CN104215727A - Graphene material based disperse and quick solid-phase extraction method - Google Patents
Graphene material based disperse and quick solid-phase extraction method Download PDFInfo
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Abstract
The invention relates to a graphene material based disperse and quick solid-phase extraction method. The graphene material based disperse and quick solid-phase extraction method comprises the steps of performing pore forming and activation on a graphene material to obtain an activated graphene material, wherein the graphene material is graphene or modified graphene; adding the activated graphene material into a chemical sample to be processed to obtain a mixture, shaking and extracting the mixture, then performing centrifugation to obtain a precipitate and supernate, wherein the supernate contains a target component to be detected. The grid cross-linking degree of the activated graphene material is improved, and the graphene material is easily separated in the centrifugal or filtered operation. By means of the method, a disperse solid-phase extraction technology and the activated graphene material serving as a solid-phase extraction solution can be combined, and a complicated operation in traditional solid-phase extraction is simplified and is simple. Impurities can be selectively absorbed by the activated graphene material, and accordingly impurity removal is effectively performed on chemical samples. Therefore, the method is good in separation effect.
Description
Technical field
The present invention relates to chemical example pretreatment technology field, particularly relate to the quick solid phase extraction method of a kind of dispersion based on grapheme material.
Background technology
In order to carry out stratographic analysis preferably, Sample Pretreatment Technique the most frequently used is at present Solid-Phase Extraction (SPE) technology, namely realize sorption extraction by the special component in component and the affinity between solid extracting agent, thus realize the separation of special component.Therefore, solid extracting agent is selected to seem very important.
Traditional solid phase extraction techniques needs the sequence of operations such as activation, upper prop, wash-out, makes testing process become complicated.Therefore, the quick Solid-Phase Extraction of efficient dispersion (DSPE) technology after improvement replaces the status of SPE just gradually.DSPE operating process is short, makes solid extracting agent extract rear solid extracting agent directly depart from from solution, enormously simplify operation by shirtsleeve operation.
Adopt grapheme material as the solid extracting agent of improvement, be conducive to realizing good separating effect.But, directly utilize Graphene to carry out disperseing quick Solid-Phase Extraction not to be operationally most suitable, mainly because the density of Graphene is too small, more difficult in centrifugal process Graphene to be separated fully from sample.Further, in current technology, be only that Graphene is used as the strong nonpolar solid extracting agent of one, utilize the advantage of Graphene not yet fully, to obtain good separating effect.
Summary of the invention
Based on this, be necessary to provide a kind of simple to operate, separating effect preferably based on the quick solid phase extraction method of dispersion of grapheme material.
The quick solid phase extraction method of dispersion based on grapheme material, comprises the steps:
Carry out pore-creating activation to grapheme material, obtain the grapheme material after activating, described grapheme material is Graphene or the Graphene through modifying; And
Grapheme material after described activation is added in pending chemical example and obtains potpourri, described potpourri is carried out concussion extraction, then carry out centrifugal, be precipitated and supernatant, containing target components to be detected in described supernatant.
Wherein in an embodiment, described the method that grapheme material carries out pore-creating activation to be specially:
Grapheme material is loaded in reactor; 300 DEG C ~ 500 DEG C are heated in blanket gas atmosphere; in described reactor, pass into water vapor again and carry out activation 1h ~ 3h; then change and pass into blanket gas; heating is stopped after 1min ~ 5min; take out described grapheme material, washing, drying obtain the grapheme material after activating.
Wherein in an embodiment, the flow velocity of described water vapor is 0.5mL/min ~ 5mL/min.
Wherein in an embodiment, 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, hydroxylation 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, the mass ratio of the grapheme material after described activation and described pending chemical example is 1 ~ 20:200.
Wherein in an embodiment, the time of described concussion extraction is 0.5min ~ 5min.
Wherein in an embodiment, described centrifugal rotating speed is 3000r/min ~ 4000r/min, and the centrifugal time is 1min ~ 3min.
