CN101550207B - Preparation of magnetic molecularly imprinted polymer and application in complex sample pre-processing - Google Patents
Preparation of magnetic molecularly imprinted polymer and application in complex sample pre-processing Download PDFInfo
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- CN101550207B CN101550207B CN2009100669630A CN200910066963A CN101550207B CN 101550207 B CN101550207 B CN 101550207B CN 2009100669630 A CN2009100669630 A CN 2009100669630A CN 200910066963 A CN200910066963 A CN 200910066963A CN 101550207 B CN101550207 B CN 101550207B
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Abstract
The present invention specifically adopts a simple method for preparing a molecularly imprinted polymer and directly applies the molecularly imprinted polymer to the extraction separation of trace substance in the complex sample pre-processing. The invention adopts a chemical coprecipitation method for preparing Fe3O4 magnetofluid. Then the surface of Fe3O4 magnetofluid is modified with oleic acid. The template molecules and functional monomers are realized with preassembling and are mixed with the cross linker and modified magnetofluid. Then the mixture is added into the polymer solvent containing dispersing agent. After the reaction is finished, magnetic field separation is executed. The polymer is dried after eluting the formwork molecules. A three-phase extraction system which is established on the base of magnetic molecularly imprinted polymer can be directly applied to the extraction separation of complex samples of food, environment and biological sample. The method of the invention has excellent selectivity and can eliminate the matrix interference in the sample. Furthermore as the polymer has excellent magnetism, the polymer can excellently realize the separation to the sample matrix after the extraction, and the polymer has broad application prospect in the complex sample pre-processing.
Description
Technical field
The invention belongs to the separate analytical technique field, specifically be to adopt a kind of simple method to prepare magnetic molecularly imprinted polymer, and it is directly applied to the extracting and separating of trace substance in the complex sample pre-treatment.
Background technology
Complex system, as the mixture that food, environmental sample and biological sample mostly are made up of many different substancess, the content of the target components that detect is often very low again, so sample pre-treatments is an important step very during complex sample is analyzed.Traditional pre-treating process needs multi-pass operations mostly, not only consumes a large amount of organic solvents, and needs the cost plenty of time, and analysis efficiency is low.
Molecular imprinting is from bionical angle, adopt the manual method preparation that specific molecular and resemblance thereof are had polymkeric substance---molecularly imprinted polymer (Molecularimprinted polymer, technology MIP) in specificity keying action and particular space structure hole.In recent years, the researchdevelopment in Materials science and isolation technique two big fields has promoted the development of molecular imprinting greatly.Because MIP has advantages such as conformation precordainment, specific recognition, permanent stability and being easy to implement property, demonstrate application prospects aspect many separating purification, immunoassay and biosimulation transmitter etc.
Magnetic polymer is a kind of new function material that is composited by magneticsubstance and non magnetic polymkeric substance.It had both had numerous characteristics of organic polymer, as by the mode of absorption or covalent bonding its surface being modified, combined with compound to be separated then; On the other hand, its superparamagnetism can be separated from medium under adding the action of a magnetic field easily, therefore is suitable for separation, the enrichment of determinand in the complex system.
If magneticsubstance can be imbedded, make magnetic molecularly imprinted polymer in MIP.Just can make the characteristics of its " selectivity " that had both had MIP absorption, has the isolating feature of magneticsubstance " dynamically " again, finish after the active of template molecule and resemblance thereof absorption and the identification at it, just can at an easy rate itself and sample matrices be separated adding under the action of a magnetic field.
The present invention is intended to prepare magnetic molecularly imprinted polymer, and has set up a kind of three phase extraction system be applied to complex sample on its basis, reaches " dynamically " extracting and separating as " selection " of the trace substance in food, environmental sample and the biological sample.
Summary of the invention
The invention provides a kind of easy, the preparation method of the magnetic molecularly imprinted polymer that suitability is wide, and on its basis, set up a kind of three phase extraction system and be applied to complex sample (food, environmental sample and biological sample, as grain, food, the extracting and separating of the trace substance soil, meat etc.) has improved the efficient of sample pre-treatments greatly.
