CN100374860C - Process for producing chloromycetin molecular engram solid phase extraction small column - Google Patents
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Abstract
The present invention relates to a preparing method of a small column for chloromycetin molecular engram solid-phase extraction, which belongs to the technical field of biological engineering. In the present invention, chloromycetin molecular engram polymer microspheres are prepared from template molecules (chloromycetin), functional monomers (methacrylic acid N, N-diethylaminoethyl methacrylate) and a crosslinking agent (ethylene glycol dimethacrylate) in a molar ratio of 1: (2 to 8): 25 by suspending polymerization; then the chloromycetin molecular engram polymer microspheres are weighed to fill into a small column for polypropylene solid-phase extraction; finally a small column for chloromycetin molecular engram solid-phase extraction is prepared. The small column for the chloromycetin molecular engram solid-phase extraction prepared by the present invention can be used to detect the selective purification and enrichment of the residual sample solution of chloromycetin in food. Compared with common liquid-liquid extration and C18 solid-phase extraction methods, the present invention has the characteristics of higher simplicity, higher speed, higher purification efficiency, etc.
Description
Technical field
What the present invention relates to is a kind of method of technical field of bioengineering, and specifically, the high selectivity that relates to the residual chloromycetin in animal derived food and the aquatic products is separated, the preparation method of the chloromycetin molecular engram solid phase extraction small column of purifying, enrichment.
Background technology
Chloromycetin (chloramphenicol is called for short CAP) is nineteen forty-seven to separate the broad-spectrum antibiotic that obtains first from the nutrient solution of Venezuela Streptothrix (Streptomyces Venezuela), and gram-positive bacteria, Gram-negative bacteria are all had inhibiting effect.Yet, owing to be with nitro on its phenyl ring, its half life of decomposition is long and have serious toxic and side effect, for residual chloromycetin, has multiple detection method, at present, developed country is more and more stricter to the requirement of its detection limit, and European Union reduces to 0.1 μ g/kg by 10 original μ g/kg, and the detection limit of U.S. FDA regulation is also reduced to 0.3 μ g/kg by 5 original μ g/kg, and more sensitive method can make detection limit reach 0.1 μ g/kg at present.Therefore, the residual chloromycetin in animal derived food and the aquatic products has become the major obstacle that China enlarges International Agricultural Trade.
At present, in the detection of residual chloromycetin, the pre-treatment process of sample is very important, solid phase extraction techniques is a kind of isolation technics better, quicker, easier than liquid-liquid extraction, but the acting force between its object of traditional Solid-Phase Extraction and the adsorbent is nonspecific, limited further developing of solid phase extraction techniques, therefore, the development of novel high selectivity recognition capability filler matrix is very important.And molecularly imprinted polymer has binding site and the hole that is complementary with template molecule, and template molecule is had single-minded recognition capability, has anti-adverse environment ability, high stability and long advantages such as serviceable life simultaneously.
Find through literature search prior art, Mena etc. are at " Anal Bioanal Chem " (bioanalysis chemistry) 2003,376, propose to use molecularly imprinted polymer extraction pillar among " the Molecularly imprinted polymers foron-line clean-up and preconcentration of chloramphenicol prior to itsvoltammetric determination " that delivers on the 18-25 (utilize chloramphenicol molecularly imprinted polymeric to carry out voltammetry and detect preceding in-line purification and preceding enrichment) and combine, can make the enrichment factor of residual chloromycetin reach 500 with voltammetry; The concrete molecularly imprinted polymer assembling extraction pillar that adopts the mass polymerization preparation after steps such as last sample, wash-out, is analyzed by voltammetry.Its weak point is to exist shortcoming such as molecularly imprinted polymer grain size heterogeneity, particle shape be irregular, and is relatively poor to the concentration effect of trace amount chloramphenicol.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of chloromycetin molecular engram solid phase extraction small column is provided, make its selectivity purifying and the enrichment that can simply, fast, efficiently measure chloromycetin in animal derived food and the aquatic products (CAP) residual quantity, can be directly used in specific selectivity separation, efficiently concentrating chloromycetin.
