CN107129562B - Magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer - Google Patents
Magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer Download PDFInfo
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- CN107129562B CN107129562B CN201710387105.0A CN201710387105A CN107129562B CN 107129562 B CN107129562 B CN 107129562B CN 201710387105 A CN201710387105 A CN 201710387105A CN 107129562 B CN107129562 B CN 107129562B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 31
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 30
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000010828 elution Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 105
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 9
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 7
- 229910000071 diazene Inorganic materials 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 abstract description 49
- 238000001179 sorption measurement Methods 0.000 abstract description 42
- 239000003814 drug Substances 0.000 abstract description 31
- 229940079593 drug Drugs 0.000 abstract description 28
- 229940124307 fluoroquinolone Drugs 0.000 abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 15
- 229960001699 ofloxacin Drugs 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 229920002678 cellulose Polymers 0.000 description 12
- 239000001913 cellulose Substances 0.000 description 12
- FABPRXSRWADJSP-MEDUHNTESA-N moxifloxacin Chemical compound COC1=C(N2C[C@H]3NCCC[C@H]3C2)C(F)=CC(C(C(C(O)=O)=C2)=O)=C1N2C1CC1 FABPRXSRWADJSP-MEDUHNTESA-N 0.000 description 11
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 8
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- XUBOMFCQGDBHNK-JTQLQIEISA-N (S)-gatifloxacin Chemical compound FC1=CC(C(C(C(O)=O)=CN2C3CC3)=O)=C2C(OC)=C1N1CCN[C@@H](C)C1 XUBOMFCQGDBHNK-JTQLQIEISA-N 0.000 description 4
- XBHBWNFJWIASRO-UHFFFAOYSA-N 6-fluoro-1-(4-fluorophenyl)-4-oxo-7-(1-piperazinyl)-3-quinolinecarboxylic acid Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1=CC=C(F)C=C1 XBHBWNFJWIASRO-UHFFFAOYSA-N 0.000 description 4
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229960003405 ciprofloxacin Drugs 0.000 description 4
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- 238000000605 extraction Methods 0.000 description 4
- 229960003923 gatifloxacin Drugs 0.000 description 4
- 229960002422 lomefloxacin Drugs 0.000 description 4
- ZEKZLJVOYLTDKK-UHFFFAOYSA-N lomefloxacin Chemical compound FC1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNC(C)C1 ZEKZLJVOYLTDKK-UHFFFAOYSA-N 0.000 description 4
- 229960003702 moxifloxacin Drugs 0.000 description 4
- 229950007734 sarafloxacin Drugs 0.000 description 4
- 229960004954 sparfloxacin Drugs 0.000 description 4
- DZZWHBIBMUVIIW-DTORHVGOSA-N sparfloxacin Chemical compound C1[C@@H](C)N[C@@H](C)CN1C1=C(F)C(N)=C2C(=O)C(C(O)=O)=CN(C3CC3)C2=C1F DZZWHBIBMUVIIW-DTORHVGOSA-N 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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Abstract
The invention belongs to the technical field of molecular imprinting polymers, and particularly discloses a magnetic nanocrystalline cellulose-grafted graphene oxide surface molecular imprinting polymer, which is prepared by grafting a magnetic nanocrystalline cellulose-grafted graphene oxide compound Fe3O4The method comprises the following steps of using @ GO-g-CNC as a carrier, using ofloxacin OFX as a template molecule, using methacrylic acid MAA as a functional monomer, forming a polymer through a polymerization reaction, and eluting the template molecule in the polymer to obtain a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer Fe3O4@ GO-g-CNC @ MIPs, Fe of the invention3O4The @ GO-g-CNC @ MIPs have the large adsorption capacity of graphene, have a spatial structure and a binding site which are completely matched with OFX, can adsorb fluoroquinolone medicines in a water body, have high selective adsorption on the fluoroquinolone medicines, can be repeatedly used through adsorption-elution, and have low treatment cost.
Description
Technical Field
The invention belongs to the technical field of molecularly imprinted polymers, and particularly relates to a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer.
Background
The fluoroquinolone medicines FQs are artificially synthesized broad-spectrum and high-efficiency antibacterial medicines, and have the advantages of good absorption, long half-life period, quick bacteriostatic and bactericidal effects and the like, so that the fluoroquinolone medicines are widely used for antibiotics taken by human bodies or are widely used for animals as veterinary medicines and feed additives. After being ingested by animals, the fluoroquinolone medicaments only leave 10 to 20 percent of small amount of the fluoroquinolone medicaments in vivo and in vitro, and most of the fluoroquinolone medicaments are discharged out of the bodies along with the feces and urine of animals or human and flow into the natural water environment through links such as sewage treatment and the like. The water bodies are treated by the conventional technology and then are used as domestic water for human beings, so that fluoroquinolone medicines in the water bodies can directly cause harm to human bodies, and can generate drug resistance to pathogenic bacteria sensitive to FQs medicines to indirectly harm human health. Therefore, the method needs to enrich and remove the Voronoquine drugs in the water environment so as to reduce FQs harm to the environment and human body. The existing methods for treating fluoroquinolone drugs comprise biochemical methods and physicochemical methods, but the biochemical methods have complex treatment conditions, harsh microbial growth conditions, long treatment period and low treatment efficiency. The physicochemical law requires a large amount of chemical reagents, and the waste generated after treatment is easy to cause pollution. Therefore, there is a need for a method for treating fluoroquinolone drugs which has a high treatment effect, a short treatment time, little contamination, and is reproducible.