The preparation method of magnetic molecularly imprinted polymer of the present invention comprises the steps:
A. adopt chemical coprecipitation to prepare Fe
3O
4Magnetic fluid.With a certain amount of FeCl
24H
2O and FeCl
36H
2O places there-necked flask, adds deionized water dissolving again, mechanical stirring, and logical nitrogen deoxygenation is warming up to 80～90 ℃, disposable adding NaOH solution reaction 0.5～1.5h; The FeCl that adds
24H
2O: FeCl
36H
2The mol ratio of O: NaOH is 1: 2: 8; After reaction finished, magnetic field separation was about to magnet and places the there-necked flask exterior bottom, attracts Fe
3O
4, then waste liquid is outwelled, use washed with de-ionized water Fe
3O
4Until neutrality, finally obtain Fe
3O
4Magnetic fluid;
B. with template molecule (be the trace substance in the complex sample---medicine, veterinary drug, agricultural chemicals or organic pollutant, as quinolone antibiotic levofloxacin, lomefloxacin, Ciprofloxacin, fleroxacin, Enrofloxacin or Sparfloxacin etc.) mix with solvent (deionized water, methyl alcohol, ethanol or acetonitrile) and function monomer (methacrylic acid, vinylformic acid, 4-vinylpridine or acrylamide), stir 30～60min, carry out template molecule and assemble in advance, obtain the pre-assembling solution of template molecule and function monomer; Wherein the mol ratio of template molecule and function monomer is 1: 4～10, and the quality of template molecule and the volume ratio of solvent are 1g: 20～50ml;
C. get the Fe that makes among a certain amount of step a
3O
4Magnetic fluid adds a certain amount of oleic acid, and concussion 5～15min carries out surface modification, Fe
3O
4The quality of magnetic fluid and oleic volume ratio are 1g: 1～2ml; Add linking agent (Ethylene glycol dimethacrylate or Viscoat 295) then, Fe
3O
4The mass ratio of magnetic fluid and linking agent is 1: 3～6; Add the template molecule that step b makes and the pre-assembling solution of function monomer at last, the mol ratio of assembling the linking agent that template molecule and back in the solution add in advance is 1: 10～20; Stir or ultra-sonic dispersion 30～60min, obtain the pre-polymer solution of magnetic molecularly imprinted polymer;
D. the pre-polymer solution of the magnetic molecularly imprinted polymer that step c is made joins (methyl alcohol, ethanol or acetonitrile in the polymer solvent that contains dispersion agent (polyvinylpyrrolidone, polyoxyethylene glycol or Natvosol), or the mixture of a kind of and deionized water in these three kinds of solvents), wherein the volume ratio of the quality of dispersion agent and polymer solvent is 1g: 200～400ml, and the volume ratio of magnetic molecularly imprinted polymer pre-polymer solution and polymer solvent is 1: 5～8; Add initiator (Diisopropyl azodicarboxylate or benzoyl peroxide) then, the quality of initiator and the volume ratio of polymer solvent are 1g: 800～1200ml; Logical nitrogen deoxygenation, the rotating speed stirring with 280～320r/min is warming up to 40～70 ℃ and carries out polyreaction 24h, obtains containing the magnetic molecularly imprinted polymer of template molecule;
E. after reaction finishes, the magnetic molecularly imprinted polymer that contains template molecule that the magnetic field separation steps d obtains, with the eluent (mixing solutions of a kind of and acetic acid in methyl alcohol, ethanol, these three kinds of solvents of acetonitrile, or the mixing solutions of acetonitrile and trifluoroacetic acid) supersound washing repeatedly, in order to the wash-out template molecule,, use washed with de-ionized water again until elutriant no template molecule after chromatogram detects, 60～90 ℃ of dryings promptly obtain magnetic molecularly imprinted polymer until constant weight behind the magnetic field separation.
