CN1811411A - Process for producing chloromycetin molecular engram polymer microsphere - Google Patents
Process for producing chloromycetin molecular engram polymer microsphere Download PDFInfo
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- CN1811411A CN1811411A CN 200610023903 CN200610023903A CN1811411A CN 1811411 A CN1811411 A CN 1811411A CN 200610023903 CN200610023903 CN 200610023903 CN 200610023903 A CN200610023903 A CN 200610023903A CN 1811411 A CN1811411 A CN 1811411A
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- molecularly imprinted
- polymeric microspheres
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- chloramphenicol
- imprinted polymeric
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- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 title claims abstract description 53
- 239000004005 microsphere Substances 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 title claims abstract description 13
- 229940097572 chloromycetin Drugs 0.000 title claims description 25
- 238000000034 method Methods 0.000 title description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229960005091 chloramphenicol Drugs 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 15
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 23
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000012749 thinning agent Substances 0.000 claims description 6
- 238000002525 ultrasonication Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 16
- 229920000344 molecularly imprinted polymer Polymers 0.000 abstract description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract 2
- 239000012620 biological material Substances 0.000 abstract 1
- 239000012154 double-distilled water Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- UJKWLAZYSLJTKA-UHFFFAOYSA-N edma Chemical compound O1CCOC2=CC(CC(C)NC)=CC=C21 UJKWLAZYSLJTKA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002649 immunization Methods 0.000 description 2
- 230000003053 immunization Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
一种氯霉素分子印迹聚合物微球的制备方法，属于生物工程技术领域。具体为：模板分子、功能单体和乙二醇二甲基丙烯酸酯的摩尔比为1∶2～8∶25；稀释剂和乙二醇二甲基丙烯酸酯的总体积与水的体积比为1∶6～14；将聚乙烯醇1788溶于水中；将功能单体和模板分子溶解在稀释剂中；将乙二醇二甲基丙烯酸酯、偶氮二异丁腈和稀释剂混合；将上述三种溶液混合，反应结束后，将产物在水中搅拌，降温过滤，依次用双蒸水、甲醇、丙酮洗涤，再通过索氏萃取除去模板分子；真空干燥，得到氯霉素分子印迹聚合物微球。本发明制得的聚合物微球可应用于食品中氯霉素检测的前处理，为食品中氯霉素的检测提供新型生物材料，在实际中具有很大的应用价值。
The invention discloses a preparation method of chloramphenicol molecularly imprinted polymer microspheres, belonging to the technical field of bioengineering. Specifically: the molar ratio of template molecules, functional monomers and ethylene glycol dimethacrylate is 1: 2 to 8: 25; the volume ratio of the total volume of diluent and ethylene glycol dimethacrylate to water is 1:6~14; dissolve polyvinyl alcohol 1788 in water; dissolve functional monomer and template molecule in diluent; mix ethylene glycol dimethacrylate, azobisisobutyronitrile and diluent; The above three solutions are mixed, after the reaction is completed, the product is stirred in water, cooled and filtered, washed with double distilled water, methanol, and acetone in turn, and the template molecules are removed by Soxhlet extraction; vacuum-dried to obtain chloramphenicol molecularly imprinted polymer Microspheres. The polymer microsphere prepared by the invention can be applied to the pretreatment of the detection of chloramphenicol in food, and provides novel biological materials for the detection of chloramphenicol in food, and has great application value in practice.
Description
Technical field
What the present invention relates to is a kind of method of technical field of bioengineering, specifically, relates to a kind of preparation method of chloramphenicol molecularly imprinted polymeric microspheres.
Background technology
Chloromycetin (chloramphenicol is called for short CAP) is nineteen forty-seven to separate the broad-spectrum antibiotic that obtains first from microbe metabolite.Yet owing to be with nitro on its phenyl ring, its half life of decomposition is long and have serious toxic and side effect, and therefore, the residual chloromycetin in animal food and the aquatic products has constituted grave danger to human health.At present, the residual chloromycetin detection method mainly contains microbial method, immunization, chromatography etc., and has adopted some coupling techniques.Microbial method have poor specificity, sensitivity low, detect limit for height (＞shortcoming such as 3mg/kg); Immunization is the analytical technology based on antigen and antibody specificity association reaction, but when other compound of containing in the sample with the chloromycetin structure similar, false positive results may occur, has a strong impact on the result and judges.Therefore, the pre-treatment process of sample is extremely important.Chromatography mainly comprises liquid phase chromatography and vapor-phase chromatography, is the residual chloromycetin quantitative detection method of generally acknowledging in the world, but its have the sample pretreatment process complexity, cost an arm and a leg, analysis speed waits shortcoming slowly, is not suitable for scene, fast detecting analysis.Adopt solid phase extraction techniques (SPE) to help the separation and the detection of complex matrices, but the acting force between its object of traditional Solid-Phase Extraction and the adsorbent is nonspecific, and the separation of different substrates need be selected different column packings with analyte, has limited further developing of solid phase extraction techniques.Molecular imprinting (MIPs) is a kind of technology of preparing for the polymkeric substance that obtains to mate fully with certain a part on space and binding site, at the multiple biosensor technique relevant with biotechnology and synthesize the application in fields such as artificial antibody.Molecular imprinting has three big characteristics: structure is imitated precordainment, specific recognition, extensive practicality.At present, MIPs and applied research thereof are very active, and coverage is very wide.