The present invention is achieved by the following technical solutions, and the preparation of chloromycetin molecular engram solid phase extraction small column of the present invention may further comprise the steps:
(1) with template molecule chloromycetin, function monomer methacrylic acid N, N-diethylamino ethyl ester (DAM) and crosslinking chemical ethylene glycol dimethacrylate (EGDMA), press template molecule: function monomer: crosslinking chemical mol ratio=1: 2～8: 25 forms chloramphenicol molecularly imprinted polymeric microspheres by suspension polymerization;
(2) weighing chloramphenicol molecularly imprinted polymeric microspheres 0.050～0.200g is filled in the 1ml-6ml polypropylene solid phase extraction column.The top of filler and bottom are loaded onto the tygon sieve plate in 20 μ m apertures respectively; Adopt methyl alcohol: isopropyl alcohol=2: 1 (v/v) vacuumizes under the state as dress post homogenate liquid, with the homogenate polypropylene solid phase extraction column of packing into, and the tight sieve plate of bonnet.
Described chloramphenicol molecularly imprinted polymeric microspheres, its preparation process is as follows:
1) mol ratio with template molecule, function monomer and crosslinking chemical is 1: 2～8: 25; The cumulative volume of thinning agent and crosslinking chemical and the volume ratio of water are 1: 6～14; As in the water, 80 ℃ are stirred 30min to its whole dissolvings with polyvinyl alcohol (PVA) 1788; The concentration of polyvinyl alcohol (PVA) 1788 (PVA1788) is 3～6%; With function monomer methacrylic acid N, N-diethylamino ethyl ester (DAM) and template molecule chloromycetin are dissolved in the thinning agent, ultrasonication 5～10min; With crosslinking chemical ethylene glycol dimethacrylate (EGDMA), initiating agent (AIBN) and mixing diluents, ultrasonication 5～10min; Above-mentioned three kinds of solution are mixed, stir 20～24h 60～75 ℃ of constant temperature 350～450rpm constant speed;
2) after reaction finishes, the molecular blotting polymer microsphere of above-mentioned prepared in reaction is stirred 60min in 80 ℃ of water, cooling is filtered then, filter the back with distilled water washing 3 times, use methanol wash again 3 times, washing with acetone 2 times, each 15min further removes template molecule by soxhlet extraction at last;
3) will remove the polymkeric substance vacuum drying (50 ℃) of template molecule, obtain chloramphenicol molecularly imprinted polymeric microspheres (average pore size is about 40～120 μ m).
Described thinning agent is octanol: the mixed solvent of chloroform volume ratio=5: 1; Described initiating agent is azoisobutyronitrile.
The chloromycetin molecular engram solid phase extraction small column of method for preparing of the present invention is applied to detect selectivity purifying, the enrichment of the sample solution of chloramphenicol residue in the food, and concrete steps are as follows:
(1) after solid phase extraction column fills, at first uses 10ml acetone, 10ml washed with methanol;
(2) add sample solution 1ml;
(3) with 1ml40% methyl alcohol drip washing 3 times;
(4) with 0.5～1.5ml methanol-eluted fractions 1 time.
The chloramphenicol molecularly imprinted polymeric microspheres that the present invention makes is a kind of macromolecule cross-linked polymer that has fixedly hole size, shape and definite arranging functional group is arranged, and the spatial structure of chloromycetin molecule is had dynamically " memory " function.The present invention adopts the chloromycetin molecular engram solid phase extraction small column of its preparation, can be applicable to measure selectivity purifying, the enrichment of the sample solution of chloramphenicol residue in animal derived food and the aquatic products, more common liquid-liquid extraction method, the C18 solid phase extraction is more simple, quick, efficient is higher.
Embodiment
Provide following examples in conjunction with content of the present invention:
Embodiment 1.
(1) preparation of chloramphenicol molecularly imprinted polymeric microspheres
(1), the mol ratio of template molecule, function monomer and crosslinking chemical is 1: 2; The cumulative volume of thinning agent and crosslinking chemical and the volume ratio of water are 1: 6; The concentration of polyvinyl alcohol (PVA) 1788 (PVA1788) is 3%; With 0.8ml function monomer methacrylic acid N, N-diethylamino ethyl ester (DAM) and 1mmol template molecule chloromycetin are dissolved in the thinning agent ultrasonication 5min; 5ml crosslinking chemical ethylene glycol dimethacrylate (EGDMA), 120mg initiating agent (AIBN) and 15ml thinning agent (octanol 10ml, chloroform 5ml) are mixed ultrasonication 5～10min; Above-mentioned three kinds of solution are mixed, stir 20h 60 ℃ of constant temperature 350rpm constant speed; (2), the molecular blotting polymer microsphere of above-mentioned prepared in reaction is stirred 60min in 80 ℃ of water, cooling is filtered then, filters the back with distilled water washing 3 times, use the 20ml methanol wash again 3 times, 20ml washing with acetone 2 times, each 15min further removes template molecule by soxhlet extraction at last; (3), will remove the polymkeric substance of template molecule, vacuum drying (50 ℃) obtains chloramphenicol molecularly imprinted polymeric microspheres (80～100 μ m).