Chinese patent CN2013104232997, entitled a method for treating ofloxacin-containing wastewater by using an electron beam irradiation technology, which is filed on application date of 2013, 9, 17, discloses a method for promoting degradation of ofloxacin by irradiating a water body containing ofloxacin pollutants by using an electron beam accelerator, but the method cannot effectively degrade a plurality of fluoroquinolone drugs at the same time, and irradiation may affect other substances in the water body.
The graphene is a honeycomb single-layer carbon atom crystal composed of sp2 hybridized atoms, the graphene can be used for loading a large number of various molecules and has very high adsorption capacity due to the single atom thickness and the two-dimensional plane structure, the surface adsorption characteristic and the pi-pi adsorption characteristic of the graphene have very high adsorption speed and capacity for organic matters containing aromatic benzene rings, and meanwhile, the connection of carbon atoms in the graphene is very flexible, so that the graphene shows good stability.
The molecular imprinting polymer is a high molecular polymer which is prepared by utilizing a molecular imprinting technology and is completely matched with template molecules in a spatial structure and a binding site. The molecular engram polymer can absorb a large amount of substances with similar molecular structures with the template, and can be used as a reactivity controlled release carrier, so that the molecular engram polymer can be used as a carrier with adsorbed drug molecules to enter a human body to gradually release the drug molecules. However, the application of the molecularly imprinted polymer in adsorbing organic pollutants has not appeared.
Disclosure of Invention
Aiming at the problems of low treatment efficiency, high cost and easy pollution risk existing in the existing method for treating the fluoroquinolone medicines, the invention aims to provide the magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer which can adsorb the fluoroquinolone medicines in a water body, has high selective adsorption on the fluoroquinolone medicines, can be repeatedly used through adsorption-elution, has low treatment cost and has no pollution to the environment.
The invention provides the following technical scheme:
the magnetic nano-crystalline cellulose grafted graphene oxide surface molecularly imprinted polymer is characterized in that a magnetic nano-crystalline cellulose grafted graphene oxide compound Fe3O4The method comprises the following steps of using @ GO-g-CNC as a carrier, using ofloxacin OFX as a template molecule, using methacrylic acid MAA as a functional monomer, forming a polymer through a polymerization reaction, and eluting the template molecule in the polymer to obtain a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer Fe3O4@GO-g-CNC@MIPs。
The preparation method of the magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer according to claim 1, comprising the following steps:
(1) dissolving OFX in dimethyl sulfoxide, adding MAA, and stirring at the speed of 30-45 r/min for 30-45 min to fully pre-assemble template molecules and functional monomers to prepare a pre-assembled solution;
(2) taking 4-4.8 m L of dimethyl sulfoxide and adding 1.0-1.2 g of Fe3O4Dissolving @ GO-g-CNC to prepare a carrier solution;
(3) taking 100-120 m L of dimethyl sulfoxide aqueous solution, adding 0.4-0.48 g of polyethylene glycol, and fully dissolving to prepare a dispersant solution, wherein the volume ratio of the dimethyl sulfoxide to the water is 9: 1;
(4) mixing the pre-assembly solution with a carrier solution, then adding 20-24 mmol of ethylene glycol dimethacrylate EGDMA, and then adding a dispersant solution to obtain a mixed solution;
(5) continuously introducing nitrogen into the mixed solution, keeping the temperature of the mixed solution at 55-65 ℃, and then adding 0.1-0.12 g of Azobisisobutyronitrile (AIBN) to initiate polymerization for 10-14 hours to obtain a polymer solution;
(6) separating the polymer from the polymer solution through a magnetic field, washing the polymer for 3-5 times by using deionized water, and eluting by using an acetic acid-methanol mixed solution until the OFX concentration in the eluent is lower than the detection lower limit of a high performance liquid chromatography, wherein the acetic acid concentration is 30-40% v/v;
(7) freeze-drying the polymer at-40 deg.C for 32h to obtain Fe3O4@GO-g-CNC@MIPs。
As an improvement of the method, the addition amount of the OFX in the step (1) is 1-1.2 mmol, the addition amount of the MAA is 4-4.8 mmol, and the volume of the dimethyl sulfoxide is 10-12 ml.
As an improvement of the process of the invention, Fe in step (2)3O4The @ GO-g-CNC is prepared by the following steps:
firstly, adding graphene into morpholine ethanesulfonic acid buffer solution for ultrasonic dissolution, then adding diimine hydrochloride and N-hydroxysuccinimide for mixing and carrying out ultrasonic auxiliary reaction for 1-1.5 h, and then centrifuging to obtain graphene oxide GO, wherein the ultrasonic frequency is 53KHz, the ultrasonic power is 100w, and the temperature of the ultrasonic solution is 20 ℃;
secondly, adding GO into a p-benzoquinone solution PBQ with the pH value of 9.5-10.5, stirring and reacting for 45-75 min at 40-50 ℃, centrifuging to obtain a precipitate, adding the precipitate into pure water, adding nanocrystalline cellulose CNC (computerized numerical control) for mixing, continuing stirring and reacting for 45-75 min at 40-50 ℃, and freeze-drying for 32h in a vacuum environment at-40 ℃ to obtain nanocrystalline cellulose grafted graphene oxide GO-g-CNC;
thirdly, adding GO-g-CNC into deionized water, introducing nitrogen to remove oxygen in water, adding FeCl3·6H2O and FeCl2·4H2Adjusting the pH value of the solution to 9-10, stirring and reacting at 70-80 ℃ for 45-75 min to obtain a composition, separating the solution and the composition through a magnetic field, and alternately cleaning the composition with deionized water and ethanol until the cleaning solution is neutral to obtain Fe3O4@GO-g-CNC。
As an improvement of the method, in the first step, the mass of the graphene is 100-120 mg, the mass of the diimine hydrochloride is 9.6-11.5 mg, the mass of the N-hydroxysuccinimide is 5.8-7.0 mg, and the volume of the morpholine ethanesulfonic acid buffer solution is 30-42 ml.