Foundation and the application in the complex sample pre-treatment thereof based on the three phase extraction system of magnetic molecularly imprinted polymer comprise the steps:
A. activation: the magnetic molecularly imprinted polymer for preparing is joined in the Erlenmeyer flask, and with the methyl alcohol activation, magnetic field separation is outwelled waste liquid; Clean with deionized water the methyl alcohol on magnetic molecularly imprinted polymer surface is removed, magnetic field separation is outwelled waste liquid, the magnetic molecularly imprinted polymer that obtains activating; Wherein the volume ratio of the quality of magnetic molecularly imprinted polymer and methyl alcohol is 1g: 20～40ml, and the volume ratio of methyl alcohol and deionized water is 1: 1;
B. extraction: in Erlenmeyer flask, add complex sample (food, environmental sample or biological sample) and extraction solvent (deionized water, methyl alcohol, ethanol, acetonitrile or buffered soln, buffered soln is as citric acid solution etc.), the magnetic molecularly imprinted polymer good with activation mixes; Stirring, extracting 5～30min under the effect of ultrasonic or microwave; The mass ratio of magnetic molecularly imprinted polymer and complex sample is 1: 10～20, and the quality of complex sample and the volume ratio of extraction solvent are 1g: 10～20ml; In this process in the complex sample trace substance to be measured earlier from the complex sample phase transition to the extraction solvent phase, and then be adsorbed onto the magnetic molecularly imprinted polymer phase;
C. separate: after extraction is finished, adopt a small test tube, a rectangular magnet is placed the test tube the inside, then test tube is put in the Erlenmeyer flask, this moment, magnetic molecularly imprinted polymer will be adsorbed to the test tube outer wall; At last, the magnetic molecularly imprinted polymer that is adsorbed onto the test tube outer wall is by eluent (methyl alcohol, ethanol, acetonitrile, or the mixture of a kind of and deionized water in these three kinds of solvents) be washed till in another Erlenmeyer flask, the quality of magnetic molecularly imprinted polymer and the volume ratio of eluent are 1g: 30～50ml;
D. drip washing: will contain the ultrasonic 20～40s of Erlenmeyer flask of magnetic molecularly imprinted polymer and eluent, magnetic field separation is outwelled waste liquid; And then the adding eluent, ultrasonic 20～40s, magnetic field separation is outwelled waste liquid;
E. wash-out: add the eluent (mixing solutions of a kind of and acetic acid in methyl alcohol, ethanol, these three kinds of solvents of acetonitrile, or the mixing solutions of acetonitrile and trifluoroacetic acid) washing magnetic molecularly imprinted polymer, the trace substance to be measured that is adsorbed onto above the magnetic molecularly imprinted polymer is eluted, the quality of magnetic molecularly imprinted polymer and the volume ratio of eluent are 1g: 10～20ml, wash-out (can carry out 20～40s) 1～4 time at every turn under ultransonic effect, magnetic field separation is collected elutriant; Under 40～50 ℃ of conditions, the elutriant that collection obtains is dried up with nitrogen, obtain residue, with 1.0mL solvent (mixture of a kind of and deionized water in methyl alcohol, these two kinds of solvents of acetonitrile) dissolved residue again, carry out the analyses of high performance liquid chromatography (HPLC) or liquid chromatography tandem mass spectrum (LC-MS/MS) after the filtration.
The present invention has following advantage:
1. the preparation method of magnetic molecularly imprinted polymer provided by the invention is simple to operate, and suitability is wide;
2. before polyreaction, with oleic acid with Fe
3O
4Modification is carried out on the surface, has strengthened that it is fat-soluble, has well solved the problem of metal oxide and organic polymer consistency, makes Fe
3O
4Well be embedded in the polymkeric substance the inside;
3. because the good magnetic of polymkeric substance, after finishing, extraction can well realize and the separating of sample matrices;
4. present method has good selectivity, when it is applied to the complex sample pre-treatment, can well remove matrix interference;
5. can save analysis time greatly based on the foundation of the three phase extraction system of magnetic molecularly imprinted polymer, the consumption of simplifying analytical procedure and reducing organic solvent has broad application prospects in the complex sample pre-treatment;
6. this method is applicable to and analyzes various complex samples, as food, environmental sample and biological sample.
