting agent multiple to be selected is mixed with many group SPE agent dispersing liquids, and the sterling of the target components for detecting in testing sample is mixed with many group target components dispersion liquids, undertaken being mixed to get organizing mixture by organizing SPE agent dispersing liquid more and organizing target components more respectively more, ultrasonic disperse is carried out by often organizing mixture, after thing sedimentation to be mixed, select the solid extracting agent in one group of mixture that sedimentation degree is minimum.
The Graphene that Graphene in one group of mixture that sedimentation degree is minimum or process are modified is better to the absorption property of target components, therefore selects the solid extracting agent in one group of mixture that sedimentation degree is minimum.
The solvent of SPE agent dispersing liquid and target components dispersion liquid is all preferably deionized water.When target components solubility is in deionized water not good, select methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane, pentane, mass percent concentration be 37% hydrochloric acid and mass percent concentration be the solvent of at least one in the aqueous solution of the NaOH of 40% as dispersion liquid.
Because the solubility of the Graphene through modifying originally in water is better, in order to truly reflect through modification Graphene to the absorption situation of target components, preferably, respectively solid extracting agent multiple to be selected and above-mentioned solvent are mixed with and organize SPE agent dispersing liquid more, concentration is 0.1mg/mL ~ 0.5mg/mL, the sterling of the target components for detecting in testing sample being also made into above-mentioned solvent with 0.5mg/mL is gradient again, and concentration is a sequence target components dispersion liquid of 0.5mg/mL ~ 5mg/mL.To be mixed to get with the ratio of volume ratio 1:1 to organize mixture more by organizing SPE agent dispersing liquid and a series of target components dispersion liquid more respectively, often organize mixture to get 1mL ~ 5mL and carry out ultrasonic disperse, after this mixture sedimentation, select the solid extracting agent in one group of mixture that sedimentation degree is minimum.
Preferably, the method for mixture sedimentation is standing sedimentation 30min ~ 60min or with the rotating speed centrifugal sedimentation 0.5min ~ 2min of 3000r/min ~ 4000r/min.
By above-mentioned Graphene or the sedimentation situation of Graphene in target components sterling to be detected and the calibrating of degree of scatter of passing through modification, determine Graphene or the adsorption strength through between the Graphene and target components to be detected of modification, also the Graphene judging fast and simply to select or the correlation of passing through Graphene and the target components to be detected of modifying can be crossed, be conducive to the selective absorption to target components, improve the vacuum reliability of the data of follow-up chromatography.
When there is no the sterling of target components to be detected, select Graphene or the Graphene through modifying according to the roughly polarity of the target components for detecting.The molecule that polarity is larger, the Graphene of corresponding selection or just should have larger polarity through grapheme modified, thus play effect target components being produced to strong absorption.
Step 120: loaded by solid extracting agent in splitter 10, is placed on the splitter 10 that solid extracting agent is housed on shaking table and vibrates 3min, and compacting solid extracting agent, obtain solid-phase extraction column.
Solid extracting agent loosely is loaded in splitter 10.Preferably, the volume of solid extracting agent accounts for 1/5 ~ 1/8 of the volume of splitter 10.Particularly, splitter 10 is put into a porous sieve plate 102, seal one end of splitter 10, then solid extracting agent is loaded, again another one porous sieve plate 102 is pressed in splitter 10, seals the other end of splitter 10, then the splitter 10 that solid extracting agent is housed is placed on shaking table and vibrates 3min, gently press porous sieve plate 102 with compacting solid extracting agent again, obtain solid-phase extraction column.
The preparation method of above-mentioned solid phase extraction column is comparatively simple, easy to prepare.
Refer to Fig. 2, the chemical example pre-treating method based on SPE of an embodiment, comprises the steps 210 to step 240.
Step 210: above-mentioned solid phase extraction column is activated.
The operation of activation is specially: added in solid-phase extraction column by activator.The object of activation is soaked by solid extracting agent, with adsorbed target component preferably.