As an improvement of the method, in the second step, the concentration of PBQ is 0.04 mol/L, the volume is 50-60 m L, and the mass of pure water with the volume of 50-60 m L is 100-120 mg.
As an improvement of the method, in the third step, the mass of GO-g-CNC is 200-240 mg, and FeCl is added3·6H2O and FeCl2·4H2The mass of the O is 2.4-2.88 g and 0.9-1.08 g respectively, and the volume of the deionized water is 80-96 m L.
As an improvement of the method, the analysis conditions of the high performance liquid chromatography in the step (6) are that a mobile phase consists of acetonitrile (A liquid) and 0.05% v/v phosphoric acid aqueous solution (B liquid), the detection wavelength is 290nm, the liquid inlet amount is 20 mu L, the temperature of a chromatographic column is 25 ℃, and the gradient elution procedure comprises 0-6 min, 85.0% v/v of the B liquid, the balance of the A liquid, 6-6.2 min, 85.0% v/v-83.0% v/v of the B liquid, the balance of the A liquid, 6.2-10 min, 83.0% v/v of the B liquid, the balance of the A liquid, 10-10.2 min, 83.0% v/v-78.0% v/v of the B liquid, the balance of the A liquid, 10.2-15 min, 78.0% v/v of the B liquid and the balance of the A liquid.
An application of a magnetic nano-crystalline cellulose grafted graphene oxide surface molecularly imprinted polymer in extraction of fluoroquinolone medicines in a water body, wherein the fluoroquinolone medicines comprise ofloxacin OFX, ciprofloxacin CIP, lomefloxacin L OM, enrofloxacin ENRO, gatifloxacin GAT, sarafloxacin SARA, sparfloxacin SPX, moxifloxacin MFX and Marpafloxacin MARBO.
The graphene surface molecularly imprinted polymer Fe3O4@ GO-g-CNC @ MIPs is a honeycomb single-layer carbon atom crystal composed of sp2 hybridized atoms, the graphene can be used for loading a large number of various molecules and has very high adsorption capacity due to the single atom thickness and the two-dimensional plane structure, the surface adsorption property and the pi-pi adsorption property of the graphene have very high adsorption speed and capacity on organic matters containing aromatic benzene rings, meanwhile, the carbon atom connection of the graphene is very flexible, the graphene shows good stability, the graphene oxide GO is obtained through functional treatment of the graphene, GO has high specific surface area and functional groups rich on the surface, the graphene is more active than the graphene, the property of the graphene can be improved through various reactions with oxygen-containing functional groups, the hydrophilic-hydrophobic property distribution is shown from the edge to the center of a sheet, the GO is connected with the GO, the obtained GO has good biological and reproducible properties and stably exists in various biological solutions, the obtained through the magnetization of the GO-G357-PEG-3, the obtained through the repeated adsorption of the PEG-3, the PEG-7-PEG-O-3, the poly-O-3-O-3-A-O.
The invention has the following beneficial effects:
the magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer has larger adsorption capacity and surface area, has a spatial structure and a binding site which are completely matched with OFX, can adsorb fluoroquinolone medicines in a water body, has high selectivity on the fluoroquinolone medicines, can be repeatedly used by adsorption-elution, has low treatment cost and does not pollute the environment.
Drawings
FIG. 1 is Fe3O4A preparation flow chart of @ GO-g-CNC @ MIPs.
FIG. 2 is an electronic scanning visualization of GO.
FIG. 3 is an electronic scanning visualization of CNC.
FIG. 4 is an electronic scanning visualization of GO-g-CNC.
FIG. 5 is Fe3O4The electronic scanning and image display of @ GO-g-CNC.
FIG. 6 is Fe3O4The electronic scanning and image display of @ GO-g-CNC @ MIPs.
FIG. 7 is Fe3O4Adsorption capacity plot of @ GO-g-CNC @ MIPs adsorption/elution OFX repeat.
Detailed Description
The following further describes the embodiments of the present invention.
The starting materials used in the present invention are commercially available or commonly used in the art, unless otherwise specified, and the methods in the following examples are conventional in the art, unless otherwise specified.