Find that through literature search molecular imprinting has begun to be applied in the detection of chloromycetin in the food at present to prior art.Levi etc. are at " Analytical Chemistry " (analytical chemistry, 1997,69, propose to use molecularly imprinted polymer among " the Optical Detection of Chloramphenicol UsingMolecularly Imprinted Polymers " that delivers 2017-2021) (using molecularly imprinted polymer chlorine detection mycin) and combine, the detection sensitivity of chloromycetin can be increased to 10-20 μ g/ml with the HPLC detection method; The concrete method of bulk polymerization that adopts makes chloramphenicol molecularly imprinted polymeric, through grinds, sieve, after a series of processing such as wash-out, obtaining size is the molecularly imprinted polymer of 25-63 μ m, by adorning the HPLC post it is carried out evaluation analysis again.Its weak point is to obtain by complicated procedures such as sub-sieves the molecularly imprinted polymer particle of required particle diameter, and it exists shortcomings such as yield is low, particle shape is irregular, bad dispersibility.Also can cause the molecular recognition and the selectivity of molecularly imprinted polymer to descend in the process of lapping.
Summary of the invention
The objective of the invention is to overcome the deficiency in enrichment that existing molecularly imprinted polymer technology of preparing and chloromycetin relates in the sample pretreatment in detecting, clarification, extraction, the separation and detection method, a kind of preparation method of chloramphenicol molecularly imprinted polymeric microspheres is provided, make it prepare molecular blotting polymer microsphere simply, efficiently with good monodispersity, molecular recognition performance, when being particularly useful for fields such as chromatographic stationary phase, Solid-Phase Extraction, have post and imitate high, good selective, can be directly used in specific selectivity separation, efficiently concentrating chloromycetin.
The present invention is achieved by the following technical solutions, and the preparation method of chloramphenicol molecularly imprinted polymeric microspheres of the present invention specifically may further comprise the steps:
1), the mol ratio of template molecule, function monomer and ethylene glycol dimethacrylate (EGDMA) 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;
2), with polyvinyl alcohol (PVA) 1788 as in the water, 80 ℃ are stirred 30min to its whole dissolvings; The concentration of polyvinyl alcohol (PVA) 1788 (PVA1788) is 3～6%;
3), function monomer and template molecule are dissolved in the thinning agent ultrasonication 5～10min;
4), with ethylene glycol dimethacrylate, initiating agent and mixing diluents, ultrasonication 5～10min;
5), above-mentioned three kinds of solution are mixed, at 60～70 ℃ of constant temperature 350～400rpm constant speed stirring 20～24h;
6) 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;
7), will remove the polymkeric substance of template molecule, vacuum drying (50 ℃) obtains chloramphenicol molecularly imprinted polymeric microspheres.
Described template is chloromycetin.
Described initiating agent is azoisobutyronitrile (AIBN).
Described thinning agent is octanol: the mixed solvent of chloroform volume ratio=5: 1.
Described function monomer is styrene, acrylamide or methacrylic acid N, N-diethylamino ethyl ester.
Keep nitrogen atmosphere in the course of reaction, flow velocity is 0.5ml/min.
Described chloramphenicol molecularly imprinted polymeric microspheres, average pore size are about 40～120 μ m, on the molecular blotting polymer microsphere surface many apertures are arranged.
The present invention prepares chloramphenicol molecularly imprinted polymeric microspheres, is dispersion medium with water in the reaction, and the special molecularly imprinted polymer of prepared chloromycetin is spherical, need not to grind, screening; Usually, the molecularly imprinted polymer that obtains by mass polymerization is bulk, needs to use through grinding and after sieving, and not only subsequent treatment work is loaded down with trivial details, time-consuming, and loss is bigger in grinding the sieve process, and shape of product is irregular, and dispersiveness is relatively poor, and separation efficiency is lower; And the molecular blotting polymer microsphere that suspension polymerization obtains need not grind, and can obtain the polymer microballoon of different-grain diameter by the different proportion of control stirring rate and adjusting spreading agent.This chloramphenicol molecularly imprinted polymeric microspheres will provide good pre-treatment material for the detection of residual chloromycetin in the food, but efficiently concentrating, accurately separate chloromycetin, in conjunction with existing detection method (as ELISA, HPLC etc.), significantly improve the detection sensitivity and the detection efficiency of residual chloromycetin, in food, have bigger application value in the detection of residual chloromycetin.
