CN101173058A - Method for producing molecular engram polyalcohol microsphere and method for separating enrofloxacin thereof - Google Patents
Method for producing molecular engram polyalcohol microsphere and method for separating enrofloxacin thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a molecularly imprinted polymer microsphere in the technical field of the chemical engineering. The invention includes the following steps: under the effect of ultrasound, the mixture is added in the solution and quickly stirred to react for 24 hours; after stirring, filtering and washing, the template molecules are removed by the soxhlet extraction; the polymer removed template molecules are dried to constant weight in vacuum, and the molecularly imprinted polymer microsphere is obtained. The method of separating enrofloxacin from the molecularly imprinted polymer microsphere includes the steps that the molecularly imprinted polymer microsphere of enrofloxacin is filled into the polypropylene solid phase extraction cartridge; the solid phase extraction cartridge is activated and decontaminated, and finally, the enrofloxacin for detecting is eluted and collected. With simple method and perfect mechanical intensity and chemical stability, the invention can be used for the extreme conditions such as acid, alkali, high temperature, etc., and is also applicable to separate, purify and enrich the enrofloxacin in such complex substrates as water-solubility medium and animal-originated food, thereby possessing a perfect application prospect.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of chemical engineering, is specifically related to a kind of preparation method of molecular blotting polymer microsphere and the method for separating enrofloxacin thereof.
Background technology
Enrofloxacin (enrofloxacin, be called for short ENR) be the chemosynthesis fungistat, belong to the 3rd generation fluoroquinolones (Fluoroquinolones) antibiotic, suppress the synthetic of DNA of bacteria by suppressing the DNA of bacteria gyrase, powerful germicidal action is arranged, be widely used on the veterinary clinic, but its in animal body the transformation period longer; The people is edible for a long time accumulate poisoning can to occur.According to the epidemiology survey to such medicine, its main toxic side effect comprises the infringement and the anaphylaxis of Digestive tract, neural system hepatic and renal function, cardiovascular systems and aspects such as blood system and joint cartilage.Its anaphylaxis that causes is seen with fash more, urticaria, erythema or skin rubefaction, heating, itch, eyelid and conjunctival congestion can occur, and this is main relevant with underlying diseases, is reversibility, disappears voluntarily after the drug withdrawal; In addition, FQs class medicine all has photosensitive toxicity, and closely related with drug dose.Secondly, medicine and drug residue cause that the eater produces toxic action at a specified future date and potential " three cause " (carcinogenic, teratogenesis, mutagenesis) effect more.In addition, residual FQs has very big potential hazard to the human consumer in the animal body, and abuse FQs class medicine causes bacterium to produce resistance.This has constituted grave danger to human health.
Current, along with the livestock and poultry cultivation scale constantly enlarges, treatment with veterinary drug and as the veterinary drug of fodder additives use in kind with quantitatively all show a considerable increase, caused serious food-safety problem thus.National governments launch respectively relevant policies, limit and even forbid the use of some veterinary drug and strengthen its detection residual in animal food.European Union and some national 20th century just stipulated its maximum residue limit(MRL) in animal tissues, the maximum residue limit(MRL) of nuisanceless poultry of China and byproduct regulation Enrofloxacin, Ciprofloxacin is 0.10mg/kg.Therefore, exploitation sensitive detection means and improvement analytical procedure, the Enrofloxacin that trace exists in the detection of complex sample is very important more efficiently.