Example 1
As shown in FIG. 1, a magnetic nano-crystalline cellulose grafted graphene oxide surface molecularly imprinted polymer is prepared by grafting a magnetic nano-crystalline cellulose grafted graphene oxide compound Fe3O4The method comprises the following steps of using @ GO-g-CNC as a carrier, using ofloxacin OFX as a template molecule, using methacrylic acid MAA as a functional monomer, forming a polymer through a polymerization reaction, and eluting the template molecule in the polymer to obtain a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer Fe3O4@GO-g-CNC@MIPs。
A preparation method of a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer comprises the following steps:
(1) dissolving 1mmol of OFX in 10ml of dimethyl sulfoxide, adding 4mmol of MAA, stirring at the speed of 30r/min for 30min to fully pre-assemble the template molecules and the functional monomers to prepare a pre-assembly solution;
(2) another 4m of L dimethyl sulfoxide was taken and 1.0g of Fe was added3O4Dissolving @ GO-g-CNC to prepare a carrier solution;
(3) taking 100m L of dimethyl sulfoxide aqueous solution, adding 0.4g of polyethylene glycol, and fully dissolving to prepare a dispersant solution, wherein the volume ratio of the dimethyl sulfoxide to the water is 9: 1;
(4) mixing the pre-assembly solution with a carrier solution, then adding 20mmol of ethylene glycol dimethacrylate EGDMA, and then adding a dispersant solution to obtain a mixed solution;
(5) continuously introducing nitrogen into the mixed solution, keeping the temperature of the mixed solution at 55 ℃, and then adding 0.1g of Azobisisobutyronitrile (AIBN) to initiate polymerization for 10 hours to obtain a polymer solution;
(6) separating the polymer from the polymer solution by a magnetic field, washing the polymer for 3 times by deionized water, and eluting by using an acetic acid-methanol mixed solution until the concentration of ofloxacin in an eluent is lower than the detection lower limit of a high performance liquid chromatography, wherein the concentration of acetic acid is 30% v/v, and the analysis conditions of the high performance liquid chromatography are as follows, wherein a mobile phase consists of acetonitrile (A solution) and 0.05% v/v phosphoric acid aqueous solution (B solution), the detection wavelength is 290nm, the liquid inlet amount is 20 mu L, the temperature of a chromatographic column is 25 ℃, the gradient elution procedure is 0-6 min, 85.0% v/v-83.0% v/v of B solution, the rest is A solution, 6.2-10 min, 83.0% v/v of B solution, the rest is A solution, 10-10.2 min, 83.0% v/v-78.0% v/v of B solution, the rest is A solution, 10-10.2 min, 83.0% v/v-78.0% v/v of B solution, the rest is A solution, 10.2min, 15.0% v/v of B solution, and;
(7) freeze-drying the polymer at-40 deg.C for 32h to obtain Fe3O4@GO-g-CNC@MIPs。
The magnetic nanocrystalline cellulose grafted graphene oxide compound in the step (2) is prepared by the following steps:
step one, adding 100mg of graphene into 30ml of morpholine ethanesulfonic acid buffer solution for ultrasonic dissolution, then adding 9.6mg of diimine hydrochloride and 5.8mg of N-hydroxysuccinimide for mixing, carrying out ultrasonic-assisted reaction for 1h, and then centrifuging to obtain graphene oxide GO, wherein the ultrasonic frequency is 53KHz, the ultrasonic power is 100w, and the temperature of the ultrasonic solution is 20 ℃;
secondly, adding GO into a 0.04 mol/L p-benzoquinone solution PBQ with the pH value of 9.5, wherein the volume of the PBQ is 50m L, stirring and reacting at 40 ℃ for 45min, centrifuging to obtain a precipitate, adding the precipitate into 50m L pure water, adding 100mg of CNC (computerized numerical control) for mixing, continuing stirring and reacting at 40 ℃ for 45min, and freeze-drying at-40 ℃ for 32h to obtain the GO-g-CNC;
thirdly, 200mg of GO-g-CNC was added to 80m L of deionized water, nitrogen was bubbled in to remove oxygen in the water, 2.4g of FeCl was added3·6H2O and 0.9g FeCl2·4H2O, adjusting the pH value of the solution to 9, stirring and reacting for 45min at 70 ℃ to obtain a compound, separating the solution and the compound through a magnetic field, and alternately cleaning the compound by using deionized water and ethanol until the cleaning solution is neutral to obtain Fe3O4@GO-g-CNC@MIPs。
An application of a magnetic nano-crystalline cellulose grafted graphene oxide surface molecularly imprinted polymer in extraction of fluoroquinolone medicines in a water body is disclosed, wherein the fluoroquinolone medicines comprise ofloxacin OFX, ciprofloxacin CIP, lomefloxacin L OM, enrofloxacin ENRO, gatifloxacin GAT, sarafloxacin SARA, sparfloxacin SPX, moxifloxacin MFX and Marpafloxacin MARBO.
Example 2
As shown in FIG. 1, a magnetic nano-crystalline cellulose grafted graphene oxide surface molecularly imprinted polymer is prepared by grafting a magnetic nano-crystalline cellulose grafted graphene oxide compound Fe3O4The method comprises the following steps of using @ GO-g-CNC as a carrier, using ofloxacin OFX as a template molecule, using methacrylic acid MAA as a functional monomer, forming a polymer through a polymerization reaction, and eluting the template molecule in the polymer to obtain a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer Fe3O4@GO-g-CNC@MIPs。
A preparation method of a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer comprises the following steps:
(1) dissolving 1.1mmol of OFX in 11ml of dimethyl sulfoxide, adding 4.4mmol of MAA (methacrylic acid), and stirring at the speed of 42r/min for 42min to fully pre-assemble the template molecules and the functional monomers to prepare a pre-assembly solution;
(2) another 4.4m of L dimethyl sulfoxide was taken and 1.1g of Fe was added3O4Dissolving @ GO-g-CNC to prepare a carrier solution;