Preferably, the volume of activator is 1/8 times ~ 1 times of the volume of splitter 10.The flow velocity of activator is 0.5mL/min ~ 2mL/min.
Preferably, activator be selected from deionized water, methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane, pentane, mass fraction be 37% hydrochloric acid and mass fraction be at least one in 40% sodium hydrate aqueous solution.Further preferably, activator be selected from methyl alcohol, ethyl acetate, ethanol, acetonitrile, chloroform, carrene, benzinum, mass fraction be 37% hydrochloric acid and mass fraction be at least one in the aqueous solution of 40% NaOH.
Above-mentioned solid phase extractant have employed the Graphene of Graphene or process modification as solid extracting agent, and the Graphene that Graphene or process are modified is insensitive to pH value, and the pH of above-mentioned activator is all applicable in 0 ~ 14 scope.
Step 220: the chemical example until pre-treatment is injected the solid-phase extraction column after activation.
Treat that the chemical example of pre-treatment contains target components.When pending chemical example is solution, direct loading.When pending chemical example is solid, to be first mixed with after solution loading again, solvent is selected can the solvent of solubilized target component.
Pending chemical example is sent in splitter 10, makes pending chemical example slowly flow across solid extracting agent, complete loading.Preferably, the volume of pending chemical example is 1/8 times ~ 1 times of the volume of splitter 10.The flow velocity of pending chemical example is 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, to remove not by impurity that solid extracting agent adsorbs.After drip washing, discard the efflux that drip washing produces.
Preferably, the volume of eluent is the volume 1/8 times ~ 1 times of splitter 10.The flow velocity of eluent is 0.1mL/min ~ 1mL/min.
The polarity of eluent is contrary with the polarity of solvent of the chemical example treating pre-treatment.Preferably, the aqueous solution that eluent is selected from deionized water, methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane, pentane, mass fraction are 10% sodium carbonate, mass fraction be 37% hydrochloric acid and mass fraction be at least one in 40% sodium hydrate aqueous solution.
Further preferably, the aqueous solution that eluent is selected from deionized water, mass fraction is 10% sodium carbonate, methyl alcohol, ethyl acetate, ethanol, acetonitrile, chloroform, carrene, benzinum, mass fraction be 37% hydrochloric acid and mass fraction be at least one in the aqueous solution of 40% NaOH.
Step 240: with eluant, eluent, wash-out is carried out to solid-phase extraction column, obtain eluent.
With eluant, eluent, wash-out is carried out to solid-phase extraction column, to be separated the target components be adsorbed on solid-phase extraction column.
Inject splitter 10 with eluant, eluent, make eluant, eluent slowly flow into solid extracting agent, the desorption of realize target component, obtains eluent.Namely the eluent obtained can be used for chromatography.
Preferably, the volume of eluant, eluent is the volume 1/8 times ~ 1/2 times of splitter 10.The flow velocity of eluant, eluent is 0.1mL/min ~ 1mL/min.
The volume of above-mentioned splitter 10 refers to the volume of the cylinder 101 of hollow.
Preferably, after obtaining eluent, then eluent nitrogen is dried up, then carry out constant volume with 1mL ~ 10mL solvent to drying up the dry thing obtained, after constant volume, this solution is sent into subsequent detection equipment, as liquid chromatograph etc. is analyzed.
Above-mentioned solvent is selected from least one in deionized water, methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane and pentane.Preferably, above-mentioned organic solvent is selected from least one in methyl alcohol, ethyl acetate, ethanol, acetonitrile, chloroform, carrene and benzinum.
The above-mentioned chemical example pre-treating method based on SPE, by Graphene or the strong suction-operated through between the Graphene and target components of modification, it is made to have crystallized ability to specific target components, and adsorption capacity is not had to non-target components, thus effectively capture the target components of trace or trace in sample, and the mensuration of concrete content can be obtained in follow-up chromatography, thus avoid target components cannot measured actual value and the problem of the data distortion existed.