Description of drawings
The porous molecular blotting polymer microsphere that Fig. 1 makes for the present invention
The porous molecular blotting polymer microsphere surface Electronic Speculum scintigram that Fig. 2 makes for the present invention
Embodiment
Embodiment 1.
The PVA1788 of 100ml 4% is added in the four-hole bottle, and logical nitrogen 10min stirs 400rpm simultaneously.
In another container, will remove 0.8ml DAM, the 5ml EDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, ultrasonic mixing 20min adds 120mg AIBN, the 5ml chloroform continues ultrasonic 5min, adds ice cube when ultrasonic, keeps low temperature then.
Keep stirring rate, the monomer for preparing is added to the good monomer dispersion of assurance in the four-hole bottle.Continue logical nitrogen, 70 ℃, 24h.The polymkeric substance of gained is carried out the wash-out processing.
Pour in the 200ml beaker after after polyreaction finishes the polymkeric substance that obtains being leached water flushing three times, 80 ℃ of distilled waters stir 60min, with 50ml methanol wash three times, twice of 50ml washing with acetone (organism such as flush away sweller, remaining organic monomer), methyl alcohol: acetate (80: 20) soxhlet extraction 24h, wash-out is removed template molecule, methyl alcohol (100%) 24h, (40 μ m) sieves, last 50 ℃ of vacuum drying 6h are to weight, obtaining the mean grain size size at last is the microballoon that there are a lot of apertures on 80 μ m, surface, and its invention effect as shown in Figure 1, 2.
Embodiment 2.
The PVA1788 of 100ml 4% is added in the four-hole bottle, and logical nitrogen 10min stirs 400rpm simultaneously.
In another container, will remove 0.8ml St, the 5ml EGDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, other operation and embodiment 1 with.The microballoon that obtain the mean grain size size at last and be about 120 μ m, there are a lot of apertures on the surface, its invention effect is equal to shown in Fig. 1,2 substantially.
Embodiment 3.
The PVA1788 of 100ml 4% is added in the four-hole bottle, and logical nitrogen 10min stirs 350rpm simultaneously.
In another container, will remove 0.8ml DAM, the 5ml EGDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, ultrasonic mixing 20min adds 120mg AIBN, the 5ml chloroform continues ultrasonic 5min, adds ice cube when ultrasonic, keeps low temperature then.
Keep stirring rate, the monomer for preparing is added to the good monomer dispersion of assurance in the four-hole bottle.Continue logical nitrogen, 70 ℃, 24h.Other operation and embodiment 1 are together.The microballoon that obtain the mean grain size size at last and be about 90 μ m, there are a lot of apertures on the surface, its invention effect is equal to shown in Fig. 1,2 substantially.
Embodiment 4.
The PVA1788 of 100ml 3% is added in the four-hole bottle, and logical nitrogen 10min stirs 400rpm simultaneously.
In another container, will remove 0.8ml DAM, the 5ml EGDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, other operation and embodiment 1 with.The microballoon that obtain the mean grain size size at last and be about 120 μ m, there are a lot of apertures on the surface, its invention effect is equal to shown in Fig. 1,2 substantially.
Embodiment 5.
The PVA1788 of 100ml 5% is added in the four-hole bottle, and logical nitrogen 10min stirs 400rpm simultaneously.
In another container, will remove 0.8ml DAM, the 5ml EGDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, other operation and embodiment 1 with.The microballoon that obtain the mean grain size size at last and be about 60 μ m, there are a lot of apertures on the surface, its invention effect is equal to shown in Fig. 1,2 substantially.
Embodiment 6.
The PVA1788 of 100ml 6% is added in the four-hole bottle, and logical nitrogen 10min stirs 400rpm simultaneously.
In another container, will remove 0.8ml DAM, the 5ml EGDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, other operation and embodiment 1 with.The microballoon that obtain the mean grain size size at last and be about 40 μ m, there are a lot of apertures on the surface, its invention effect is equal to shown in Fig. 1,2 substantially.
Embodiment 7.
The PVA1788 of 100ml 4% is added in the four-hole bottle, and logical nitrogen 10min stirs 400rpm simultaneously.
In another container, will remove 0.4ml DAM, the 5ml EDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, ultrasonic mixing 20min adds 120mg AIBN, the 5ml chloroform continues ultrasonic 5min, adds ice cube when ultrasonic, keeps low temperature then.
Keep stirring rate, the monomer for preparing is added to the good monomer dispersion of assurance in the four-hole bottle.Continue logical nitrogen, 70 ℃, 24h.The polymkeric substance of gained is carried out the wash-out processing.