(3) taking 110m L of dimethyl sulfoxide aqueous solution, adding 0.44g of polyethylene glycol, and fully dissolving to prepare a dispersant solution, wherein the volume ratio of the dimethyl sulfoxide to the water is 9: 1;
(4) mixing the pre-assembly solution with a carrier solution, then adding 22mmol of ethylene glycol dimethacrylate FGDMA, and then adding a dispersant solution to obtain a mixed solution;
(5) continuously introducing nitrogen into the mixed solution, keeping the temperature of the mixed solution at 60 ℃, and then adding 0.11g of Azobisisobutyronitrile (AIBN) to initiate polymerization for 12 hours to obtain a polymer solution;
(6) separating the polymer from the polymer solution by a magnetic field, washing the polymer for 4 times by deionized water, and eluting by using an acetic acid-methanol mixed solution until the concentration of ofloxacin in an eluent is lower than the detection lower limit of a high performance liquid chromatography, wherein the concentration of acetic acid is 35% v/v, and the analysis conditions of the high performance liquid chromatography are as follows, wherein a mobile phase consists of acetonitrile (A solution) and 0.05% v/v phosphoric acid aqueous solution (B solution), the detection wavelength is 290nm, the liquid inlet amount is 20 mu L, the temperature of a chromatographic column is 25 ℃, the gradient elution procedure is 0-6 min, 85.0% v/v of B solution is 85.0% v/v, the rest is A solution, 6.2-10 min, 83.0% v/v of B solution is 10-10.2 min, 83.0% v/v-78.0% v/v, the rest is A solution, 10-10.2 min, 83.0% v/v-78.0% v/v of B solution is 10.0% v/v, the rest is A solution;
(7) freeze-drying the polymer at-40 deg.C for 32h to obtain Fe3O4@GO-g-CNC@MIPs。
The magnetic nanocrystalline cellulose grafted graphene oxide compound in the step (2) is prepared by the following steps:
firstly, adding 110mg of graphene into 36ml of morpholine ethanesulfonic acid buffer solution for ultrasonic dissolution, then adding 10.55mg of diimine hydrochloride and 6.4mg of N-hydroxysuccinimide for mixing and carrying out ultrasonic-assisted reaction for 1-1.5 h, and then centrifuging to obtain graphene oxide GO, wherein the ultrasonic frequency is 53KHz, the ultrasonic power is 100w, and the temperature of the ultrasonic solution is 20 ℃;
secondly, adding GO into a 0.04 mol/L p-benzoquinone solution PBQ with the pH value of 10, wherein the volume of the PBQ is 55m L, stirring and reacting at 45 ℃ for 60min, centrifuging to obtain a precipitate, adding the precipitate into 55m L pure water, adding 110mg of nanocrystalline cellulose CNC (computer numerical control) for mixing, continuing stirring and reacting at 45 ℃ for 60min, and then freeze-drying at-40 ℃ for 32h in a vacuum environment to obtain nanocrystalline cellulose grafted graphene oxide GO-g-CNC;
third, add 220mg GO-g-CNC into 88m L DI water, remove oxygen in the water by nitrogen, add 2.64g FeCl3·6H2O and 0.99g FeCl2·4H2O, adjusting the pH value of the solution to 9.5, stirring and reacting for 60min at 75 ℃ to obtain a composition, separating the solution and the composition through a magnetic field, and alternately cleaning the composition by using deionized water and ethanol until the cleaning solution is neutral to obtain Fe3O4@GO-g-CNC@MIPs。
An application of a magnetic nano-crystalline cellulose grafted graphene oxide surface molecularly imprinted polymer in extraction of fluoroquinolone medicines in a water body, wherein the fluoroquinolone medicines comprise ofloxacin OFX, ciprofloxacin CIP, lomefloxacin L OM, enrofloxacin ENRO, gatifloxacin GAT, sarafloxacin SARA, sparfloxacin SPX, moxifloxacin MFX and Marpafloxacin MARBO.
Example 3
As shown in FIG. 1, a magnetic nano-crystalline cellulose grafted graphene oxide surface molecularly imprinted polymer is prepared by grafting a magnetic nano-crystalline cellulose grafted graphene oxide compound Fe3O4The method comprises the following steps of using @ GO-g-CNC as a carrier, using ofloxacin OFX as a template molecule, using methacrylic acid MAA as a functional monomer, forming a polymer through a polymerization reaction, and eluting the template molecule in the polymer to obtain a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer Fe3O4@GO-g-CNC@MIPs。
A preparation method of a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer comprises the following steps:
(1) dissolving 1.2mmol of OFX in 12ml of dimethyl sulfoxide, adding 4.8mmol of MAA, and stirring at 45r/min for 45min to fully pre-assemble template molecules and functional monomers to prepare a pre-assembly solution;
(2) another 4.8m L m of dimethyl sulfoxide was taken and 1.2g of Fe was added3O4Dissolving @ GO-g-CNC to prepare a carrier solution;
(3) taking 120m L of dimethyl sulfoxide aqueous solution, adding 0.48g of polyethylene glycol, and fully dissolving to prepare a dispersant solution, wherein the volume ratio of the dimethyl sulfoxide to the water is 9: 1;
(4) mixing the pre-assembly solution with a carrier solution, then adding 24mmol of ethylene glycol dimethacrylate EGDMA, and then adding a dispersant solution to obtain a mixed solution;
(5) continuously introducing nitrogen into the mixed solution, keeping the temperature of the mixed solution at 65 ℃, and then adding 0.12g of Azobisisobutyronitrile (AIBN) to initiate polymerization for 14 hours to obtain a polymer solution;