Further, above-mentioned based in the chemical example pre-treating method of SPE, the Graphene that use Graphene or process are modified, as solid extracting agent, effectively reduces the use amount of solid extracting agent, the waste in analytic process is reduced, and cost reduces.
The above-mentioned Graphene major part through modifying adopts LomedaJR, DoyleCD, KosynkinDV, HwangWF, TourJ M.J.Am.Chem.Soc., and in 2008,130:16201-16206, the diazol method of report carries out functionalized modification.
Carry out modification as alkylating reagent to Graphene to detergent alkylate aryldiazonium salt obtain as, dodecyl functionalized graphene adopts, after carboxylated Graphene adopts diazo ester reaction, hydrolysis is carried out carboxylated and is carried out modification to Graphene and obtain.
Amination Graphene separately adopts Krabbenborg S, Naber W J M, Velders A H, Reinhoudt D N, Wiel W G.Chem-Eur J., in 2009,15:8235-8240, the Azide-reduction of report is carried out amination and is carried out modification to Graphene and obtain; Hydroxylating Graphene adopts the method for sodium borohydride selective reduction graphene oxide to carry out hydroxylating degree Graphene to carry out modification and obtain.
It is below specific embodiment.
Embodiment 1
1, select few layer graphene as solid extracting agent according to component polarity.In the polypropylene plastics cylinder that loose for few layer graphene loading one end porous aluminum oxide sieve plate is sealed, the volume of solid extracting agent accounts for 1/5 of the volume of polypropylene plastics cylinder, then polypropylene plastics cylinder is sealed with another porous aluminum oxide oxidation sieve plate, the polypropylene plastics cylinder that few layer graphene is housed is placed on shaking table and vibrates 3min, gently press porous aluminum oxide sieve plate with compacting solid extracting agent again, obtain solid-phase extraction column.
2, prepare the working solution of α-nitronaphthalene, phenol, pentaerythrite, benzoic acid and naphthalene respectively, solvent is carrene, and concentration is 100ug/L, then adds methyl red as impurity composition, and the concentration of methyl red is 1mg/L.
3, added in solid-phase extraction column by methyl alcohol and activate solid-phase extraction column, the flow velocity of methyl alcohol is 1mL/min, and the volume of methyl alcohol is 1/8 times of the volume of polypropylene plastics cylinder.
4, get the above-mentioned working solution of 100mL respectively and inject the above-mentioned solid phase extraction column after activating, carry out loading.The volume of above-mentioned working solution is 1/8 times of the volume of polypropylene plastics cylinder, and flow velocity is 1mL/min.
5, carry out drip washing with ethanol to above-mentioned solid phase extractant, the volume of ethanol is 1/8 times of the volume of polypropylene plastics cylinder, and flow velocity is 1mL/min.
6, carry out wash-out with the mixed solution 0.5mL that acetonitrile and benzinum mix for 1:1 by volume again and obtain eluent, 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.
7, above-mentioned eluent nitrogen is dried up obtain dry thing, constant volume is carried out again with 1mL ethanol, get 20uL sample introduction and carry out liquid-phase chromatographic analysis (use Agilent 1100 high performance liquid chromatography work station, mobile phase is the mixed solvent of acetonitrile and water 1:1 mixing by volume, flow velocity is 0.5mL/min), the spectrogram obtained is as shown in Figure 3.
As seen from Figure 3, the few layer graphene of above-mentioned use can be good at selective seizure as the solid-phase extraction column of solid extracting agent to above-mentioned the objectives component and dissociates, and can remove impurity methyl red preferably.
Embodiment 2
1, select hydroxylating Graphene as solid extracting agent according to component polarity.In the polypropylene plastics cylinder that loose for hydroxylating Graphene loading one end porous aluminum oxide sieve plate is sealed, the volume of solid extracting agent accounts for 1/8 of the volume of polypropylene plastics cylinder, then polypropylene plastics cylinder is sealed with another porous aluminum oxide sieve plate, the polypropylene plastics cylinder that hydroxylating Graphene is housed is placed on shaking table and vibrates 3min, gently press porous aluminum oxide sieve plate with compacting solid extracting agent again, obtain solid-phase extraction column.
