CN101628955B - Method for preparing molecular imprinted polymer for recognizing chloromycetin, thiamphenicol and florfenicol simultaneously - Google Patents
Method for preparing molecular imprinted polymer for recognizing chloromycetin, thiamphenicol and florfenicol simultaneously Download PDFInfo
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Abstract
The invention relates to a method for preparing a molecular imprinted polymer capable of recognizing chloromycetin, thiamphenicol and florfenicol simultaneously, which belongs to the technical field of bioengineering. The method comprises the following concrete steps: adding a functional monomer and a cross-linking agent into a pore-forming agent, uniformly mixing and heating; then adding template molecule thiamphenicol and an initiating agent, further ultrasonically degassing the mixed solution, sealing in a nitrogen or vacuum pumping state and carrying out polymerization reaction; after the polymerization reaction is finished, taking the compounded polymer out to grind and screen; eluting by organic solvent to remove template molecules by a combined method of Soxhlet extraction and solid phase-extraction cartridges till the template molecules are not detected by a high performance liquid chromatography-mass spectrometry; finally removing the polymer of the template molecules and drying in vacuum to obtain the molecular imprinted polymer. The polymer can be simultaneously applied to the pre-processing of the antibiotic detection of chloromycetin, thiamphenicol and florfenicol in foods and realizes the specific and selective separation and the efficient enrichment of the chloromycetin, the thiamphenicol and the florfenicol.
Description
Technical field
The present invention relates to the preparation method of molecularly imprinted polymer, specifically, relate to a kind of preparation method who discerns the molecularly imprinted polymer of paraxin, thiamphenicol and Florfenicol simultaneously.
Background technology
Paraxin (Chloramphenicol, CAP), thiamphenicol (Thiamphenicol, TAP) and Florfenicol (Floramphenicol FF) belongs to chloromycetin series antibiotics, paraxin is owing to be with nitro on its phenyl ring, half life of decomposition is longer, and has serious toxic side effect, therefore, residual chloromycetin in animal food and the fishery products has constituted grave danger to human health, at present, be inhibited in the animal derived food and used, its maximum residue limit(MRL) is 0.1 μ g/kg.Thiamphenicol and Florfenicol are because toxicity is little than paraxin, alternative medicine as paraxin is widely used, but along with progress of research discovery thiamphenicol and its toxic side effect of Florfenicol still exist, its maximum residue limit(MRL) standard is generally 50～100 μ g/kg.Therefore, for guaranteeing the edible safety of animal food, qualitative checking method is very important accurately and reliably in foundation.At present, the method for chlorine detection mycin, thiamphenicol and Florfenicol is less simultaneously, mainly contains high performance liquid chromatography (HPLC) method, gas chromatography-mass spectrum (GC-MS) method and liquid chromatography-mass spectrography (LC-MS/LC-MS/MS) method etc.; There is the sample pretreatment process complexity in these methods, costs an arm and a leg, analysis speed waits shortcoming slowly, therefore, reinforcement is to chloromycetin series antibiotics forbidden drug residue detection, especially carry out the detection of how residual composition, press for novel, highly selective, preparation easy, have an antibiotic filler matrix of a certain class of single-minded identification.Molecular imprinting (Molecularly imprinting technique based on molecular recognition theory, MIT) be a kind of analog antibody-AI, can obtain on space and binding site and the technology a certain or polymkeric substance that certain molecule is complementary, molecularly imprinted polymer (the Molecularly imprinted polymers that obtains, MIPs) owing to have selectivity and higher physical strength preferably, the filler that can be used as Solid-Phase Extraction and liquid-phase chromatographic column, compare with traditional solid phase extraction filler, can be from complex sample selective separation and enrichment target molecule or with the compound of structural similitude, have high specific and highly selective, preparation is simple, good stability and advantage such as reusable.Find that through literature search molecular imprinting has begun to be applied in the detection of paraxin in the food at present to prior art.But, mainly be based at present the specific isolation design of this simple target compound of paraxin about the research of the molecularly imprinted polymer of chloromycetin series antibiotics, and the conventional wash-out processing of process can not be removed template molecule fully from polymkeric substance, in each step of the Solid-Phase Extraction of carrying out subsequently, comprise the seepage phenomenon of usually finding template molecule in the operations such as sample, drip washing, wash-out, concerning the detection of trace substance, increase systematic error, directly influenced the molecular engram solid phase extraction broad application.