(6) separating the polymer from the polymer solution by a magnetic field, washing the polymer for 5 times by deionized water, and eluting by using an acetic acid-methanol mixed solution until the concentration of ofloxacin in an eluent is lower than the detection lower limit of a high performance liquid chromatography, wherein the concentration of acetic acid is 40% v/v, and the analysis conditions of the high performance liquid chromatography are as follows, wherein a mobile phase consists of acetonitrile (A solution) and 0.05% v/v phosphoric acid aqueous solution (B solution), the detection wavelength is 290nm, the liquid inlet amount is 20 mu L, the temperature of a chromatographic column is 25 ℃, the gradient elution procedure is 0-6 min, 85.0% v/v of B solution is 85.0% v/v, the rest is A solution, 6.2-10 min, 83.0% v/v of B solution is 10-10.2 min, 83.0% v/v-78.0% v/v, the rest is A solution, 10-10.2 min, 83.0% v/v-78.0% v/v of B solution is 10.0% v/v, the rest is A solution;
(7) freeze-drying the polymer at-40 deg.C for 32h to obtain Fe3O4@GO-g-CNC@MIPs。
The magnetic nanocrystalline cellulose grafted graphene oxide compound in the step (2) is prepared by the following steps:
step one, adding 120mg of graphene into 42ml of morpholine ethanesulfonic acid buffer solution for ultrasonic dissolution, then adding 11.5mg of diimine hydrochloride and 7.0mg of N-hydroxysuccinimide for mixing and carrying out ultrasonic-assisted reaction for 1-1.5 h, and then centrifuging to obtain graphene oxide GO, wherein the ultrasonic frequency is 53KHz, the ultrasonic power is 100w, and the temperature of the ultrasonic solution is 20 ℃;
secondly, adding GO into a 0.04 mol/L p-benzoquinone solution PBQ with the pH value of 10.5, wherein the volume of the PBQ solution is 60m L, stirring and reacting at 50 ℃ for 75min, centrifuging to obtain a precipitate, adding the precipitate into pure water with the volume of 60m L, adding 120mg of nanocrystalline cellulose CNC (computerized numerical control) for mixing, continuously stirring and reacting at 50 ℃ for 75min, and then freeze-drying at-40 ℃ for 32h in a vacuum environment to obtain nanocrystalline cellulose grafted graphene GO-g-CNC;
third, 240mg of GO-g-CNC was added to 96m L of deionized water, nitrogen was bubbled through to remove oxygen in the water, 2.88g of FeCl was added3·6H2O and 1.08g of FeCl2·4H2Adjusting the pH value of the solution to 9-10, stirring and reacting at 80 ℃ for 75min to obtain a composition, separating the solution and the composition through a magnetic field, and alternately cleaning the composition with deionized water and ethanol until the cleaning solution is neutral to obtain Fe3O4@GO-g-CNC@MIPs。
An application of a magnetic nano-crystalline cellulose grafted graphene oxide surface molecularly imprinted polymer in extraction of fluoroquinolone medicines in a water body is disclosed, wherein the fluoroquinolone medicines comprise ofloxacin OFX, ciprofloxacin CIP, lomefloxacin L OM, enrofloxacin ENRO, gatifloxacin GAT, sarafloxacin SARA, sparfloxacin SPX, moxifloxacin MFX and Marpafloxacin MARBO.
Performance index
1.Fe3O4Electronic scanning image display of @ GO-g-CNC @ MIPs
As shown in fig. 2, GO has a sheet structure, a smooth surface and a relatively large surface area. As can be seen from fig. 3, the surface of the CNC shows a collection of several spherical particles, and part of the particles are in a triangular or tetragonal structure. Due to the grafted CNC, as shown in fig. 4, the surface of GO becomes a flaky structure after GO is coupled with CNC, reflecting its layered microstructure and relatively rough surface. As shown in FIG. 5, in Fe3O4Irregularly shaped particles and a rougher surface can be observed in @ GO-g-CNC, due to the magnetic Fe3O4Are aggregated with each other, and Fe3O4Is combined with the surface of GO-g-CNC. From FIG. 6, a random fibrous and very dense surface was observed, which indicates that in Fe3O4The surface molecular imprinting layer is formed around the @ GO-g-CNC particles, and the existence of the surface molecular imprinting layer influences the finally formed Fe3O4The structure of @ GO-g-CNC @ MIPs.
2.Fe3O4Repeated adsorption/elution Capacity of @ GO-g-CNC @ MIPs on OFX
10mg of Fe are weighed3O4@ GO-g-CNC @ MIPs were placed in an erlenmeyer flask, 1mg/m L OFX solution 10m L was added, adsorption was performed with shaking at 23 + -2 ℃ for 2h, the shaking frequency was 150rpm, the concentration of OFX in the supernatant at equilibrium was determined with HP L C, and then Fe was eluted with 30% v/v acetic acid/methanol solution3O4@ GO-g-CNC @ MIPs to remove OFX, Fe3O4@ GO-g-CNC @ MIPs were added again to 10m L of 1mg/m L OFX solution, the adsorption/elution was repeated so many times, the concentration of OFX in the supernatant at equilibrium was determined, and Fe was calculated3O4O/F (ion exchange capacity) Q of @ GO-g-CNC @ MIPs on OFX (OFX)OFXThe results are shown in FIG. 7. As can be seen from FIG. 7, Fe was observed with the increase of the adsorption/elution times3O4The adsorption capacity of @ GO-g-CNC @ MIPs to OFX is gradually reduced, after the OFX is adsorbed and used for 7 times, the adsorption capacity is reduced by 13%, the OFX still has good adsorption performance, and the adsorption capacity is over 66mg/g, which shows that Fe3O4The @ GO-g-CNC @ MIPs have good and stable cyclic utilization performance for adsorbing OFX, and are suitable for recycling.
3.Fe3O4FQs adsorption recovery from water body by @ GO-g-CNC @ MIPs
Detecting a water sample in a river in Zhoshan of Zhejiang by HP L C, detecting that no FQs residue is detected in the water sample, then taking 3 water samples of 5m L respectively, carrying out standard adding treatment on 9 water samples of FQs, wherein the standard adding concentrations of the 9 water samples of FQs are respectively 0.1 mu g/m L, 0.5 mu g/m L and 1 mu g/m L, and then adding 10mg of Fe3O4@ GO-g-CNC @ MIPs were adsorbed for 50min, then eluted with 30% v/v acetic acid/methanol solution, and FQs content in the water sample was determined using HP L C, the calculation results are shown in Table 1 below.