The quick solid phase extraction method of the above-mentioned dispersion based on grapheme material uses the grapheme material after activation as solid extracting agent, degree of crosslinking between the grid of the grapheme material after activation increases, it is made easilier separatedly to get off in operation that is centrifugal or that filter, therefore, dispersive solid-phase extraction technology can combine as solid extracting agent with the grapheme material after activation by the method, simplify the troublesome operation in traditional Solid-Phase Extraction, only need to carry out concussion and the centrifugal pre-treatment that can complete chemical example, operate comparatively simple.
And, by the grapheme material after activation and the strong suction-operated between impurity, it is made to have absorption crystallized ability to specific impurity, and adsorptive power is not had to target components to be detected, thus effectively chemical example has been carried out removal of impurities, make target components to be detected in follow-up stratographic analysis, obtain the mensuration of concrete content.Therefore, the separating effect of the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material is better.
The quick solid phase extraction method of dispersion based on grapheme material, comprises the steps:
Carry out pore-creating activation to grapheme material, obtain the grapheme material after activating, described grapheme material is Graphene or the Graphene through modifying;
Grapheme material after described activation is added in pending chemical example and obtains the first potpourri, described first potpourri is carried out concussion extraction, then carry out centrifugal, obtain the first precipitation and the first supernatant; And
Described first precipitation and eluant, eluent are carried out being mixed to get the second potpourri, described second potpourri is carried out shaking, filtering, obtains the second precipitation and the second supernatant, containing target components to be detected in described second supernatant.
The hydrochloric acid that wherein in an embodiment, described eluant, eluent is selected from deionized water, methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, methylene chloride, phenixin, ether, toluene, benzene, cyclohexane, sherwood oil, hexane, pentane, massfraction are 37%, massfraction are at least one in the aqueous solution of 40% NaOH and deionized water.
Wherein in an embodiment, it is characterized in that, described first precipitation is 1mg:1 ~ 50mL with the mass volume ratio of described eluant, eluent.
The quick solid phase extraction method of the above-mentioned dispersion based on grapheme material uses the grapheme material after activation as solid extracting agent, degree of crosslinking between the grid of the grapheme material after activation increases, it is made easilier separatedly to get off in operation that is centrifugal or that filter, therefore, dispersive solid-phase extraction technology can combine as solid extracting agent with the grapheme material after activation by the method, simplify the troublesome operation in traditional Solid-Phase Extraction, only need to carry out shaking and filter the pre-treatment that can complete chemical example, operate comparatively simple.
And, by the grapheme material after activation and the strong suction-operated of target components to be detected, it is made to have absorption crystallized ability to specific target components to be detected, and adsorptive power is not had to impurity, thus effectively chemical example has been carried out removal of impurities, make target components to be detected in follow-up stratographic analysis, obtain the mensuration of concrete content.Therefore, the separating effect of the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material is better.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the quick solid phase extraction method of the dispersion based on grapheme material of an embodiment;
Fig. 2 is the process flow diagram of the quick solid phase extraction method of the dispersion based on grapheme material of another 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.
Embodiment
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 quick solid phase extraction method of the dispersion based on grapheme material of an embodiment, comprises the steps 110 and step 120.
Step 110: carry out pore-creating activation to grapheme material, obtains the grapheme material after activating, and grapheme material is Graphene or the Graphene through modifying.
Graphene is single-layer graphene or few layer graphene.Graphenic surface is made up of the large π key of conjugation, has extremely strong nonpolar, and can realize strong π-π with the organic molecule containing aromatic ring and interact, thus realizes reversible adsorption.Therefore, Graphene is excellent solid extracting agent.
Graphene through modifying is selected from least one in amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylation 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.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.Graphene is modified, just effectively can change the polar character on its surface, even make reversal of poles, thus be applicable to be separated more sample.Specific functional group is introduced on the surface of Graphene, realize catching flutterring of target molecule, improve absorption property, make full use of the advantage of Graphene, and not only using Graphene as the strong nonpolar solid extracting agent of one, contribute to the kind expanding pending chemical example.