Description of drawings
Fig. 1: based on the foundation of the three phase extraction system of magnetic molecularly imprinted polymer and the applying step synoptic diagram in the complex sample pre-treatment thereof;
Fig. 2: for the present invention is prepared is the electron scanning micrograph of the magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin; As we know from the figure, the present invention preparation be that the magnetic molecularly imprinted polymer of template molecule is loose porous shape with the Ciprofloxacin, help absorption to quinolone antibiotic;
Fig. 3: for the present invention is prepared is the infrared spectrogram of the magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin; Among the figure, 3435cm
-1The place is the stretching vibration absorption peak of O-H; 2954cm
-1The place is the stretching vibration absorption peak of C-H; 1728cm
-1The place is C=O stretching vibration absorption peak; 1457cm
-1With 1389 places be C-H cm
-1The flexural vibration absorption peak; 1256cm
-1The place is the stretching vibration absorption peak of C-O; 586cm
-1The place is Fe
3O
4Absorption peak, show Fe
3O
4Successful being wrapped into is the magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin.
Fig. 4: for the present invention is prepared is the magnetic hysteresis loop figure of the magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin; As seen from the figure, the present invention is prepared is that the magnetic molecularly imprinted polymer of template molecule has good superparamagnetism with the Ciprofloxacin, and saturation magnetization is 9.75emug
-1, thereby can be rapidly under the effect of externally-applied magnetic field from separating the sample solution on every side.
Fig. 5: (a) for Ciprofloxacin (CIP) with the Ciprofloxacin be template molecule magnetic molecularly imprinted polymer combine isothermal map, (b) combine the Scatchard graphic representation of character with the magnetic molecularly imprinted polymer that with the Ciprofloxacin is template molecule for the evaluation Ciprofloxacin.By the Scatchard curve among the figure, Ciprofloxacin and be to have two class binding sites between the magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin as can be known is according to formula (Q/[CIP])=(Q
Max-Q)/K
d(Q is that to be attached to the Ciprofloxacin be the amount of the CIP on the magnetic molecularly imprinted polymer of template molecule; [CIP] is the equilibrium concentration of CIP in adsorbent solution; K
dDissociation constant for binding site; Q
MaxBe the apparent binding capacity of maximum), can obtain K
D1=117.5 μ mol L
-1, Q
Max1=75.4 μ molg
-1K
D2=1355 μ molL
-1, Q
Max2=232.4 μ molg
-1
Fig. 6: (the mark-on concentration of every kind of material is 10ng g to extract ion figure based on the LC-MS/MS of three phase extraction system quinolone antibiotic in extraction mark-on chicken meat sample (six kinds of quinolone antibiotics that will detect join in the middle of the chicken meat sample in advance) that with the Ciprofloxacin is the magnetic molecularly imprinted polymer of template molecule
-1).Wherein M/Z is a mass-to-charge ratio.(a) levofloxacin; (b) lomefloxacin; (c) Ciprofloxacin; (d) fleroxacin; (e) Enrofloxacin; (f) Sparfloxacin.As seen from the figure, being the prepared magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin all has good effect of extracting to Ciprofloxacin and resemblance thereof such as levofloxacin, lomefloxacin, fleroxacin, Enrofloxacin and Sparfloxacin.
Embodiment
Embodiment 1:
Use content of the present invention, adopt Ciprofloxacin, the preparation magnetic molecularly imprinted polymer as template molecule.
1. be the preparation of the magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin, comprise the steps:
A. adopt chemical coprecipitation to prepare Fe
3O
4Magnetic fluid.With 10mmol FeCl
24H
2O and 20mmolFeCl
36H
2O places the 250ml there-necked flask, adds the 100ml deionized water dissolving again, mechanical stirring, and logical nitrogen deoxygenation is warming up to 80 ℃, the NaOH solution reaction 1.0h of disposable adding 80mmol; After reaction finished, magnetic field separation was about to magnet and places the there-necked flask exterior bottom, attracts Fe
3O
4, then waste liquid is outwelled, use washed with de-ionized water Fe
3O
4Until neutrality, the Fe that finally obtains
3O
4The quality of magnetic fluid is 2.3g;
B. 1.0mmol Ciprofloxacin (0.367g) is mixed with 10ml deionized water and 8.0mmol (0.689g) methacrylic acid, stir 30min, carry out template molecule and assemble in advance, obtain the pre-assembling solution (about 20ml) of template molecule and function monomer.