2, prepare the working solution of chloropropene, acrylamide, acrylic acid and propenyl respectively, solvent is methyl alcohol, and concentration is 100ug/L, then adds guinea green B as impurity composition, and the concentration of guinea green B is 1mg/L.
3, added in solid-phase extraction column by the mixed solvent of ethyl acetate and ethanol 1:1 mixing by volume and activate solid-phase extraction column, the flow velocity of mixed solvent is 1.5mL/min, and the volume of mixed solvent is 1/8 times of the volume of polypropylene plastics cylinder.
4, get the above-mentioned working solution of 100mL respectively and inject the above-mentioned solid phase extraction column after activating, carry out loading.The volume of above-mentioned working solution is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 1mL/min.
5, carry out drip washing with isopropyl alcohol to above-mentioned solid phase extractant, the volume of isopropyl alcohol is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 0.5mL/min.
6, carry out wash-out by ethyl acetate and methylene chloride volume than the mixed solution 0.5mL being 2:1 again and obtain eluent, 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.
7, above-mentioned eluent nitrogen is dried up obtain dry thing, constant volume is carried out again with 1mL acetonitrile, get 20uL sample introduction and carry out liquid-phase chromatographic analysis (use Agilent 1100 high performance liquid chromatography work station, mobile phase is the mixed solvent of first alcohol and water 4:1 mixing by volume, flow velocity is 0.5mL/min), the spectrogram obtained is as shown in Figure 4.
As seen from Figure 4, above-mentioned use hydroxylating Graphene can be good at selective seizure as the solid-phase extraction column of solid extracting agent to above-mentioned the objectives component and dissociates, and can remove impurity guinea green B preferably.
Embodiment 3
1, add solid extracting agent multiple to be selected in ethanol to be mixed with to organize SPE agent dispersing liquid respectively more, concentration is 0.1mg/mL, the sterling of the target components for detecting in testing sample being also made into above-mentioned solvent with 0.5mg/mL is gradient again, concentration is a sequence target components dispersion liquid of 0.5mg/mL ~ 5mg/mL, wherein, the sterling of target components is respectively methyl α-naphthyl acetate, indolebutyric acid, salicylic acid and benzene sulfonic acid.Respectively SPE agent dispersing liquid and target components dispersion liquid are mixed to get many parts of mixtures with the ratio of volume ratio 1:1, every part of mixture is got 1mL and is carried out ultrasonic disperse, after this mixture quiescent settling 30min, the sedimentation degree of the mixture containing amination Graphene is minimum, selects amination Graphene as solid extracting agent.
2, select amination Graphene as solid extracting agent.In the polypropylene plastics cylinder that loose for amination Graphene loading one end porous aluminum oxide sieve plate is sealed, the volume of solid extracting agent accounts for 1/6 of the volume of polypropylene plastics cylinder, then polypropylene plastics cylinder is sealed with another porous aluminum oxide sieve plate, the polypropylene plastics cylinder that amination Graphene is housed is placed on shaking table and vibrates 3min, gently press porous aluminum oxide sieve plate with compacting solid extracting agent again, obtain solid-phase extraction column.
3, prepare the working solution of methyl α-naphthyl acetate, indolebutyric acid, salicylic acid and benzene sulfonic acid respectively, solvent is ethanol, and concentration is 100ug/L, then adds dimethylbenzene green grass or young crops as impurity composition, and the concentration of dimethylbenzene green grass or young crops is 1mg/L.
4, added in solid-phase extraction column by acetonitrile and activate solid-phase extraction column, the flow velocity of acetonitrile is 1mL/min, and the volume of acetonitrile is 1 times of the volume of polypropylene plastics cylinder.