As can be seen from Table 1, under three different standard concentrations, the standard recovery rate of FQs in the water sample is 79.2-96.1%, the relative standard deviation range is 1.1-7.1%, the detection limit (signal-to-noise ratio is 3) of FQs is 6.5-50.9 ng/m L, the quantification limit (signal-to-noise ratio is 10) is 21.6-169.5 ng/m L. Fe3O4The @ GO-g-CNC @ MIPs effectively adsorb and enrich fluoroquinolone drugs, and the recovery effect is stable and reliable.
TABLE 1
4.Fe3O4Selective absorption of @ GO-g-CNC @ MIPs to FQs
Firstly according to the preparation of Fe3O4Method for preparing magnetic nanocrystalline cellulose grafted graphene oxide surface molecular non-imprinted polymer Fe by @ GO-g-CNC @ MIPs3O4@GO-g-CNC@NIPs，Fe3O4Preparation method of @ GO-g-CNC @ NIPs and Fe3O4The difference of the preparation method of @ GO-g-CNC @ MIPs is that the preparation process is not carried outThe template molecule OFX was added. Then testing Fe3O4@ GO-g-CNC @ MIPs and Fe3O4The selective adsorption effect of @ GO-g-CNC @ NIPs on 9 FQs types comprises the following specific steps:
9 parts of 10mg Fe were weighed out separately3O4@ GO-g-CNC @ MIPs are placed in 9 conical flasks, and 9 parts of 10mg Fe are weighed simultaneously3O4@ GO-g-CNC @ NIPs are placed in another 9 conical flasks, 9 mixed solutions of OFX, CIP, L OM, ENRO, GAT, SARA, SPX, MFX, MARBO and SMZ are respectively prepared by taking sulfamethoxazole SMZ as competitive molecules, the solute concentration in each mixed solution is 20 mug/m L, and 5m L of each mixed solution is respectively added into the mixed solution containing Fe3O4Adjusting the pH value to 6 in an @ GO-g-CNC @ MIPs conical flask, carrying out oscillation adsorption for 2h at 25 ℃, and respectively adding 5m L of mixed solution into the conical flask containing Fe3O4Adjusting the pH value to 6 in an @ GO-g-CNC @ NIPs conical flask, carrying out oscillation adsorption for 2h at 25 ℃, determining the concentration of each solute in the mixed solution, and calculating Fe3O4@ GO-g-CNC @ MIPs and Fe3O4Adsorption quantity Q, Fe of @ GO-g-CNC @ NIPs to each solute3O4@GO-g-CNC@MIP、Fe3O4Selection coefficient SC of @ GO-g-CNC @ MIP for FQs and SMZ respectivelyMIP、SCNIP，Fe3O4@ GO-g-CNC @ MIP vs. Fe3O4@ GO-g-CNC @ NIPs adsorbed FQs for imprinting factor IF, with results shown in Table 2.
IF＝QMIP/QNIP，SCMIP＝QMFQs/QMSMZ，SCNIP＝QNFQs/QNSMZ；
Wherein Q isMIPRepresents Fe3O4The adsorption capacity of @ GO-g-CNC @ MIPs to each solute, QMFQsRepresents Fe3O4Adsorption capacity of @ GO-g-CNC @ MIPs to FQs, QMSMZRepresents Fe3O4Adsorption capacity of @ GO-g-CNC @ MIPs to SMZ, QNIPRepresents Fe3O4The adsorption capacity of @ GO-g-CNC @ NIPs to each solute, QNFQsRepresents Fe3O4Adsorption capacity of @ GO-g-CNC @ NIPs to FQs, QNSMZRepresents Fe3O4@ GO-g-CNC @ NIPs pairsAmount of SMZ adsorbed.
TABLE 2
| FQs | MARBO | OFX | CIP | LOM | ENRO | GAT | SARA | SPX | MFX | SMZ |
| QMIP(mg/g) | 4.90 | 13.04 | 5.29 | 4.93 | 10.39 | 7.62 | 10.51 | 8.63 | 11.61 | 3.61 |
| QNIP(mg/g) | 3.39 | 4.18 | 3.71 | 3.18 | 4.16 | 3.54 | 4.07 | 3.25 | 3.95 | 3.52 |
| Blotting factor IF | 1.45 | 3.12 | 1.43 | 1.55 | 2.50 | 2.15 | 2.48 | 2.66 | 2.94 | 1.03 |
| Selection system SCMIP | 1.36 | 3.61 | 1.46 | 1.37 | 2.88 | 2.11 | 2.91 | 2.39 | 3.22 | - |
| Selection system SCNIP | 0.96 | 1.19 | 1.05 | 0.90 | 1.18 | 1.01 | 1.16 | 0.92 | 1.12 | - |
As can be seen from Table 2, Fe3O4The adsorption quantity Q of @ GO-g-CNC @ MIPs to each solute respectivelyMIPIs obviously greater than Fe3O4Adsorption quantity Q of @ GO-g-CNC @ NIPs to each solute respectivelyNIPMeanwhile, the imprinting factor IF is obviously larger than 1, which indicates that Fe is caused by elution of the template molecule OFX3O4There are more adsorption sites in @ GO-g-CNC @ MIPs, resulting in Fe3O4@ GO-g-CNC @ MIPs vs. Fe3O4@ GO-g-CNC @ NIPs have greater adsorption capacity. Selecting coefficients SC simultaneouslyMIPA significant increase in 1 indicates Fe3O4The @ GO-g-CNC @ MIPs pair FQs has better selective adsorption effect than SMZ, and the selection coefficient SCNIPThe value of (A) is 0.9 to 1.12, indicating that relative to SMZ, Fe3O4The selective adsorption of @ GO-g-CNC @ NIPs to FQs is not obvious, mainly because MARBO, CIP, L OM, ENRO, GAT, SARA, SPX, MFX and OFX have similar spatial structures which can be complemented with imprinting holes on the surface of Fe3O4@ GO-g-CNC @ MIPs, so that Fe3O4@ GO-g-CNC @ MIPs have adsorption selectivity to FQs, while SMZ can only carry out physical adsorption due to mismatching with binding sites, and the adsorption quantity and the selectivity are low.