Preferably, the method that grapheme material carries out pore-creating activation is specially:
Grapheme material is loaded in reactor; 300 DEG C ~ 500 DEG C are heated in blanket gas atmosphere; in reactor, pass into water vapor again carry out activation 1h ~ 3h; then change and pass into blanket gas; heating is stopped after 1min ~ 5min; take out grapheme material, washing, drying obtain the grapheme material after activating.
Reactor can be tubular furnace, muffle furnace etc.Blanket gas can be nitrogen or inert gas.
Above-mentioned method of grapheme material being carried out to pore-creating activation introduces hole by the mode of steam activation at Graphene or on the Graphene modified, increase its surface area, improve Graphene or the strong suction-operated through between the Graphene and impurity of modification, be conducive to improving separating effect.And, after activating, degree of crosslinking between the grid of grapheme material increases, and makes it easilier separatedly in operation that is centrifugal or that filter get off, overcome the difficult problem being difficult to Graphene to separate from sample fully, thus grapheme material can be applied to dispersion rapid extraction technology.
And above-mentioned method of grapheme material being carried out to pore-creating activation is by means of only heating and use steam activation, without the need to using other chemical activating agents, comparatively environmental protection.
Preferably, the flow velocity of water vapor is 0.5mL/min ~ 5mL/min.
Preferably, the method for above-mentioned washing is by grapheme material rinsed with deionized water 2 ~ 3 times.Drying is dry 1h ~ 2h at 60 DEG C ~ 80 DEG C.
Be appreciated that in other embodiments, other pore-creating activation method can be adopted.Such as, chemical activating agent is adopted on grapheme material, to carry out pore-creating as potassium hydroxide etc. and the activation that realizes grapheme material.
Step 120: added in pending chemical example by the grapheme material after activation and obtain potpourri, carries out concussion extraction, then carries out centrifugal, be precipitated and supernatant, containing target components to be detected in supernatant by potpourri.
Preferably, the mass ratio of the grapheme material after activation and pending chemical example is 1 ~ 20:200, to guarantee complete adsorbing contaminant and don't can cause the waste of grapheme material.
Potpourri is carried out concussion extraction, realize the grapheme material after activation to the absorption of impurity.Grapheme material after activation has larger specific surface area and has stronger adsorptive power, and therefore, the concussion extraction shorter time can ensure that the grapheme material after activating is to the absorption completely of impurity, raises the efficiency.Preferably, the time of concussion extraction is 0.5min ~ 5min.
Preferably, centrifugal rotating speed is 3000r/min ~ 4000r/min, and the centrifugal time is 1min ~ 3min.
After centrifugal, be precipitated and supernatant.
What the grapheme material after activation adsorbed is impurity, is precipitated as the grapheme material after the activation of having adsorbed impurity, containing target components to be detected in supernatant.Supernatant is stored in sample injection bottle, for subsequent analysis, as carried out liquid chromatography demarcation etc. with the filtering with microporous membrane of 0.22 μm.Precipitation is carried out subsequent treatment, the impurity adsorbed with desorption and reclaim grapheme material.Such as, wash-out can be carried out to make impurity desorption with eluant, eluent to precipitation.
The quick solid phase extraction method of the above-mentioned dispersion based on grapheme material uses the grapheme material after activation as solid extracting agent, degree of crosslinking between the grid of the grapheme material after activation increases, it is made easilier separatedly to get off in operation that is centrifugal or that filter, therefore, dispersive solid-phase extraction technology can combine as solid extracting agent with the grapheme material after activation by the method, simplify the troublesome operation in traditional Solid-Phase Extraction, only need to carry out concussion and the centrifugal pre-treatment that can complete chemical example, operate comparatively simple.
And, by the grapheme material after activation and the strong suction-operated between impurity, it is made to have absorption crystallized ability to specific impurity, and adsorptive power is not had to target components to be detected, thus effectively chemical example has been carried out removal of impurities, make target components to be detected can obtain the mensuration of concrete content in follow-up stratographic analysis.Therefore, the separating effect of the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material is better.