5, get the above-mentioned working solution of 100mL respectively and inject the above-mentioned solid phase extraction column after activating, carry out loading.The volume of above-mentioned working solution is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 0.1mL/min.
6, carry out drip washing with isopropyl alcohol to above-mentioned solid phase extractant, the volume of isopropyl alcohol is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 0.8mL/min.
7, carry out wash-out with the mixed solution 0.5mL that acetonitrile and water volume ratio are 1:1 again and obtain eluent, the volume of mixed solution is 1/2 times of the volume of polypropylene plastics stock column, and the flow velocity of mixed solution is 0.1mL/min.
8, above-mentioned eluent nitrogen is dried up obtain dry thing, constant volume is carried out again with 1mL ethyl acetate, get 20uL sample introduction and carry out liquid-phase chromatographic analysis (use Agilent 1100 high performance liquid chromatography work station, mobile phase is the mixed solvent of acetonitrile and water 1:1 mixing by volume, flow velocity is 0.5mL/min), the spectrogram obtained is as shown in Figure 5.
As seen from Figure 5, above-mentioned use amination Graphene can be good at selective seizure as the solid-phase extraction column of solid extracting agent to above-mentioned the objectives component and dissociates, can preferably except removal xylene is blue or green.
Embodiment 4
1, add solid extracting agent multiple to be selected in carrene to be mixed with to organize SPE agent dispersing liquid respectively more, concentration is 0.5mg/mL, the sterling of the target components for detecting in testing sample being also made into above-mentioned solvent with 0.5mg/mL is gradient again, concentration is a sequence target components dispersion liquid of 0.5mg/mL ~ 5mg/mL, wherein, the sterling of target components is respectively lutein, chlorophyll b, chlorophyll a and alkene.Respectively SPE agent dispersing liquid and target components dispersion liquid are mixed to get many parts of mixtures with the ratio of volume ratio 1:1, every part of mixture is got 5mL and is carried out ultrasonic disperse, after this mixture quiescent settling 60min, the sedimentation degree of the mixture containing dodecyl functionalized graphene is minimum, selects dodecyl functionalized graphene as solid extracting agent.
2, select dodecyl functionalized graphene as solid extracting agent.In the polypropylene plastics cylinder that loose for dodecyl functionalized graphene loading one end porous aluminum oxide sieve plate is sealed, the volume of solid extracting agent accounts for 1/6 of the volume of polypropylene plastics cylinder, then polypropylene plastics cylinder is sealed with another porous aluminum oxide sieve plate, the polypropylene plastics cylinder that dodecyl functionalized graphene is housed is placed on shaking table and vibrates 3min, gently press porous aluminum oxide sieve plate with compacting solid extracting agent again, obtain solid-phase extraction column.
3, prepare the working solution of lutein, chlorophyll b, chlorophyll a and alkene respectively, solvent is ethyl acetate, and concentration is 100ug/L, then to add Congo red as impurity composition, Congo red concentration be 1mg/L.
4, added in solid-phase extraction column by the mixed solvent of carrene and benzinum 1:2 mixing by volume and activate solid-phase extraction column, the flow velocity of mixed solvent is 2mL/min, and the volume of mixed solvent is 1 times of the volume of polypropylene plastics cylinder.
5, get the above-mentioned working solution of 100mL respectively and inject the above-mentioned solid phase extraction column after activating, carry out loading.Above-mentioned working solution volume is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 0.5mL/min.
6, carry out drip washing with the mixed solvent above-mentioned solid phase extractant of chloroform and carrene 1:2 mixing by volume, the volume of mixed solvent is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 0.1mL/min.
7, carry out wash-out with the mixed solution 0.5mL that ethyl acetate and benzinum mix for 2:1 by volume again and obtain eluent, 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.
8, above-mentioned eluent nitrogen is dried up obtain dry thing, constant volume is carried out again with 1mL chloroform, get 20uL sample introduction and carry out liquid-phase chromatographic analysis (use Agilent 1100 high performance liquid chromatography work station, mobile phase is the mixed solvent of first alcohol and water 4:1 mixing by volume, flow velocity is 0.5mL/min), the spectrogram obtained is as shown in Figure 6.