At present, the enrofloxacin residual detection method mainly contains microbial method, immunization, chromatography, high performance liquid chromatography, liquid chromatography-mass spectrography etc.Although these methods respectively have the relative merits of self, but when being used for when animal food detects the Enrofloxacin that trace exists, for reducing the interference of complex matrices, generally all needing sample pre-treatments. the method for pre-treatment commonly used has Solid-Phase Extraction, the distribution of liquid liquid, immune column chromatography technology etc. at present, compare with liquid-liquid extraction, solid phase extraction techniques is simple to operate, and processing speed is fast, save reagent, and can handle a plurality of samples simultaneously.But the filler of Solid-Phase Extraction commonly used lacks selectivity with the effect of absorption target compound at present, is subject to the interference of analogue in the complex matrices.Though and immune column chromatography has specificity, used antibody costs an arm and a leg, and stability is not enough, can not be used for extreme environments such as strong acid, highly basic and high temperature.Therefore, develop novel solid phase extraction filler, can discern the Enrofloxacin in the sample specifically, thereby selective enrichment, purification assays thing efficiently there are good reality needs.
Molecular imprinting is based on the technology of preparing of the new polymers of molecular recognition, the specific recognition site energy and the assay selectively acting that in trace, form, and this effect is a reversible.The mechanical strength of this chemosynthesis and chemical stability are good, can use in extreme environment.In recent years, molecular imprinting is applied to Solid-Phase Extraction, and molecularly imprinted polymer as solid phase extraction filler, has been produced a field with wide application future, is mainly used in the analysis of sample in the extraction, particularly biofluid of material in the biological sample.
Find through literature search, begun to explore the method that molecular imprinting detects Enrofloxacin in the food of using at present prior art.Ester Caro etc. are at " Analytica Chimica Acta " (2006,562, propose to use molecularly imprinted polymer among " the Novel enrofloxacin imprinted polymer applied to thesolid-phase extraction of fluorinated quinolones from urine and tissuesamples " that delivers 145-151) (use molecularly imprinted polymer and detect Enrofloxacin) and combine, the detection sensitivity of Enrofloxacin can be increased to 50 μ g/kg with the HPLC detection method; But, the method of their used mass polymerization need obtain the molecularly imprinted polymer particle of required particle diameter by complicated procedures such as sub-sieves, and it exists shortcomings such as yield is low, particle shape is irregular, bad dispersibility, and also can cause the molecular recognition of molecularly imprinted polymer and selectivity to descend in the process of lapping, product can not directly extract assay from the aqueous solution.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of preparation method of molecular blotting polymer microsphere and the method for separating enrofloxacin thereof are provided.Make it by adjusting the molecular blotting polymer microsphere that molecularly imprinted polymer directly prepares appropriate particle size, be filled in the solid phase extraction column, directly separation, the residual Enrofloxacin of purifying from rich water medium are removed the impurity in the food substrate.
The present invention is achieved by the following technical solutions, the present invention adjusts molecularly imprinted polymer at Enrofloxacin test sample pretreatment stage, prepare molecular blotting polymer microsphere with good molecular recognition performance, and further Solid-Phase Extraction, separation, the efficiently concentrating of the specific selectivity of Enrofloxacin improve the sensitivity that detects in food substrate (as milk etc.).
The present invention relates to the preparation method of molecular blotting polymer microsphere, specifically may further comprise the steps:
1. the mixture ultrasonication 5～10min that will form by function monomer, Enrofloxacin (template molecule), pore-creating agent chloroform, linking agent ethylene glycol dimethacrylate (EGDMA) and initiator Diisopropyl azodicarboxylate (AIBN), add the preparation polyvinyl alcohol solution, at the uniform velocity stir reaction 24h;
Described polyvinyl alcohol solution is meant: polyvinyl alcohol 1788 aqueous solution, concentration are 3-5%.
The mol ratio of described function monomer, Enrofloxacin and ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate is 4: 0.3～1: 25: 0.5～1; The cumulative volume of chloroform and ethylene glycol dimethacrylate and the volume ratio of water are 1: 5～14.
Described function monomer is meant: methacrylic acid, 4-vinylpyridine, methyl methacrylate, methacrylic acid N or N-diethylamino ethyl ester are as function monomer.
Described at the uniform velocity stirring, stirring velocity: 400～500rpm; Whipping temp: 60～70 ℃.
Described reaction keeps nitrogen atmosphere in the reaction process.