The quick solid phase extraction method of the above-mentioned dispersion based on grapheme material is simple to operate, and extraction time is short, and efficiency is high.
Refer to Fig. 2, the quick solid phase extraction method of the dispersion based on grapheme material of another embodiment, comprises the steps 210 to step 230.
Step 210: carry out pore-creating activation to grapheme material, obtains the grapheme material after activating, and grapheme material is Graphene or the Graphene through modifying.
Step 210 is identical with the step 110 of the quick solid phase extraction method of the dispersion based on grapheme material of above-mentioned embodiment.
Adopt the mode of steam activation to activate grapheme material, improve Graphene or the strong suction-operated through between the Graphene and target components to be detected of modification, be conducive to improving separating effect.And, after activating, degree of crosslinking between the grid of grapheme material increases, and makes it easilier separatedly in operation that is centrifugal or that filter get off, overcome the difficult problem being difficult to Graphene to separate from sample fully, thus grapheme material can be applied to dispersion rapid extraction technology.
Step 220: added in pending chemical example by the grapheme material after activation and obtain the first potpourri, carries out concussion extraction, then carries out centrifugal, obtain the first precipitation and the first supernatant by the first potpourri.
In step 220, what the grapheme material after activation adsorbed is target components to be detected, and first is precipitated as the grapheme material after the activation of having adsorbed target components to be detected, containing impurity in the first supernatant.Discard the first supernatant, the first precipitation is carried out subsequent treatment, to collect the higher target components to be detected of purity.
The time of concussion extraction is preferably 0.5min ~ 5min.
Preferably, centrifugal rotating speed is 3000r/min ~ 4000r/min, and the centrifugal time is 1min ~ 3min.
Step 230: the first precipitation and eluant, eluent are carried out being mixed to get the second potpourri, the second potpourri is carried out shake, filter, obtain the second precipitation and the second supernatant, containing target components to be detected in the second supernatant.
The hydrochloric acid that eluant, eluent is selected from deionized water, methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, methylene chloride, phenixin, ether, toluene, benzene, cyclohexane, sherwood oil, hexane, pentane, massfraction are 37%, massfraction are at least one in 40% sodium hydrate aqueous solution and deionized water.
Target components to be detected in grapheme material after using eluent to be adsorbed in activation.Preferably, the first precipitation is 1mg:1 ~ 50mL with the mass volume ratio of eluant, eluent, to ensure complete for target components to be detected wash-out.
Carry out shaking the wash-out being conducive to target components to be detected.Preferably, the time of concussion is 0.5min ~ 5min.
Filter after concussion, obtain the second precipitation and the second supernatant.
Second is precipitated as the grapheme material after the activation of desorption target components to be detected, containing target components to be detected in the second supernatant.Second supernatant is deposited in sample injection bottle, for subsequent analysis, as carried out liquid chromatography demarcation etc. with the filtering with microporous membrane of 0.22 μm.
Grapheme material after the desorption activation of target components to be detected can also be recycled, and such as, again carries out pre-treatment as solid extracting agent to chemical example.
The quick solid phase extraction method of the above-mentioned dispersion based on grapheme material uses the grapheme material after activation as solid extracting agent, degree of crosslinking between the grid of the grapheme material after activation increases, it is made easilier separatedly to get off in operation that is centrifugal or that filter, therefore, dispersive solid-phase extraction technology can combine as solid extracting agent with the grapheme material after activation by the method, simplify the troublesome operation in traditional Solid-Phase Extraction, only need to carry out shaking and filter the pre-treatment that can complete chemical example, operate comparatively simple.
And, by the Graphene after activation or through the Graphene of modification and the strong suction-operated of target components to be detected, it is made to have absorption crystallized ability to specific target components to be detected, and adsorptive power is not had to the impurity of non-targeted, thus the target components to be detected of the trace effectively captured in chemical example or trace, make target components to be detected in follow-up stratographic analysis, obtain the mensuration of concrete content.Therefore, the separating effect of the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material is better.