As seen from Figure 6, above-mentioned use dodecyl functionalized graphene can be good at selective seizure as the solid-phase extraction column of solid extracting agent to above-mentioned the objectives component and dissociates, and can remove Congo red preferably.
Embodiment 5
1, add solid extracting agent multiple to be selected in carrene to be mixed with to organize SPE agent dispersing liquid respectively more, concentration is 0.5mg/mL, the sterling of the target components for detecting in testing sample being also made into above-mentioned solvent with 0.5mg/mL is gradient again, concentration is a sequence target components dispersion liquid of 0.5mg/mL ~ 5mg/mL, wherein, the sterling of target components is α-BHC.Respectively SPE agent dispersing liquid and target components dispersion liquid are mixed to get many parts of mixtures with the ratio of volume ratio 1:1, every part of mixture is got 5mL and is carried out ultrasonic disperse, after this mixture quiescent settling 60min, the sedimentation degree of the mixture containing dodecyl functionalized graphene is minimum, selects dodecyl functionalized graphene as solid extracting agent.
2, select dodecyl functionalized graphene as solid extracting agent.In the polypropylene plastics cylinder that loose for dodecyl functionalized graphene loading one end porous aluminum oxide sieve plate is sealed, the volume of solid extracting agent accounts for 1/6 of the volume of polypropylene plastics cylinder, then polypropylene plastics cylinder is sealed with another porous aluminum oxide sieve plate, the polypropylene plastics cylinder that dodecyl functionalized graphene is housed is placed on shaking table and vibrates 3min, gently press porous aluminum oxide sieve plate with compacting solid extracting agent again, obtain solid-phase extraction column.
3, cross 50 mesh sieves after being pulverized by the Tea Samples polluted by α-BHC and obtain tea leaf powder, get 2.5g tea leaf powder to add in the mixed liquor of 20mL n-hexane-acetone (volume ratio of n-hexane and acetone is 97.5:2.5) and extract, 40min is extracted in the shaking table concussion being placed in 45 DEG C, obtains extract.
4, by mass fraction be 37% hydrochloric acid add in solid-phase extraction column solid-phase extraction column activated, the flow velocity of hydrochloric acid is 0.5mL/min, and the volume of mixed solvent is 1 times of the volume of polypropylene plastics cylinder.
5, the above-mentioned solid phase extraction column after 5mL said extracted liquid being injected activation carries out loading, and the volume of said extracted liquid is 1/8 times of the volume of polypropylene plastics cylinder, and flow velocity is 1mL/min.
6, carry out drip washing with acetonitrile to above-mentioned solid phase extractant, the volume of acetonitrile is 1 times of the volume of polypropylene plastics cylinder, and flow velocity is 1mL/min.
7, carry out wash-out with the mixed solution 25mL that ethyl acetate and benzinum mix for 1:9 by volume again and obtain eluent, the pigment in tealeaves is retained in eluent, remove other compositions in residues of pesticides and tealeaves, wherein 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 1mL/min.
8, above-mentioned eluent nitrogen is dried up rear 1mL n-hexane constant volume, solution after constant volume is got 20uL sample introduction and carry out liquid-phase chromatographic analysis (use Agilent 1100 high performance liquid chromatography work station, mobile phase is the mixed solvent of acetonitrile and water 1:1 mixing by volume, and flow velocity is 0.5mL/min).Separately get the pesticide sample solution that α-BHC is made into 100ng/mL, extracting sample solution 20uL sample introduction, for demarcating the α-BHC in Tea Samples.The spectrogram finally demarcated is as Fig. 7, and non-pigment is mixed peak interference, and α-BHC effectively can be made to be eluted, prove that Graphene solid-phase extraction column completes the function of its removal of impurities pigment effectively.