C. get the Fe that makes among the 1.0g step a
3O
4Magnetic fluid adds 1.0ml oleic acid, and vibration 10min carries out surface modification; Add 20mmol (3.964g) Ethylene glycol dimethacrylate then; Add the template molecule that step b makes and the pre-assembling solution of function monomer at last, dispersed with stirring 30min, obtaining with the Ciprofloxacin is the pre-polymer solution of the magnetic molecularly imprinted polymer of template molecule.
What d. step c is made is that the pre-polymer solution of the magnetic molecularly imprinted polymer of template molecule joins in the 100ml ethanol that contains the 0.4g polyvinylpyrrolidone with the Ciprofloxacin, add the 0.1g Diisopropyl azodicarboxylate then, logical nitrogen deoxygenation, rotating speed with 300r/min stirs, be warming up to 60 ℃ and carry out polyreaction 24h, obtain containing the magnetic molecularly imprinted polymer of template molecule Ciprofloxacin;
E. after reaction finishes, the magnetic molecularly imprinted polymer that contains the template molecule Ciprofloxacin that the magnetic field separation steps d obtains, with volume ratio is the mixing solutions supersound washing repeatedly of 1: 1 methyl alcohol and acetic acid, in order to wash-out template molecule Ciprofloxacin, until elutriant no template molecule Ciprofloxacin after chromatogram detects, use washed with de-ionized water again, 60 ℃ of dryings are until constant weight behind the magnetic field separation, promptly obtaining with the Ciprofloxacin is the magnetic molecularly imprinted polymer of template molecule, and quality is 5.6g.
Embodiment 2:
Based on the foundation of three phase extraction system and the application aspect the quinolone antibiotic in the extracting and separating chicken meat sample (annotate: as template molecule, the magnetic molecularly imprinted polymer of preparing can extract Ciprofloxacin and resemblance such as levofloxacin, lomefloxacin, fleroxacin, Enrofloxacin and Sparfloxacin simultaneously with Ciprofloxacin) thereof that with the Ciprofloxacin are the magnetic molecularly imprinted polymer of template molecule.As shown in Figure 1, comprise the steps:
A. activation: what 80mg embodiment 1 was prepared is that the magnetic molecularly imprinted polymer of template molecule joins in the Erlenmeyer flask with the Ciprofloxacin, and with the activation of 3.0mL methyl alcohol, magnetic field separation is outwelled waste liquid; Cleaning with the 3.0mL deionized water will be that the methyl alcohol on the magnetic molecularly imprinted polymer surface of template molecule is removed with the Ciprofloxacin again, and magnetic field separation is outwelled waste liquid, and what obtain activating is the magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin;
B. extraction: add good chicken meat sample of 1.0g homogenate and extraction solvent (20mL, pH value are 9 50% methanol aqueous solution) in Erlenmeyer flask, what get well with activation is that the magnetic molecularly imprinted polymer of template molecule mixes high-speed stirring 20min with the Ciprofloxacin; Quinolone antibiotic in this process in the chicken meat sample earlier from the chicken meat sample phase transition to the extraction solvent phase, and then to be adsorbed onto with the Ciprofloxacin be the magnetic molecularly imprinted polymer phase of template molecule;
C. separate: after extraction is finished, adopt a small test tube, one rectangular magnet is placed the test tube the inside, then test tube is put in the Erlenmeyer flask, be that the magnetic molecularly imprinted polymer of template molecule will be adsorbed to the test tube outer wall this moment with the Ciprofloxacin, what at last, be adsorbed onto the test tube outer wall is that the magnetic molecularly imprinted polymer of template molecule is washed till in another Erlenmeyer flask by the 3mL acetonitrile with the Ciprofloxacin;
D. drip washing: will contain with the Ciprofloxacin is the magnetic molecularly imprinted polymer of template molecule and the ultrasonic 30s of Erlenmeyer flask of 3mL acetonitrile, and magnetic field separation is outwelled waste liquid.And then add the 3mL acetonitrile, and ultrasonic 30s, magnetic field separation is outwelled waste liquid;
E. wash-out: adding the methanol solution washing that contains 5% acetic acid is the magnetic molecularly imprinted polymer of template molecule with the Ciprofloxacin, elutes wash-out 3 times, a 1.0ml, each ultrasonic 30s with being adsorbed onto top quinolone antibiotic; Magnetic field separation is collected elutriant, with nitrogen the elutriant that collection obtains is dried up under 40 ℃ of conditions, obtains residue, with 1.0mL, 20% methanol aqueous solution dissolved residue again, carries out liquid chromatography tandem mass spectrum (LC-MS/MS) analysis after the filtration.