The quick solid phase extraction method of the above-mentioned dispersion based on grapheme material is simple to operate, and extraction time is short, and efficiency is high.
Be appreciated that, grapheme material after solid extracting agent-activation in the quick solid phase extraction method of dispersion based on grapheme material of above-mentioned two kinds of embodiments can only impurity in the same pending chemical example of selective adsorption or target components to be detected, and the impurity that can not simultaneously adsorb in same pending chemical example and target components to be detected, the target components to be detected of namely pending chemical example and the different in kind of impurity make the grapheme material after activating can one in selective adsorption target components to be detected and impurity.
Modify graphene-based that pass through in the quick solid phase extraction method of dispersion based on grapheme material of above-mentioned two kinds of embodiments all adopts LomedaJR, DoyleCD, KosynkinDV, HwangWF, TourJ M.J.Am.Chem.Soc., in 2008,130:16201-16206, the diazo salt method of report is carried out functionalized.
Such as, dodecyl functionalized graphene carries out modification as alkylating reagent to Graphene to dodecyl benzene aryldiazonium salt obtain for adopting, carboxylated namely adopt diazo ester reaction after hydrolysis carry out carboxylatedly carrying out modification to Graphene and obtaining.
Wherein amination Graphene separately adopts Krabbenborg S, Naber W J M, Velders A H, Reinhoudt D N, Wiel W G.Chem-Eur J., and the Azide-reduction reported in 2009,15:8235-8240 is carried out amination and obtained; Hydroxylation Graphene then adopts the method for sodium borohydride selective reduction graphene oxide to carry out hydroxylation to carry out modification to Graphene and obtain.
Below by way of specific embodiment, the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material is set forth further.
Embodiment 1
1, load in tubular furnace by single-layer graphene, pass into nitrogen, be heated to 300 DEG C in nitrogen atmosphere, stop passing into nitrogen, in tubular furnace, pass into water vapor carry out activation 3h, wherein, the flow velocity of water vapor is 5mL/min.Then, stop passing into water vapor, change and pass into nitrogen, after 5min, stop heating, take out grapheme material, by rinsed with deionized water 3 times, and at 60 DEG C dry 2h, obtain the single-layer graphene after activating.
2, by phenol, 4,4 '-DCBP, biphenyl, naphthalene and pyrene mix and the concentration being mixed with often kind of component is the working solution of 100 μ g/Kg, and solvent is methylene chloride, then adds porphyrin as impurity composition, and the concentration of porphyrin is 1mg/L.
3, the above-mentioned working solution of 5g is got, in the ratio adding 30mg solid extracting agent in every gram often kind component the single-layer graphene after above-mentioned activation added in the above-mentioned working solution of 5g and obtain the first potpourri, first potpourri is carried out on shaking table concussion extraction 0.5min, then centrifugal 3min under 3000r/min, obtains the first precipitation and the first supernatant.
4, this first precipitation is placed in conical flask with sherwood oil to carry out being mixed to get the second potpourri, the first precipitation is 1mg:2mL with the mass volume ratio of sherwood oil.Conical flask is placed in shaking table and shakes 0.5min, then filter, obtain the second precipitation and the second supernatant, with filtering with microporous membrane second supernatant of 0.22 μm, the the second supernatant sample introduction got after 20 μ L filtrations carries out liquid-phase chromatographic analysis and (uses Agilent 1100 high performance liquid chromatography workstation, mobile phase is the mixed solvent of acetonitrile and water 1:1 mixing by volume, and flow velocity is 0.5mL/min), gained spectrogram is as shown in Figure 3.
As seen from Figure 3, the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material can be good at catching to every component and dissociate, and can remove the porphyrin impurity of large ring preferably.
Embodiment 2
1, loaded in tubular furnace by amination Graphene, pass into nitrogen, be heated to 500 DEG C in nitrogen atmosphere, stop passing into nitrogen, in tubular furnace, pass into water vapor carry out activation 1h, wherein, the flow velocity of water vapor is 0.5mL/min.Then, stop passing into water vapor, change and pass into nitrogen, after 1min, stop heating, take out grapheme material, by rinsed with deionized water 3 times, and at 80 DEG C dry 1h, obtain the amination Graphene after activating.