Claims (5)
1. A preparation method of a magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer comprises the following steps:
(1) dissolving OFX in dimethyl sulfoxide, adding MAA, and stirring at the speed of 30-45 r/min for 30-45 min to fully pre-assemble template molecules and functional monomers to prepare a pre-assembled solution;
(2) taking 4-4.8 m L of dimethyl sulfoxide and adding 1.0-1.2 g of Fe3O4Dissolving @ GO-g-CNC to prepare a carrier solution;
(3) taking 100-120 m L of dimethyl sulfoxide aqueous solution, adding 0.4-0.48 g of polyethylene glycol, and fully dissolving to prepare a dispersant solution, wherein the volume ratio of the dimethyl sulfoxide to the water is 9: 1;
(4) mixing the pre-assembly solution with a carrier solution, then adding 20-24 mmol of ethylene glycol dimethacrylate EGDMA, and then adding a dispersant solution to obtain a mixed solution;
(5) continuously introducing nitrogen into the mixed solution, keeping the temperature of the mixed solution at 55-65 ℃, and then adding 0.1-0.12 g of Azobisisobutyronitrile (AIBN) to initiate polymerization for 10-14 hours to obtain a polymer solution;
(6) separating the polymer from the polymer solution through a magnetic field, washing the polymer for 3-5 times by using deionized water, and eluting by using an acetic acid-methanol mixed solution until the OFX concentration in the eluent is lower than the detection lower limit of a high performance liquid chromatography, wherein the acetic acid concentration is 30-40% v/v;
(7) freeze-drying the polymer at-40 deg.C for 32h to obtain Fe3O4@GO-g-CNC@MIPs；
The addition amount of OFX in the step (1) is 1-1.2 mmol, the addition amount of MAA is 4-4.8 mmol, and the volume of dimethyl sulfoxide is 10-12 ml;
fe in step (2)3O4The @ GO-g-CNC is prepared by the following steps:
firstly, adding graphene into morpholine ethanesulfonic acid buffer solution for ultrasonic dissolution, then adding diimine hydrochloride and N-hydroxysuccinimide for mixing and carrying out ultrasonic auxiliary reaction for 1-1.5 h, and then centrifuging to obtain graphene oxide GO, wherein the ultrasonic frequency is 53KHz, the ultrasonic power is 100w, and the temperature of the ultrasonic solution is 20 ℃;
secondly, adding GO into a p-benzoquinone solution PBQ with the pH value of 9.5-10.5, stirring and reacting for 45-75 min at 40-50 ℃, centrifuging to obtain a precipitate, adding the precipitate into pure water, adding nanocrystalline cellulose CNC (computerized numerical control) for mixing, continuing stirring and reacting for 45-75 min at 40-50 ℃, and freeze-drying for 32h in a vacuum environment at-40 ℃ to obtain nanocrystalline cellulose grafted graphene oxide GO-g-CNC;
thirdly, adding GO-g-CNC into deionized water, introducing nitrogen to remove oxygen in water, adding FeCl3·6H2O and FeCl2·4H2Adjusting the pH value of the solution to 9-10, stirring and reacting at 70-80 ℃ for 45-75 min to obtain a composition, separating the solution and the composition through a magnetic field, and alternately cleaning the composition with deionized water and ethanol until the cleaning solution is neutral to obtain Fe3O4@GO-g-CNC。
2. The preparation method of the magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer according to claim 1, wherein in the first step, the mass of graphene is 100-120 mg, the mass of diimine hydrochloride is 9.6-11.5 mg, the mass of N-hydroxysuccinimide is 5.8-7.0 mg, and the volume of morpholine ethanesulfonic acid buffer solution is 30-42 ml.
3. The preparation method of the magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer according to claim 1, wherein in the second step, the concentration of PBQ is 0.04 mol/L, the volume is 50-60 m L, and the mass of pure water with the volume of 50-60 m L is 100-120 mg.
4. The preparation method of the magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer according to claim 1, wherein the mass of GO-g-CNC in the third step is 200-240 mg, and FeCl is used as a material3·6H2O and FeCl2·4H2The mass of the O is 2.4-2.88 g and 0.9-1.08 g respectively, and the volume of the deionized water is 80-96 m L.
5. The preparation method of the magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer according to claim 1, wherein the analysis conditions of the high performance liquid chromatography in the step (6) are that a mobile phase consists of acetonitrile (A liquid) and 0.05% v/v phosphoric acid aqueous solution (B liquid), the detection wavelength is 290nm, the liquid inlet amount is 20 μ L, the temperature of a chromatographic column is 25 ℃, the gradient elution procedure is that 0-6 min, 85.0% v/v of B liquid and the balance of A liquid are 0-6.2 min, 85.0% v/v-83.0% v/v of B liquid and the balance of A liquid, 6.2-10 min, 83.0% v/v of B liquid and the balance of A liquid, 10-10.2 min, 83.0% v/v-78.0% v/v of B liquid and the balance of A liquid.
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