Summary of the invention
Technical problem to be solved by this invention is that the present situation at prior art provides a kind of preparation method that can effectively discern the molecularly imprinted polymer of paraxin, thiamphenicol and Florfenicol simultaneously.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this discerns the preparation method of the molecularly imprinted polymer of paraxin, thiamphenicol, Florfenicol simultaneously, it is characterized in that may further comprise the steps:
(1), function monomer, linking agent are joined in the pore-creating agent, under 40～50 ℃ of conditions, heat, add template molecule then and mix, obtain mixing solutions;
(2), in the mixing solutions that step (1) obtains, add initiator, ultrasonic degas 5～10min; Logical then nitrogen 10～15min vacuumizes or nitrogen state lower seal;
(3), be thermal-initiated polymerization under 60～70 ℃ the condition in temperature, the reaction times is 36～48h;
(4), after polyreaction finishes, the polymkeric substance that obtains taken out grind, screening, remove template molecule by organic solvent;
(5), the polymkeric substance vacuum-drying that will remove template molecule, obtain discerning simultaneously the molecularly imprinted polymer of paraxin, thiamphenicol and Florfenicol;
Wherein, described template molecule is a thiamphenicol, and described pore-creating agent is an acetonitrile, and described linking agent is trimethylolpropane trimethacrylate (TRIM) or ethylene glycol dimethacrylate (EGDMA); Described function monomer is methacrylic acid N, N-diethylamino ethyl ester, methacrylic acid or trifluoromethyl acrylate;
The mol ratio of described template molecule, function monomer, linking agent is 1: 1～8: 25; And the volume ratio of pore-creating agent and linking agent is 1: 6～14.
Preferably, obtaining the particulate median size after grinding in the step (4), sieving is 40～60 μ m.
Removing the method that template molecule adopted in the step (4) can be that soxhlet extraction and solid-phase extraction column wash-out are united use.
The used solvent of described soxhlet extraction and solid-phase extraction column wash-out can be respectively the mixing solutions and the methyl alcohol of methyl alcohol and formic acid, and the volume ratio of methyl alcohol and formic acid is 9: 1 in the mixing solutions of wherein said methyl alcohol and formic acid.
Described vacuum-drying temperature can be 45～50 ℃, and be 8h time of drying.
Compared with prior art, the present invention with thiamphenicol as template molecule, by selecting suitable target analytes as template molecule and set up suitable elution program and make the molecularly imprinted polymer that to discern simultaneously, separate paraxin, thiamphenicol and Florfenicol, and having solved the problems such as template seepage that molecularly imprinted polymer exists usually, the molecularly imprinted polymer of acquisition can be used for the specific selectivity of paraxin, thiamphenicol and Florfenicol is separated and efficiently concentrating.This molecularly imprinted polymer not only has stronger recognition capability to paraxin, thiamphenicol and Florfenicol, and three kinds of materials are had higher selectivity and sensitivity, can be used for the separating of paraxin, thiamphenicol and Florfenicol in biology and the environmental sample, enrichment and purifying.This molecularly imprinted polymer will provide good pre-treatment material for the residual detection of paraxin, thiamphenicol and Florfenicol, in conjunction with existing detection method, as ELISA, HPLC, HPLC/GC-MS etc., can significantly improve three kinds of detection sensitivity and detection efficiencies that material is residual, have bigger application value.Simultaneously, molecularly imprinted polymer provided by the present invention can be used as the filler of Solid-Phase Extraction and liquid-phase chromatographic column, realizes the separating of paraxin, thiamphenicol and Florfenicol, purifying and enrichment.