2, phenylalanine, leucine, histidine, lysine mixed and the concentration being mixed with often kind of component is the working solution of 100 μ g/L, solvent is acetonitrile, then adds methyl violet as impurity composition, and the concentration of methyl violet is 1mg/L.
3, the above-mentioned working solution of 5g is got, in the ratio adding 5mg solid extracting agent in every gram often kind component the amination Graphene after above-mentioned activation added in the above-mentioned working solution of 5g and obtain the first potpourri, first potpourri is carried out on shaking table concussion extraction 5min, then centrifugal 1min under 4000r/min, obtains the first precipitation and the first supernatant.
4, this first precipitation is placed in conical flask with ethanol to carry out being mixed to get the second potpourri, the first precipitation is 1mg:1mL with the mass volume ratio of ethanol.Conical flask is placed in shaking table and shakes 5min, then filter, obtain the second precipitation and the second supernatant, with filtering with microporous membrane second supernatant of 0.22 μm, the the second supernatant sample introduction got after 20 μ L filtrations carries out liquid-phase chromatographic analysis and (uses Agilent 1100 high performance liquid chromatography workstation, mobile phase is the mixed solvent of first alcohol and water 4:1 mixing by volume, and flow velocity is 0.5mL/min), gained spectrogram is as shown in Figure 4.
As seen from Figure 4, the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material can be good at catching to every component and dissociate, and can remove methyl violet preferably.
Embodiment 3
1, loaded in tubular furnace by carboxylated Graphene, pass into nitrogen, be heated to 400 DEG C in nitrogen atmosphere, stop passing into nitrogen, in tubular furnace, pass into water vapor carry out activation 2h, wherein, the flow velocity of water vapor is 2mL/min.Then, stop passing into water vapor, change and pass into nitrogen, after 3min, stop heating, take out grapheme material, by rinsed with deionized water 3 times, and at 70 DEG C dry 1.5h, obtain the carboxylated Graphene after activating.
2, cross 100 mesh sieves after being pulverized with food masher by the coptis and obtain Golden Thread, getting 0.5g Golden Thread again adds in the mixed solvent 200ml of hydrochloric acid-methanol (volume ratio of hydrochloric acid and methyl alcohol is 1:100), 2h is extracted in 60 DEG C of water-baths, then ultrasonication residue coptis residue.Finally filter and remove coptis residue, obtain coptis extract solution as working solution.
3, the above-mentioned working solution of 5g is got, in the ratio adding 100mg solid extracting agent in every gram often kind component the carboxylated Graphene after above-mentioned activation added in the above-mentioned working solution of 5g and obtain potpourri, potpourri is carried out on shaking table concussion extraction 3min, then centrifugal 1min under 3500r/min, is precipitated and supernatant.
4, with the filtering with microporous membrane supernatant of 0.22 μm, the supernatant sample introduction got after 20 μ L filtrations carries out liquid-phase chromatographic analysis and (uses Agilent 1100 high performance liquid chromatography workstation, mobile phase is the mixed solvent of acetonitrile and water 1:1 mixing by volume, flow velocity is 0.5mL/min), gained spectrogram is as shown in Figure 5.
As seen from Figure 5, the carboxylated Graphene of the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material can effectively by the impurity in coptis extract, and suction-operated is not had to target component alkaloid to be detected, can natural products that effectively purifying is to be analyzed.
Embodiment 4
1, loaded in tubular furnace by dodecyl functionalized graphene, pass into nitrogen, be heated to 450 DEG C in nitrogen atmosphere, stop passing into nitrogen, in tubular furnace, pass into water vapor carry out activation 1.5h, wherein, the flow velocity of water vapor is 3mL/min.Then, stop passing into water vapor, change and pass into nitrogen, after 2min, stop heating, take out grapheme material, by rinsed with deionized water 3 times, and at 75 DEG C dry 1h, obtain the dodecyl functionalized graphene after activating.