2. in water, stir and filter, clean then, remove template molecule by soxhlet extraction at last;
Described stirring is meant: stir 60min in 70 ℃ of water.
Described cleaning is meant: successively with distilled water washing 2 times, methanol wash 3 times, washing with acetone 2 times.
Described cleaning, sonic oscillation during washing, each 10min.
3. will remove the polymkeric substance of template molecule, vacuum-drying obtains molecular blotting polymer microsphere to constant weight.
Described vacuum-drying, its temperature is: 50 ℃.
Described Enrofloxacin molecular blotting polymer microsphere, median size are about 14～55 μ m, on the molecular blotting polymer microsphere surface many apertures are arranged.
The present invention relates to method, specifically may further comprise the steps with the molecular blotting polymer microsphere separating enrofloxacin:
1. with the methyl alcohol homogenate of the molecular blotting polymer microsphere of Enrofloxacin, be filled in the polypropylene solid phase extraction column, two ends add poly sieve plate up and down, vacuumize to compress filler;
Described sieve plate, the aperture of sieve plate are 0.5 μ m.
2. successively the distilled water mixed solution activates solid-phase extraction column, and further impurity is removed in drip washing, and wash-out, collection Enrofloxacin promptly can be used for detecting.
Described distilled water mixed solution is meant: 15ml methyl alcohol: acetate, and part by weight: 90: 10, the 5ml distilled water.
Described drip washing is meant: with the miscellany drip washing of methyl alcohol and B-R damping fluid, and mixed relationship: 4: 1, v/v, pH:11.
Described wash-out is meant: with methyl alcohol: acetate mixed solution wash-out, part by weight: 90: 10.
Solid phase extraction column of the present invention has single-minded selectivity to Enrofloxacin, is 73.6% to the rate of recovery of Enrofloxacin in the milk sample, and other material is not had specific adsorption.(as HPLC) combines with existing detection method, and detection sensitivity is increased to 10 μ g/kg.The present invention is template molecule with the Enrofloxacin, the employing aqueous suspension polymerization obtains the molecular blotting polymer microsphere at Enrofloxacin, template molecule there is stronger recognition capability, show very high selectivity and sensitivity, can separation, the Enrofloxacin in the purifying, enriched food matrix (as milk), can be used for the pre-treatment of actual sample.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1.
One. the molecular blotting polymer microsphere preparation of Enrofloxacin:
(1) mol ratio of Enrofloxacin, function monomer and ethylene glycol dimethacrylate is 1: 4: 25; The cumulative volume of chloroform and ethylene glycol dimethacrylate and the volume ratio of water are 1: 8; The concentration of polyvinyl alcohol 1788 (PVA1788) is 3%; 0.339ml function monomer methacrylic acid and 1mmol Enrofloxacin are dissolved in the chloroform ultrasonication 5～10min; 5ml ethylene glycol dimethacrylate, 120mg Diisopropyl azodicarboxylate and 15ml chloroform are mixed ultrasonication 5～10min;
Above-mentioned three kinds of solution are mixed, 60～70 ℃ of water-baths, 400～500rpm keeps nitrogen atmosphere to stir 24h; (2) after reaction finishes, stir 60min in 70 ℃ of water, filter, successively with 50ml distilled water washing 2 times, 50ml methanol wash 3 times, 50ml washing with acetone 2 times (removing organism such as residual dispersion agent, monomer), each 10min, sonic oscillation during washing, pass through methyl alcohol at last: acetate (90: 10), methyl alcohol (100%) soxhlet extraction are further removed template molecule; (3) will remove the polymkeric substance of template molecule, vacuum-drying (50 ℃) obtains the polymer microballoon of Enrofloxacin trace to constant weight.