Description of drawings
The porous molecularly imprinted polymer of Fig. 1 for making in the embodiment of the invention 1;
Fig. 2 is the surperficial Electronic Speculum scintigram of the porous molecularly imprinted polymer that makes in the embodiment of the invention 1;
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
Function monomer methacrylic acid (MAA) 1mmol is joined among the pore-creating agent acetonitrile 5ml, add linking agent ethylene glycol dimethacrylate (EGDMA) 25mmol, after mixing, 40 ℃ of heating 2min, add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.60 ℃ are reacted 36h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 45 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Embodiment 2
Function monomer methacrylic acid (MAA) 8mmol is joined among the pore-creating agent acetonitrile 5ml, add linking agent ethylene glycol dimethacrylate (EGDMA) 25mmol, after mixing, 50 ℃ of heating 2min, add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.60 ℃ are reacted 36h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 45 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Embodiment 3
With function monomer methacrylic acid N, N-diethylamino ethyl ester (DEAEM) 1mmol joins among the pore-creating agent acetonitrile 5ml, add linking agent ethylene glycol dimethacrylate (EGDMA) 25mmol, after mixing, 40 ℃ of heating 2min add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.70 ℃ are reacted 36h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v 9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 45 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Embodiment 4
Function monomer methacrylic acid (MAA) 1mmol is joined among the pore-creating agent acetonitrile 5ml, add linking agent ethylene glycol dimethacrylate (EGDMA) 25mmol, after mixing, 40 ℃ of heating 2min, add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.60 ℃ are reacted 48h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 50 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Embodiment 5
Function monomer methacrylic acid (MAA) 6mmol is joined among the pore-creating agent acetonitrile 5ml, add linking agent ethylene glycol dimethacrylate (EGDMA) 25mmol, after mixing, 40 ℃ of heating 2min, add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.60 ℃ are reacted 48h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 50 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Embodiment 6
Function monomer methacrylic acid (MAA) 6mmol is joined among the pore-creating agent acetonitrile 5ml, add linking agent ethylene glycol dimethacrylate (EGDMA) 25mmol, after mixing, 45 ℃ of heating 2min, add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.60 ℃ are reacted 48h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 50 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Embodiment 7
Function monomer methacrylic acid (MAA) 6mmol is joined among the pore-creating agent acetonitrile 5ml, add linking agent trimethylolpropane trimethacrylate (TRIM) 25mmol, after mixing, 45 ℃ of heating 2min, add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.60 ℃ are reacted 48h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v 9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 50 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Embodiment 8
Function monomer trifluoromethyl acrylate (TFMAA) 1mmol is joined among the pore-creating agent acetonitrile 5ml, add linking agent ethylene glycol dimethacrylate (EGDMA) 25mmol, after mixing, 50 ℃ of heating 2min, add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.60 ℃ are reacted 36h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v 9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 45 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Embodiment 9
Function monomer trifluoromethyl acrylate (TFMAA) 8mmol is joined among the pore-creating agent acetonitrile 5ml, add linking agent trimethylolpropane trimethacrylate (TRIM) 25mmol, after mixing, 50 ℃ of heating 2min, add template molecule thiamphenicol 1mmol then and feed nitrogen 10～15min, add initiator Diisopropyl azodicarboxylate (AIBN), ultrasonic degas 5～10min, nitrogen state or vacuumize the state lower seal.60 ℃ are reacted 36h down; After polyreaction finishes, the synthetic polymkeric substance is taken out the back of grinding, sieve use methyl alcohol: formic acid acid (v/v 9/1), methyl alcohol are removed template molecule by soxhlet extraction, the solid phase extraction column of further molecularly imprinted polymer that obtains being packed into, use methyl alcohol successively: formic acid (v/v 9/1), methyl alcohol drip washing, by high performance liquid chromatography-mass spectrometric detection, till detecting less than template molecule; To remove the polymkeric substance of template molecule, 45 ℃ of vacuum-dryings obtain molecularly imprinted polymer, and the median size size of Huo Deing is 40～60 μ m at last.