The result shows that the recovery of standard addition of the quinolone antibiotic that the method for being set up by the present invention obtains is 75.3%～92.8%, and precision is represented with RSD, less than 8.4%.The setting-out line scope is 10～1000ng g
-1Detecting of six kinds of quinolone antibiotics is limited to 1.5～3.3ng g in the analyzed chicken meat sample
-1
Claims (8)
1. the preparation method of a magnetic molecularly imprinted polymer comprises the steps:
A. adopt chemical coprecipitation to prepare Fe
3O
4Magnetic fluid;
B. template molecule is mixed with solvent and function monomer, carry out template molecule and assemble in advance, obtain the pre-assembling solution of template molecule and function monomer; Wherein the mol ratio of template molecule and function monomer is 1: 4～10, and the quality of template molecule and the volume ratio of solvent are 1g: 20～50ml; Template molecule is a Ciprofloxacin, and function monomer is a methacrylic acid;
C. get the Fe that makes among the step a
3O
4Magnetic fluid adds oleic acid, and concussion 5～15min carries out surface modification, Fe
3O
4The quality of magnetic fluid and oleic volume ratio are 1g: 1～2ml; Add linking agent then, Fe
3O
4The mass ratio of magnetic fluid and linking agent is 1: 3～6; Add step at last
The pre-assembling solution of template molecule that b makes and function monomer, the mol ratio of assembling the linking agent of template molecule in the solution and adding in advance is 1: 10～20; Stir or ultra-sonic dispersion 30～60min, obtain the pre-polymer solution of magnetic molecularly imprinted polymer;
D. the pre-polymer solution of the magnetic molecularly imprinted polymer that step c is made joins in the polymer solvent that contains dispersion agent, wherein the volume ratio of the quality of dispersion agent and polymer solvent is 1g: 200～400ml, and the volume ratio of magnetic molecularly imprinted polymer pre-polymer solution and polymer solvent is 1: 5～8; Add initiator then, the quality of initiator and the volume ratio of polymer solvent are 1g: 800～1200ml; Logical nitrogen deoxygenation, the rotating speed stirring with 280～320r/min is warming up to 40～70 ℃ and carries out polyreaction 24h, obtains containing the magnetic molecularly imprinted polymer of template molecule;
E. after reaction finishes, the magnetic molecularly imprinted polymer that contains template molecule that the magnetic field separation steps d obtains, with eluent supersound washing repeatedly, in order to the wash-out template molecule, until elutriant no template molecule after chromatogram detects, use washed with de-ionized water again, 60～90 ℃ of dryings promptly obtain magnetic molecularly imprinted polymer until constant weight behind the magnetic field separation.
2. the preparation method of a kind of magnetic molecularly imprinted polymer as claimed in claim 1 is characterized in that: be with FeCl
24H
2O and FeCl
36H
2O places there-necked flask, adds deionized water dissolving again, mechanical stirring, and logical nitrogen deoxygenation is warming up to 80～90 ℃, disposable adding NaOH solution reaction 0.5～1.5h; The FeCl that adds
24H
2O: FeCl
36H
2The mol ratio of O: NaOH is 1: 2: 8; After reaction finished, magnetic field separation was outwelled waste liquid then, uses washed with de-ionized water Fe
3O
4Until neutrality, finally obtain Fe
3O
4Magnetic fluid.