Two. the preparation of Enrofloxacin molecular imprinted solid phase extraction cartridge
With 5ml washed with methanol column wall, the molecular blotting polymer microsphere 0.100g that accurately takes by weighing Enrofloxacin places methyl alcohol, is filled in the 3ml polypropylene solid phase extraction column earlier, and two ends add the polyethylene sieve plate, vacuumize at last to compress sieve plate;
Three. use the enrichment of Enrofloxacin molecular imprinted solid phase extraction cartridge, the Enrofloxacin in the purifying milk is used 15ml methyl alcohol earlier: acetate (90: 10), 5ml distilled water activate solid-phase extraction column, and sample solution is crossed post; Use then 5ml methyl alcohol and B-R damping fluid miscellany (4: 1, v/v, impurity is removed in pH:11) drip washing; Adopt 2ml methyl alcohol at last: acetate (90: 10) wash-out, collect Enrofloxacin; 0.22 behind the μ m membrane filtration, detect by high performance liquid chromatography.
Four. the solid phase extraction column performance analysis is estimated
(1) use 15ml methyl alcohol earlier: acetate (part by weight: 90: 10) is washed post, washes post with the 5ml distilled water then, removes residual liquid, and filler is drained off.
(2) go up sample, get 2ml and go up sample solution; Last sample solution has Enrofloxacin standard substance and analogue (terramycin, nitrofural) thereof; Wherein Enrofloxacin standardized solution preparation: the 0.036g Enrofloxacin is dissolved in the standardized solution of preparation 1mmol/L in the 100.0mL methyl alcohol, adopts distilled water to be diluted to 0.01mmol/L; Flow velocity is 0.50ml/min, and vacuum pump vacuumizes to remove liquid residual in the post (＜1 min).
(3) drip washing, with the miscellany drip washing of 5ml methyl alcohol and B-R damping fluid, mixed relationship: 4: 1, v/v, pH:11, flow velocity＜1min/ml.
(4) wash-out, with 2ml methyl alcohol: acetate mixed solution wash-out, part by weight: 90: 10, collect eluting liquid, go up sample behind the 0.22 μ m membrane filtration, HPLC analyzes.
The effect of present embodiment is, the molecular blotting polymer microsphere of preparation can be discerned Enrofloxacin specifically, as the solid phase extraction column of filler separation, enrichment and the purifying of Enrofloxacin had single-minded selectivity.The rate of recovery to the Enrofloxacin of adding in the milk is 68.3%.Medicine to other kind does not have specific absorption.
Embodiment 2.
One. the molecular blotting polymer microsphere preparation of Enrofloxacin:
(1) mol ratio of template molecule, function monomer and ethylene glycol dimethacrylate is 0.5: 4: 25; The cumulative volume of chloroform and ethylene glycol dimethacrylate and the volume ratio of water are 1: 5; The concentration of polyvinyl alcohol 1788 (PVA1788) is 4%; 0.339ml function monomer methyl methacrylate and 0.5mmol Enrofloxacin are dissolved in the chloroform ultrasonication 5～10min; 5ml ethylene glycol dimethacrylate, 120mg Diisopropyl azodicarboxylate and 15ml chloroform are mixed ultrasonication 5～10min; Above-mentioned three kinds of solution are mixed, 60～70 ℃ of water-baths, 400～500rpm keeps nitrogen atmosphere to stir 24h; (2) after reaction finishes, stir 60min in 70 ℃ of water, filter, successively with 50ml distilled water washing 2 times, 50ml methanol wash 3 times, 50ml washing with acetone 2 times (removing organism such as residual dispersion agent, monomer), each 10min, sonic oscillation during washing, pass through methyl alcohol at last: acetate (90: 10), methyl alcohol (100%) soxhlet extraction are further removed template molecule; (3) will remove the polymkeric substance of template molecule, vacuum-drying (50 ℃) obtains the polymer microballoon of Enrofloxacin trace to constant weight.