Embodiment 6
1, add solid extracting agent multiple to be selected in carrene to be mixed with to organize SPE agent dispersing liquid respectively more, concentration is 0.5mg/mL, the sterling of the target components for detecting in testing sample being also made into above-mentioned solvent with 0.5mg/mL is gradient again, concentration is a sequence target components dispersion liquid of 0.5mg/mL ~ 5mg/mL, wherein, the sterling of target components is respectively lutein, chlorophyll b, chlorophyll a and alkene.Respectively SPE agent dispersing liquid and target components dispersion liquid are mixed to get many parts of mixtures with the ratio of volume ratio 1:1, every part of mixture is got 5mL and is carried out ultrasonic disperse, after this mixture quiescent settling 60min, the sedimentation degree of the mixture containing dodecyl functionalized graphene is minimum, selects dodecyl functionalized graphene as solid extracting agent.
2, select dodecyl functionalized graphene as solid extracting agent.In the polypropylene plastics cylinder that loose for dodecyl functionalized graphene loading one end porous aluminum oxide sieve plate is sealed, the volume of solid extracting agent accounts for 1/6 of the volume of polypropylene plastics cylinder, then polypropylene plastics cylinder is sealed with another porous aluminum oxide sieve plate, the polypropylene plastics cylinder that dodecyl functionalized graphene is housed is placed on shaking table and vibrates 3min, gently press porous aluminum oxide sieve plate with compacting solid extracting agent again, obtain solid-phase extraction column.
3, be polished into homogenate by sending into pulverizer after the stripping and slicing of tomato sample, then get 0.5g strained tomatoes and add 10ml acetone, extract under 120w is ultrasonic, leach tomato residue after 10min, obtain extract.
4, added in solid-phase extraction column by the mixed solvent of carrene and chloroform 1:2 mixing by volume and activate solid-phase extraction column, the flow velocity of mixed solvent is 0.8mL/min, and the volume of mixed solvent is 1 times of the volume of polypropylene plastics cylinder.
5, the above-mentioned solid phase extraction column after 2mL said extracted liquid being injected activation carries out loading, and the volume of said extracted liquid is 1/9 times of the volume of polypropylene plastics cylinder, flow velocity 1mL/min.
6, the 10% sodium carbonate liquor drip washing of 5mL is used again, then the hydrochloric acid drip washing of 37% of 5mL is used, waste liquid containing impurity after washing discards, wherein, the cumulative volume of sodium carbonate liquor and hydrochloric acid is 1 times of the volume of polypropylene plastics cylinder, the flow velocity of sodium carbonate liquor is 0.5mL/min, and the flow velocity of hydrochloric acid is 0.5mL/min.
7, finally use n-hexane 15mL wash-out pigment, obtain eluent.The volume of n-hexane is 1/6 times of the volume of polypropylene plastics stock column, and the flow velocity of n-hexane is 0.3mL/min.
8, above-mentioned eluent nitrogen is dried up the n-hexane constant volume of rear 1mL, gone by solution after constant volume 20uL sample introduction to carry out liquid-phase chromatographic analysis and (use Agilent 1100 high performance liquid chromatography work station, mobile phase is the mixed solvent of acetonitrile and water 1:1 mixing by volume, flow velocity is 0.5mL/min), obtain spectrogram as Fig. 8, demonstrate Graphene solid-phase extraction column can effectively the lycopene in tomato and beta carotene be retained, and effectively by the organic acid in drip washing wash-out tamato fruit, make it not disturb in follow-up chromatogram.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a solid-phase extraction column, is characterized in that, comprises splitter and is filled in the solid extracting agent in described splitter, and described solid extracting agent is Graphene or the Graphene through modifying; Described Graphene is single-layer graphene or few layer graphene, and the described Graphene through modifying is selected from least one in amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, fluorinated graphene, bromination Graphene, chlorination Graphene and iodate Graphene.