(2) preparation of chloromycetin solid phase extraction column
At first use 5ml washed with methanol column wall, take by weighing then 0.050g MIPs (methyl alcohol: isopropyl alcohol=2: 1v/v) dress post (1ml solid phase extraction column), loading height is about 1cm, the top of filler and bottom are equipped with the tygon sieve plate in 20 μ m apertures respectively; Adopt methyl alcohol: isopropyl alcohol=2: 1 (v/v) vacuumizes under the state as dress post homogenate liquid, with the homogenate polypropylene solid phase extraction column of packing into, covers tight sieve plate then.
(3) chloromycetin molecular engram solid phase extraction small column is applied to detect selectivity purifying, the enrichment of the sample solution of chloramphenicol residue in the food, and concrete steps are as follows:
After solid phase extraction column fills, at first use 10ml acetone, 10ml washed with methanol; Add sample solution 1ml then; With 1ml 40% methyl alcohol drip washing 3 times; With 0.5～1.5ml methanol-eluted fractions 1 time.
(4) the solid phase extraction column performance evaluation is estimated
(1), with 3ml methyl alcohol rinse pillar, and keep 2min, use sample solution on the 3ml phosphate buffer (each 1ml) rinse pillar then, remove residual liquid, keep moistening, do not allow filler drain off before the last sample;
(2), go up sample, get 1ml and go up sample solution; Last sample solution has chloromycetin standard items and analog (terramycin, streptomysin and tetracycline) thereof; Wherein chloromycetin standard solution preparation: 0.016g chloromycetin is dissolved in the chloromycetin standard solution of a series of concentration gradients of preparation (0.01,0.05,0.5,2.5,5,25 μ g/ml) in the 5.0mL methyl alcohol, adopts the phosphate buffer dilution; Flow velocity is 0.20ml/min, vacuum pump vacuumize with remove liquid residual in the post (＜1min).Collect trickle, go up sample behind the 0.22 μ m membrane filtration;
(3), drip washing, 3 * 1ml leacheate (40% methyl alcohol) drip washing, flow velocity＜1min/ml;
(4), wash-out, at first add the static 2min of 0.25ml methyl alcohol, add 0.25ml methyl alcohol then and vacuumize wash-out, collect eluting liquid, add the 1.5ml phosphate buffer, go up sample behind the 0.22 μ m membrane filtration, HPLC analyzes.
It is pure that above reagent is analysis, available from U.S. sigma company; Other reagent: methyl alcohol, acetone (analyze pure) available from Chinese traditional Chinese medicines group
Its invention effect is, this solid phase extraction column has single-minded selectivity to chloromycetin, is 85.6% to the recovery of chloromycetin standard model, and other analog is not had specific adsorption.
Embodiment 2.
(1) preparation of chloramphenicol molecularly imprinted polymeric microspheres
(1), the mol ratio with template molecule, function monomer and crosslinking chemical is 1: 4; The cumulative volume of thinning agent and crosslinking chemical and the volume ratio of water are 1: 8; The concentration of polyvinyl alcohol (PVA) 1788 (PVA1788) is 4%; With 0.8ml function monomer methacrylic acid N, N-diethylamino ethyl ester (DAM) and 1mmol template molecule chloromycetin are dissolved in the thinning agent ultrasonication 5～10min; 5ml crosslinking chemical ethylene glycol dimethacrylate (EGDMA), 120mg initiating agent (AIBN) and 15ml thinning agent (octanol 10ml, chloroform 5ml) are mixed ultrasonication 5～10min; Above-mentioned three kinds of solution are mixed, stir 22h 65 ℃ of constant temperature 400rpm constant speed; (2), the molecular blotting polymer microsphere of above-mentioned prepared in reaction is stirred 60min in 80 ℃ of water, cooling is filtered then, filters the back with distilled water washing 3 times, use the 20ml methanol wash again 3 times, 20ml washing with acetone 2 times, each 15min further removes template molecule by soxhlet extraction at last; (3), will remove the polymkeric substance of template molecule, vacuum drying (50 ℃) obtains chloramphenicol molecularly imprinted polymeric microspheres (80～100 μ m);
(2) preparation of chloromycetin solid phase extraction column
At first use 5ml washed with methanol column wall, take by weighing then 0.200g MIPs (methyl alcohol: isopropyl alcohol=2: 1v/v) dress post (6ml solid phase extraction column), loading height is about 1cm, the top of filler and bottom are equipped with the tygon sieve plate in 20 μ m apertures respectively; Adopt methyl alcohol: isopropyl alcohol=2: l (v/v) as dress post homogenate liquid, vacuumize under the state,, cover tight sieve plate then the homogenate polypropylene solid phase extraction column of packing into.