Two. the preparation of Enrofloxacin molecular imprinted solid phase extraction cartridge
With 5ml washed with methanol column wall, the molecular blotting polymer microsphere 0.200g that accurately takes by weighing Enrofloxacin places methyl alcohol, is filled in the 3ml polypropylene solid phase extraction column earlier, and two ends add the polyethylene sieve plate, vacuumize at last to compress sieve plate;
Three. use the enrichment of Enrofloxacin molecular imprinted solid phase extraction cartridge, the Enrofloxacin in the purifying milk
Earlier use 15ml methyl alcohol: acetate (90: 10), 5ml distilled water activate solid-phase extraction column, and sample solution is crossed post; Use then 5ml methyl alcohol and B-R damping fluid miscellany (4: 1, v/v, impurity is removed in pH:11) drip washing; Adopt 2ml methyl alcohol at last: acetate (90: 10) wash-out, collect Enrofloxacin; 0.22 behind the μ m membrane filtration, detect by high performance liquid chromatography.
The effect of present embodiment is, the molecular blotting polymer microsphere of preparation can be discerned Enrofloxacin specifically, as the solid phase extraction column of filler separation, enrichment and the purifying of Enrofloxacin had single-minded selectivity.The rate of recovery to the Enrofloxacin of adding in the milk is 73.6%.Medicine to other kind does not have specific absorption.
Embodiment 3.
One. the molecular blotting polymer microsphere preparation of Enrofloxacin:
(1) mol ratio of template molecule, function monomer and ethylene glycol dimethacrylate is 0.33: 4: 25; The cumulative volume of chloroform and ethylene glycol dimethacrylate and the volume ratio of water are 1: 6; The concentration of polyvinyl alcohol 1788 (PVA1788) is 5%; 0.339ml function monomer N-diethylamino ethyl ester or 4-vinylpyridine or methacrylic acid N and 0.33mmol Enrofloxacin are dissolved in the chloroform ultrasonication 5～10min; 5ml ethylene glycol dimethacrylate, 120mg Diisopropyl azodicarboxylate and 15ml chloroform are mixed ultrasonication 5～10min; Above-mentioned three kinds of solution are mixed, 60～70 ℃ of water-baths, 400～500rpm keeps nitrogen atmosphere to stir 24h; (2) after reaction finishes, stir 60min in 70 ℃ of water, filter, successively with 50ml distilled water washing 2 times, 50ml methanol wash 3 times, 50ml washing with acetone 2 times (removing organism such as residual dispersion agent, monomer), each 10min, sonic oscillation during washing, pass through methyl alcohol at last: acetate (90: 10), methyl alcohol (100%) soxhlet extraction are further removed template molecule; (3) will remove the polymkeric substance of template molecule, vacuum-drying (50 ℃) obtains the polymer microballoon of Enrofloxacin trace to constant weight.
Two. the preparation of Enrofloxacin molecular imprinted solid phase extraction cartridge
With 5ml washed with methanol column wall, the molecular blotting polymer microsphere 0.300g that accurately takes by weighing Enrofloxacin places methyl alcohol, is filled in the 3ml polypropylene solid phase extraction column earlier, and two ends add the polyethylene sieve plate, vacuumize at last to compress sieve plate;
Three. use the enrichment of Enrofloxacin molecular imprinted solid phase extraction cartridge, the Enrofloxacin in the purifying milk
Earlier use 15ml methyl alcohol: acetate (90: 10), 5ml distilled water activate solid-phase extraction column, and sample solution is crossed post; Use then 5ml methyl alcohol and B-R damping fluid miscellany (4: 1, v/v, impurity is removed in pH:11) drip washing; Adopt 2ml methyl alcohol at last: acetate (90: 10) wash-out, collect Enrofloxacin; 0.22 behind the μ m membrane filtration, detect by high performance liquid chromatography.
The effect of present embodiment is, the molecular blotting polymer microsphere of preparation can be discerned Enrofloxacin specifically, as the solid phase extraction column of filler separation, enrichment and the purifying of Enrofloxacin had single-minded selectivity.The rate of recovery to the Enrofloxacin of adding in the milk is 71.2%.Medicine to other kind does not have specific absorption.