3. the preparation method of a kind of magnetic molecularly imprinted polymer as claimed in claim 1, it is characterized in that: linking agent is Ethylene glycol dimethacrylate or Viscoat 295.
4. the preparation method of a kind of magnetic molecularly imprinted polymer as claimed in claim 1, it is characterized in that: polymer solvent is methyl alcohol, ethanol or acetonitrile, or the mixture of a kind of and deionized water in these three kinds of solvents; Dispersion agent is polyvinylpyrrolidone, polyoxyethylene glycol or Natvosol; Initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
5. the preparation method of a kind of magnetic molecularly imprinted polymer as claimed in claim 1, it is characterized in that: eluent is the mixing solutions of a kind of and acetic acid in methyl alcohol, ethanol, these three kinds of solvents of acetonitrile, or the mixing solutions of acetonitrile and trifluoroacetic acid.
6. the application of magnetic molecularly imprinted polymer in the meat sample pre-treatments of any one described method preparation of claim 1～5.
7. the application of magnetic molecularly imprinted polymer as claimed in claim 6 in the meat sample pre-treatments the steps include:
A. activation: the magnetic molecularly imprinted polymer for preparing is joined in the Erlenmeyer flask, and with the methyl alcohol activation, magnetic field separation is outwelled waste liquid; Clean with deionized water the methyl alcohol on magnetic molecularly imprinted polymer surface is removed, magnetic field separation is outwelled waste liquid, the magnetic molecularly imprinted polymer that obtains activating; Wherein the volume ratio of the quality of magnetic molecularly imprinted polymer and methyl alcohol is 1g: 20～40ml, and the volume ratio of methyl alcohol and deionized water is 1: 1;
B. extraction: add meat sample and extraction solvent in Erlenmeyer flask, the magnetic molecularly imprinted polymer good with activation mixes; Stirring, extracting 5～30min under the effect of ultrasonic or microwave; The mass ratio of magnetic molecularly imprinted polymer and meat sample is 1: 10～20, and the quality of meat sample and the volume ratio of extraction solvent are 1g: 10～20ml;
C. separate: after extraction is finished, adopt a small test tube, a rectangular magnet is placed the test tube the inside, then test tube is put in the Erlenmeyer flask, this moment, magnetic molecularly imprinted polymer will be adsorbed to the test tube outer wall; At last, the magnetic molecularly imprinted polymer that is adsorbed onto the test tube outer wall is washed till in another Erlenmeyer flask by eluent, and the quality of magnetic molecularly imprinted polymer and the volume ratio of eluent are 1g: 30～50ml;
D. drip washing: will contain the ultrasonic 20～40s of Erlenmeyer flask of magnetic molecularly imprinted polymer and eluent, magnetic field separation is outwelled waste liquid; And then the adding eluent, ultrasonic 20～40s, magnetic field separation is outwelled waste liquid;
E. wash-out: add eluent washing magnetic molecularly imprinted polymer, the trace substance to be measured that is adsorbed onto above the magnetic molecularly imprinted polymer is eluted, the quality of magnetic molecularly imprinted polymer and the volume ratio of eluent are 1g: 10～20m l, wash-out 1～4 time, magnetic field separation is collected elutriant; Under 40～50 ℃ of conditions, the elutriant that collection obtains is dried up, obtain residue,, carry out high performance liquid chromatography or the analysis of liquid chromatography tandem mass spectrum after the filtration with 1.0mL solvent dissolved residue again with nitrogen.
8. the application of magnetic molecularly imprinted polymer as claimed in claim 7 in the meat sample pre-treatments is characterized in that: extraction solvent is deionized water, methyl alcohol, ethanol, acetonitrile or buffered soln; Eluent is methyl alcohol, ethanol, acetonitrile, or the mixture of a kind of and deionized water in these three kinds of solvents; Eluent is the mixing solutions of a kind of and acetic acid in methyl alcohol, ethanol, these three kinds of solvents of acetonitrile, or the mixing solutions of acetonitrile and trifluoroacetic acid; After nitrogen dried up, the solvent of dissolved residue was the mixture of a kind of and deionized water in methyl alcohol, these two kinds of solvents of acetonitrile.
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