2, beta-myrcene, geraniol, vanillic aldehyde, α-citral mixed and the concentration being mixed with often kind of component is the working solution of 100 μ g/L, solvent is cyclohexane, then adds methylene blue as impurity composition, and the concentration of methylene blue is 1mg/L.
3, the above-mentioned working solution of 5g is got, in the ratio adding 75mg solid extracting agent in every gram often kind component the dodecyl functionalized graphene after above-mentioned activation added in the above-mentioned working solution of 5g and obtain the first potpourri, first potpourri is carried out on shaking table concussion extraction 2min, then centrifugal 1.5min under 3200r/min, obtains the first precipitation and the first supernatant.
4, this first precipitation is placed in conical flask with ethyl acetate and ethanol to carry out being mixed to get the second potpourri, the mass volume ratio of the first precipitation, ethyl acetate and ethanol is 1mg:10mL:10mL.Conical flask is placed in shaking table and shakes 4min, then filter, obtain the second precipitation and the second supernatant, with filtering with microporous membrane second supernatant of 0.22 μm, the the second supernatant sample introduction got after 20 μ L filtrations carries out liquid-phase chromatographic analysis and (uses Agilent 1100 high performance liquid chromatography workstation, mobile phase is the mixed solvent of first alcohol and water 4:1 mixing by volume, and flow velocity is 0.5mL/min), gained spectrogram is as shown in Figure 6.
As seen from Figure 6, the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material can be good at catching to every component and dissociate, and can remove methylene blue preferably.
Embodiment 5
1, loaded in tubular furnace by hydroxylation Graphene, pass into nitrogen, be heated to 350 DEG C in nitrogen atmosphere, stop passing into nitrogen, in tubular furnace, pass into water vapor carry out activation 2.5h, wherein, the flow velocity of water vapor is 4mL/min.Then, stop passing into water vapor, change and pass into nitrogen, after 4min, stop heating, take out grapheme material, by rinsed with deionized water 3 times, and at 65 DEG C dry 2h, obtain the hydroxylation Graphene after activating.
2, estradiol, progesterone, cholesterol, aldosterone mixed and the concentration being mixed with often kind of component is the working solution of 100 μ g/L, solvent is tetrahydrofuran, then adds haematine as impurity composition, and hematoxylic concentration is 1mg/L.
3, the above-mentioned working solution of 5g is got, in the ratio adding 50mg solid extracting agent in every gram often kind component the hydroxylation Graphene after above-mentioned activation added in the above-mentioned working solution of 5g and obtain the first potpourri, first potpourri is carried out on shaking table concussion extraction 4min, then centrifugal 1.5min under 3800r/min, obtains the first precipitation and the first supernatant.
4, this first precipitation is placed in conical flask with methylene chloride to carry out being mixed to get the second potpourri, the first precipitation is 1mg:15mL with the mass volume ratio of methylene chloride.Conical flask is placed in shaking table and shakes 2min, then filter, obtain the second precipitation and the second supernatant, with filtering with microporous membrane second supernatant of 0.22 μm, the the second supernatant sample introduction got after 20 μ L filtrations carries out liquid-phase chromatographic analysis and (uses Agilent 1100 high performance liquid chromatography workstation, mobile phase is the mixed solvent of acetonitrile and water 1:1 mixing by volume, and flow velocity is 0.5mL/min), gained spectrogram is as shown in Figure 7.
As seen from Figure 7, the quick solid phase extraction method of the above-mentioned dispersion based on grapheme material can be good at catching to every component and dissociate, and can remove haematine preferably.
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., based on the quick solid phase extraction method of dispersion of grapheme material, comprise the steps:
Carry out pore-creating activation to grapheme material, obtain the grapheme material after activating, described grapheme material is Graphene or the Graphene through modifying; And
Grapheme material after described activation is added in pending chemical example and obtains potpourri, described potpourri is carried out concussion extraction, then carry out centrifugal, be precipitated and supernatant, containing target components to be detected in described supernatant.