Claims (10)
1. the preparation method of a molecular blotting polymer microsphere is characterized in that, may further comprise the steps:
1. the mixture ultrasonication 5～10min that will be made up of function monomer, Enrofloxacin template, pore-creating agent chloroform, ethylene glycol dimethacrylate linking agent and Diisopropyl azodicarboxylate initiator adds the preparation polyvinyl alcohol solution, at the uniform velocity stirs reaction 24h;
2. in water, stir and filter, clean then, remove template molecule by soxhlet extraction at last;
3. will remove the polymkeric substance of template molecule, vacuum-drying obtains molecular blotting polymer microsphere to constant weight.
2. the preparation method of molecular blotting polymer microsphere according to claim 1 is characterized in that, the mol ratio of described function monomer, Enrofloxacin and ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate is 4: 0.3～1: 25: 0.5～1; The cumulative volume of chloroform and ethylene glycol dimethacrylate and the volume ratio of water are 1: 5～14.
3. according to the preparation method of claim 1 or 2 described molecular blotting polymer microspheres, it is characterized in that described function monomer is meant: methacrylic acid, 4-vinylpyridine, methyl methacrylate, methacrylic acid N or N-diethylamino ethyl ester.
4. the preparation method of molecular blotting polymer microsphere according to claim 1 is characterized in that, described cleaning is meant: successively with distilled water washing 2 times, and methanol wash 3 times, washing with acetone 2 times, sonic oscillation during washing, each 10min.
5. the preparation method of molecular blotting polymer microsphere according to claim 1 is characterized in that, described Enrofloxacin molecular blotting polymer microsphere, and median size is about 14～55 μ m, on the molecular blotting polymer microsphere surface many apertures is arranged.
6. a method that adopts molecular blotting polymer microsphere separating enrofloxacin as claimed in claim 1 is characterized in that, specifically may further comprise the steps:
1. with the methyl alcohol homogenate of the molecular blotting polymer microsphere of Enrofloxacin, be filled in the polypropylene solid phase extraction column, two ends add poly sieve plate up and down, vacuumize to compress filler;
2. successively the distilled water mixed solution activates solid-phase extraction column, and further impurity is removed in drip washing, and wash-out, collection Enrofloxacin promptly can be used for detecting.
7. the method for molecular blotting polymer microsphere separating enrofloxacin according to claim 6 is characterized in that, described sieve plate, and the aperture of sieve plate is 0.5 μ m.
8. the method for molecular blotting polymer microsphere separating enrofloxacin according to claim 6 is characterized in that, described distilled water mixed solution is meant: 15ml methyl alcohol: acetate, and part by weight: 90: 10, the 5ml distilled water.
9. the method for molecular blotting polymer microsphere separating enrofloxacin according to claim 6 is characterized in that, described drip washing is meant: with the miscellany drip washing of methyl alcohol and B-R damping fluid, and mixed relationship: 4: 1, v/v, pH:11.
10. the method for molecular blotting polymer microsphere separating enrofloxacin according to claim 6 is characterized in that, described wash-out is meant: with methyl alcohol: acetate mixed solution wash-out, part by weight: 90: 10.
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| CN111443152B (en) * | 2020-03-26 | 2022-08-23 | 中国检验检疫科学研究院 | Method and kit for detecting content of quinolone compounds |
| CN113533279A (en) * | 2021-07-15 | 2021-10-22 | 河北农业大学 | Method for detecting enrofloxacin by using fluorescent dipeptide nano microspheres/nucleic acid aptamer |
| CN113817217A (en) * | 2021-10-19 | 2021-12-21 | 肇庆学院 | Porous polymer microsphere for high selective adsorption of enrofloxacin and preparation method thereof |
| CN115181465A (en) * | 2022-07-07 | 2022-10-14 | 浙江工业大学 | Preparation method of molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles |
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