2. solid-phase extraction column according to claim 1, is characterized in that, described splitter comprises the polypropylene plastics stock column of hollow and is removable installed in two porous aluminum oxide sieve plates of described polypropylene plastics stock column inside; Described solid extracting agent is filled between described two porous aluminum oxide sieve plates.
3. a preparation method for solid-phase extraction column, comprises the steps:
Select a kind of from solid extracting agent multiple to be selected, described in solid extracting agent to be selected be Graphene or the Graphene through modifying; Described Graphene is single-layer graphene or few layer graphene, and the described Graphene through modifying is selected from least one in amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, the Graphene that methylates, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, fluorinated graphene, bromination Graphene, chlorination Graphene and iodate Graphene;
Selected solid extracting agent is loaded in splitter, the splitter that described solid extracting agent is housed is placed on shaking table and vibrates 3min, and solid extracting agent described in compacting, obtain described solid-phase extraction column.
4. the preparation method of solid-phase extraction column according to claim 3, is characterized in that, describedly from solid extracting agent multiple to be selected, selects a kind of method to be specially:
Respectively solid extracting agent multiple to be selected is mixed with many group SPE agent dispersing liquids, and the sterling of the target components for detecting in testing sample is mixed with many group target components dispersion liquids, undertaken being mixed to get organizing mixture by organizing SPE agent dispersing liquid more and organizing target components dispersion liquid more respectively more, ultrasonic disperse is carried out by often organizing described mixture, after described mixture sedimentation, select the solid extracting agent in one group of mixture that sedimentation degree is minimum;
Described multiple solid extracting agent to be selected is Graphene or the Graphene through modifying, and described Graphene is single-layer graphene or few layer graphene, and the described Graphene through modifying is selected from amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylating Graphene, sulfhydrylation Graphene, methylate Graphene, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, 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, methylate Graphene, allylation Graphene, trifluoromethyl functionalized graphene, dodecyl functionalized graphene, octadecyl functionalized graphene, fluorinated graphene, bromination Graphene, at least one in chlorination Graphene and iodate Graphene.
5., based on a chemical example pre-treating method for SPE, it is characterized in that, comprise the steps:
Solid-phase extraction column described in any one of claim 1 ~ 2 is activated;
Chemical example until pre-treatment is injected the described solid-phase extraction column after activation;
With eluent, drip washing is carried out to described solid-phase extraction column; And
With eluant, eluent, wash-out is carried out to described solid-phase extraction column, obtain eluent.
6. the chemical example pre-treating method based on SPE according to claim 5, it is characterized in that, be specially the operation that the solid-phase extraction column described in any one of claim 1 ~ 2 activates: added by activator in described solid-phase extraction column, the volume of described activator is 1/8 times ~ 1 times of the volume of described splitter; Described activator is selected from methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane, pentane, mass fraction be 37% hydrochloric acid and mass fraction be at least one in 40% sodium hydrate aqueous solution.
7. the chemical example pre-treating method based on SPE according to claim 5, is characterized in that, treats that the volume of the chemical example of pre-treatment is 1/8 times ~ 1 times of the volume of described splitter.
8. the chemical example pre-treating method based on SPE according to claim 5, is characterized in that, the volume of described eluent is 1/8 times ~ 1 times of the volume of described splitter; Described eluent is selected from methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane, pentane, mass fraction be 37% hydrochloric acid and mass fraction be at least one in 40% sodium hydrate aqueous solution.
9. the chemical example pre-treating method based on SPE according to claim 5, is characterized in that, the volume of described eluant, eluent is 1/8 times ~ 1/2 times of the volume of described splitter; Described eluant, eluent is selected from least one in methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, carrene, carbon tetrachloride, ether, toluene, benzene, cyclohexane, benzinum, hexane and pentane.
10. the chemical example pre-treating method based on SPE according to claim 5, it is characterized in that, also comprise the step that described eluent is processed, described the step that eluent processes to be specially: described eluent nitrogen is dried up and obtains dry thing, then with described eluant, eluent, constant volume is carried out to described dry thing.
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