Test
After the molecularly imprinted polymer of embodiment 1 preparation made solid phase extraction column, the mark-on sample after the solid phase extraction column separation and purification, is detected with LC-MS/MS, be applied to the detected result of paraxin, thiamphenicol, Florfenicol in fish, the shrimp sample.The test result of embodiment 2 to embodiment 9 is basic identical.
Claims (5)
1. preparation method who discerns the molecularly imprinted polymer of paraxin, thiamphenicol, Florfenicol simultaneously is characterized in that may further comprise the steps:
(1), function monomer, linking agent are joined in the pore-creating agent, under 40～50 ℃ of conditions, heat, add template molecule then and mix, obtain mixing solutions;
(2), in the mixing solutions that step (1) obtains, add initiator, ultrasonic degas 5～10min; Logical then nitrogen 10～15min vacuumizes or nitrogen state lower seal;
(3), be thermal-initiated polymerization under 60～70 ℃ the condition in temperature, the reaction times is 36～48h;
(4), after polyreaction finishes, the polymkeric substance that obtains taken out grind, screening, remove template molecule by organic solvent;
(5), the polymkeric substance vacuum-drying that will remove template molecule, obtain discerning simultaneously the molecularly imprinted polymer of paraxin, thiamphenicol and Florfenicol;
Wherein, described template molecule is a thiamphenicol, and described pore-creating agent is an acetonitrile, and described linking agent is trimethylolpropane trimethacrylate (TRIM) or ethylene glycol dimethacrylate (EGDMA); Described function monomer is methacrylic acid N, N-diethylamino ethyl ester, methacrylic acid or trifluoromethyl acrylate;
The mol ratio of described template molecule, function monomer, linking agent is 1: 1～8: 25; And the volume ratio of pore-creating agent and linking agent is 1: 6～14.
2. the preparation method who discerns the molecularly imprinted polymer of paraxin, thiamphenicol, Florfenicol simultaneously according to claim 1, obtaining the particulate median size after it is characterized in that grinding in the step (4), sieving is 40～60 μ m.
3. the preparation method who discerns the molecularly imprinted polymer of paraxin, thiamphenicol, Florfenicol simultaneously according to claim 1 is characterized in that removing the method that template molecule adopted in the step (4) is that soxhlet extraction and solid-phase extraction column wash-out are united use.
4. the preparation method who discerns the molecularly imprinted polymer of paraxin, thiamphenicol, Florfenicol simultaneously according to claim 3, it is characterized in that the used solvent of described soxhlet extraction is the mixing solutions of methyl alcohol and formic acid, the used solvent of described solid-phase extraction column wash-out is a methyl alcohol, and the volume ratio of methyl alcohol and formic acid is 9: 1 in the mixing solutions of wherein said methyl alcohol and formic acid.
5. the preparation method who discerns the molecularly imprinted polymer of paraxin, thiamphenicol, Florfenicol simultaneously according to claim 1 is characterized in that described vacuum-drying temperature is 45～50 ℃, and be 8h time of drying.
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| CN102336859B (en) * | 2010-07-21 | 2015-04-22 | 天津科技大学 | Preparation method of ractopamine bionic antibody |
| CN103232358B (en) * | 2012-11-05 | 2015-07-29 | 南京工业大学 | Vesicle probe for detecting neomycin, application and preparation method |
| CN103102448A (en) * | 2013-02-04 | 2013-05-15 | 天津科技大学 | Preparation method of molecularly imprinted polymer capable of simultaneously identifying quinoxaline-2-carboxylic acid and 3-methyl- quinoxaline-2-carboxylic acid |
| CN105111370B (en) * | 2015-09-29 | 2017-12-19 | 徐州工程学院 | A kind of chloramphenicol molecularly imprinted polymeric and preparation method thereof |
| CN109187509B (en) * | 2018-08-12 | 2021-11-12 | 河北农业大学 | Chemiluminescent kit for specific detection of chloramphenicol, detection method and application |
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| CN1811411A (en) * | 2006-02-16 | 2006-08-02 | 上海交通大学 | Process for producing chloromycetin molecular engram polymer microsphere |
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