2. the quick solid phase extraction method of the dispersion based on grapheme material according to claim 1, is characterized in that, is describedly specially the method that grapheme material carries out pore-creating activation:
Grapheme material is loaded in reactor; 300 DEG C ~ 500 DEG C are heated in blanket gas atmosphere; in described reactor, pass into water vapor again and carry out activation 1h ~ 3h; then change and pass into blanket gas; heating is stopped after 1min ~ 5min; take out described grapheme material, washing, drying obtain the grapheme material after activating.
3. the quick solid phase extraction method of the dispersion based on grapheme material according to claim 1, is characterized in that, the flow velocity of described water vapor is 0.5mL/min ~ 5mL/min.
4. the quick solid phase extraction method of the dispersion based on grapheme material according to claim 1, it is characterized in that, described Graphene is single-layer graphene or few layer graphene, the described Graphene through modifying is selected from amination Graphene, carboxylated Graphene, cyano group Graphene, nitro Graphene, boronate Graphene, phosphate Graphene, hydroxylation 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. the quick solid phase extraction method of the dispersion based on grapheme material according to claim 1, is characterized in that, the mass ratio of the grapheme material after described activation and described pending chemical example is 1 ~ 20:200.
6. the quick solid phase extraction method of the dispersion based on grapheme material according to claim 1, is characterized in that, the time of described concussion extraction is 0.5min ~ 5min.
7. the quick solid phase extraction method of the dispersion based on grapheme material according to claim 1, is characterized in that, described centrifugal rotating speed is 3000r/min ~ 4000r/min, and the centrifugal time is 1min ~ 3min.
8., based on the quick solid phase extraction method of dispersion of grapheme material, comprise the steps:
Carry out pore-creating activation to grapheme material, obtain the grapheme material after activating, described grapheme material is Graphene or the Graphene through modifying;
Grapheme material after described activation is added in pending chemical example and obtains the first potpourri, described first potpourri is carried out concussion extraction, then carry out centrifugal, obtain the first precipitation and the first supernatant; And
Described first precipitation and eluant, eluent are carried out being mixed to get the second potpourri, described second potpourri is carried out shaking, filtering, obtains the second precipitation and the second supernatant, containing target components to be detected in described second supernatant.
9. the quick solid phase extraction method of the dispersion based on grapheme material according to claim 8, it is characterized in that, described eluant, eluent is selected from deionized water, at least one in aqueous solution that hydrochloric acid that methyl alcohol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, chloroform, methylene chloride, phenixin, ether, toluene, benzene, cyclohexane, sherwood oil, hexane, pentane, massfraction are 37%, massfraction are 40% NaOH and deionized water.
10. the quick solid phase extraction method of the dispersion based on grapheme material according to claim 8, is characterized in that, it is characterized in that, described first precipitation is 1mg:1 ~ 50mL with the mass volume ratio of described eluant, eluent.
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| CN108344871A (en) * | 2017-01-23 | 2018-07-31 | 复旦大学 | A method of based on fluorine solid phase extraction concentration peptide fragment containing cysteine and carrying out mass spectral analysis |
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| CN105148880A (en) * | 2015-07-16 | 2015-12-16 | 东华大学 | Preparation method and application method for graphene microsphere solid-phase extractant |
| CN106018641A (en) * | 2016-06-17 | 2016-10-12 | 中华人民共和国金华出入境检验检疫局 | Method for detecting phthalic acid ester in water-based food simulants through dispersive solid-phase extraction-gas chromatography-mass spectrometry |
| CN108344871A (en) * | 2017-01-23 | 2018-07-31 | 复旦大学 | A method of based on fluorine solid phase extraction concentration peptide fragment containing cysteine and carrying out mass spectral analysis |
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| CN108499549A (en) * | 2018-03-30 | 2018-09-07 | 广州质量监督检测研究院 | Solid phase micro-extracting head and preparation method thereof for being enriched with perfluorochemical |
| 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 |
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