(3) chloromycetin molecular engram solid phase extraction small column is applied to detect selectivity purifying, the enrichment of the sample solution of chloramphenicol residue in the food, and concrete steps are as follows:
After solid phase extraction column fills, at first use 10ml acetone, 10ml washed with methanol; Add sample solution 1ml then; With 1ml40% methyl alcohol drip washing 3 times; With 0.5～1.5ml methanol-eluted fractions 1 time.
Its invention effect, this solid phase extraction column has single-minded selectivity to chloromycetin, is 82.6% to the recovery of chloromycetin standard model, and other analog is not had specific adsorption.
Embodiment 3
(1) preparation of chloramphenicol molecularly imprinted polymeric microspheres
(1), the mol ratio with template molecule, function monomer and crosslinking chemical is 8: 25; The cumulative volume of thinning agent and crosslinking chemical and the volume ratio of water are 114; The concentration of polyvinyl alcohol (PVA) 1788 (PVA1788) is 6%; With 0.8ml function monomer methacrylic acid N, N-diethylamino ethyl ester (DAM) and 1mmol template molecule chloromycetin are dissolved in the thinning agent ultrasonication 10min; 5ml crosslinking chemical ethylene glycol dimethacrylate (EGDMA), 120mg initiating agent (AIBN) and 15ml thinning agent (octanol 10ml, chloroform 5ml) are mixed ultrasonication 10min; Above-mentioned three kinds of solution are mixed, stir 24h 75 ℃ of constant temperature 450rpm constant speed; (2), the molecular blotting polymer microsphere of above-mentioned prepared in reaction is stirred 60min in 80 ℃ of water, cooling is filtered then, filters the back with distilled water washing 3 times, use the 20ml methanol wash again 3 times, 20ml washing with acetone 2 times, each 15min further removes template molecule by soxhlet extraction at last; (3), will remove the polymkeric substance of template molecule, vacuum drying (50 ℃) obtains chloramphenicol molecularly imprinted polymeric microspheres (60～80 μ m);
(2) preparation of chloromycetin solid phase extraction column
At first use 5ml washed with methanol column wall, take by weighing then 0.300g MIPs (methyl alcohol: isopropyl alcohol=2: 1v/v) dress post (6ml solid phase extraction column), loading height is about 1cm, the top of filler and bottom are equipped with the tygon sieve plate in 20 μ m apertures respectively; Adopt methyl alcohol: isopropyl alcohol=2: 1 (v/v) vacuumizes under the state as dress post homogenate liquid, with the homogenate polypropylene solid phase extraction column of packing into, covers tight sieve plate then.
(3) chloromycetin molecular engram solid phase extraction small column is applied to detect selectivity purifying, the enrichment of the sample solution of chloramphenicol residue in the food, and concrete steps are as follows:
After solid phase extraction column fills, at first use 10ml acetone, 10ml washed with methanol; Add sample solution 1ml then; With 1ml 40% methyl alcohol drip washing 3 times; With 0.5～1.5ml methanol-eluted fractions 1 time.
Its invention effect, this solid phase extraction column has single-minded selective to chloramphenicol, to the chloramphenicol standard sample The rate of recovery of product is 85.6%, and other analog is not had specific adsorption.
Claims (8)
1. the preparation method of a chloromycetin molecular engram solid phase extraction small column is characterized in that: may further comprise the steps:
(1) with template molecule chloromycetin, function monomer methacrylic acid N, N-diethylamino ethyl ester and crosslinking chemical ethylene glycol dimethacrylate, press template molecule: function monomer: crosslinking chemical mol ratio=1: 2～8: 25 forms chloramphenicol molecularly imprinted polymeric microspheres by suspension polymerization;
(2) weighing chloramphenicol molecularly imprinted polymeric microspheres is filled in the polypropylene solid phase extraction column, and the top of filler and bottom are loaded onto the tygon sieve plate respectively; Adopt methyl alcohol: isopropyl alcohol volume ratio=2: 1 vacuumizes under the state as dress post homogenate liquid, with the homogenate polypropylene solid phase extraction column of packing into, and the tight sieve plate of bonnet;
Described chloramphenicol molecularly imprinted polymeric microspheres, its preparation process is as follows:
1) chloromycetin, methacrylic acid N, the mol ratio of N-diethylamino ethyl ester and ethylene glycol dimethacrylate is 1: 2～8: 25; The cumulative volume of thinning agent and ethylene glycol dimethacrylate and the volume ratio of water are 1: 6～14; Polyvinyl alcohol (PVA) 1788 is added in the entry, be stirred to its whole dissolvings; With methacrylic acid N, N-diethylamino ethyl ester and chloromycetin are dissolved in the thinning agent, ultrasonication; With ethylene glycol dimethacrylate, initiating agent and mixing diluents, ultrasonication; Above-mentioned three kinds of solution are mixed, and the constant temperature constant speed stirs;
2) after reaction finishes, the chloramphenicol molecularly imprinted polymeric microspheres of above-mentioned prepared in reaction is stirred in water, cooling is filtered then, filters the back and washs successively with distilled water, methyl alcohol, acetone, further removes template molecule chloromycetin by soxhlet extraction at last;
3) will remove the polymkeric substance vacuum drying of template molecule chloromycetin, obtain chloramphenicol molecularly imprinted polymeric microspheres.
2. the preparation method of chloromycetin molecular engram solid phase extraction small column according to claim 1 is characterized in that, weighing chloramphenicol molecularly imprinted polymeric microspheres 0.050～0.200g is filled in the 1ml-6ml polypropylene solid phase extraction column.
3. the preparation method of chloromycetin molecular engram solid phase extraction small column according to claim 1 is characterized in that, described tygon sieve plate, and its aperture is 20 μ m.
4. the preparation method of chloromycetin molecular engram solid phase extraction small column according to claim 1 is characterized in that, in the step, described thinning agent is octanol: the mixed solvent of chloroform, volume ratio are 5: 1; Described initiating agent is azoisobutyronitrile.
5. the preparation method of chloromycetin molecular engram solid phase extraction small column according to claim 1 is characterized in that, in the step 1), the concentration of polyvinyl alcohol (PVA) 1788 is 3～6%, 80 ℃ and stirs 30min to its all dissolving in water.
6. the preparation method of chloromycetin molecular engram solid phase extraction small column according to claim 1 is characterized in that, in the step 1), the ultrasonication time is 5～10min; The constant temperature constant speed stirs and is meant: stir 20～24h 60～70 ℃ of constant temperature 350～400rpm constant speed.
7. the preparation method of chloromycetin molecular engram solid phase extraction small column according to claim 1, it is characterized in that, step 2) in, molecular blotting polymer microsphere stirs 60min in 80 ℃ of water, cooling is filtered then, filters the back with distilled water washing 3 times, uses methanol wash again 3 times, washing with acetone 2 times, each 15min.
8. the preparation method of chloromycetin molecular engram solid phase extraction small column according to claim 1 is characterized in that, in the step 3), the vacuum drying temperature is 50 ℃, and obtaining average pore size is 40～120 μ m chloramphenicol molecularly imprinted polymeric microspheres.
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| CN101498701B (en) * | 2009-03-09 | 2011-05-25 | 南京大学 | Detection method for phthalate ester residue |
| CN101591412B (en) * | 2009-06-03 | 2011-05-18 | 中国农业科学院农业质量标准与检测技术研究所 | Method for preparing chloramphenicol molecularly imprinted polymeric microspheres |
| CN101628955B (en) * | 2009-07-31 | 2011-07-27 | 宁波大学 | Method for preparing molecular imprinted polymer for recognizing chloromycetin, thiamphenicol and florfenicol simultaneously |
| CN101914189A (en) * | 2010-08-04 | 2010-12-15 | 上海交通大学 | Preparation method and application of molecular imprinted polymer on silica surface for specifically adsorbing patulin |
| CN102228825B (en) * | 2011-06-28 | 2012-12-19 | 江苏大学 | Preparation method and application of chlordimeform molecular imprinting solid phase extraction column |
| CN107179367B (en) * | 2017-06-15 | 2024-01-26 | 青岛贞正分析仪器有限公司 | Solid phase extraction series column for toxin detection and preparation method thereof |
| CN112110861B (en) * | 2020-08-10 | 2023-03-28 | 广东省农业科学院蚕业与农产品加工研究所 | Carbendazim virtual template molecularly imprinted polymer and preparation method thereof |
| CN114917881A (en) * | 2022-05-19 | 2022-08-19 | 中国烟草总公司郑州烟草研究院 | Heterocyclic amine molecularly imprinted composite material and preparation method and application thereof |
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