Pour in the 200ml beaker after after polyreaction finishes the polymkeric substance that obtains being leached water flushing three times, 80 ℃ of distilled waters stir 60min, with 50ml methanol wash three times, twice of 50ml washing with acetone (organism such as flush away sweller, remaining organic monomer), methyl alcohol: acetate (80: 20) soxhlet extraction 24h, wash-out is removed template molecule, methyl alcohol (100%) 24h, (40 μ m) sieves, last 50 ℃ of vacuum drying 6h are to weight, obtaining the mean grain size size at last is the microballoon that there are a lot of apertures on 80 μ m, surface, and its invention effect as shown in Figure 1, 2.
Embodiment 8.
The PVA1788 of 100ml 4% is added in the four-hole bottle, and logical nitrogen 10min stirs 400rpm simultaneously.
In another container, will remove 0.2ml DAM, the 5ml EDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, ultrasonic mixing 20min adds 120mg AIBN, the 5ml chloroform continues ultrasonic 5min, adds ice cube when ultrasonic, keeps low temperature then.
Keep stirring rate, the monomer for preparing is added to the good monomer dispersion of assurance in the four-hole bottle.Continue logical nitrogen, 70 ℃, 24h.The polymkeric substance of gained is carried out the wash-out processing.
Pour in the 200ml beaker after after polyreaction finishes the polymkeric substance that obtains being leached water flushing three times, 80 ℃ of distilled waters stir 60min, with 50ml methanol wash three times, twice of 50ml washing with acetone (organism such as flush away sweller, remaining organic monomer), methyl alcohol: acetate (80: 20) soxhlet extraction 24h, wash-out is removed template molecule, methyl alcohol (100%) 24h, (40 μ m) sieves, last 50 ℃ of vacuum drying 6h are to weight, obtaining the mean grain size size at last is the microballoon that there are a lot of apertures on 80 μ m, surface, and its invention effect as shown in Figure 1, 2.
Embodiment 9.
The PVA1788 of 100ml 4% is added in the four-hole bottle, and logical nitrogen 10min stirs 400rpm simultaneously.
In another container, will remove 0.8ml DAM, the 5ml EDMA of polymerization inhibitor and 10ml octanol, 0.32g chloromycetin, ultrasonic mixing 20min adds 120mg AIBN, the 5ml chloroform continues ultrasonic 5min, adds ice cube when ultrasonic, keeps low temperature then.
Keep stirring rate, the monomer for preparing is added to the good monomer dispersion of assurance in the four-hole bottle.Continue logical nitrogen, 60 ℃, 24h.The polymkeric substance of gained is carried out the wash-out processing.
Pour in the 200ml beaker after after polyreaction finishes the polymkeric substance that obtains being leached water flushing three times, 80 ℃ of distilled waters stir 60min, with 50ml methanol wash three times, twice of 50ml washing with acetone (organism such as flush away sweller, remaining organic monomer), methyl alcohol: acetate (80: 20) soxhlet extraction 24h, wash-out is removed template molecule, methyl alcohol (100%) 24h, (40 μ m) sieves, last 50 ℃ of vacuum drying 6h are to weight, obtaining the mean grain size size at last is the microballoon that there are a lot of apertures on 80 μ m, surface, and its invention effect as shown in Figure 1, 2.
Claims (10)
1, a kind of preparation method of chloramphenicol molecularly imprinted polymeric microspheres is characterized in that may further comprise the steps:
1) mol ratio of template molecule, function monomer 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;
2) with polyvinyl alcohol (PVA) 1788 as in the water, be stirred to its whole dissolvings;
3) function monomer and template molecule are dissolved in the thinning agent ultrasonication;
4) with ethylene glycol dimethacrylate, azoisobutyronitrile and mixing diluents, ultrasonication;
5) above-mentioned three kinds of solution are mixed, the constant temperature constant speed stirs;
6) after reaction finishes, the molecular blotting polymer microsphere of above-mentioned prepared in reaction is stirred in water, cooling is filtered then, after the filtration successively with distilled water wash, methyl alcohol, washing with acetone, further remove template molecule by soxhlet extraction at last;
7) will remove the polymkeric substance of template molecule, vacuum drying obtains chloramphenicol molecularly imprinted polymeric microspheres.
2, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1, it is characterized in that described 2) in, with polyvinyl alcohol (PVA) 1788 as in the water, 80 ℃ are stirred 30min to its whole dissolvings, and the concentration of described polyvinyl alcohol (PVA) 1788 is 3～6%.
3, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1 is characterized in that, described 3) and 4) in, the ultrasonication time is 5～10min.
4, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1 is characterized in that, described 5) in, the constant temperature constant speed stirs, and is meant: stir 20～24h 60～70 ℃ of constant temperature 350～400rpm constant speed.
5, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1, it is characterized in that, described 6) in, molecular blotting polymer microsphere is stirred 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.
6, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1 is characterized in that, described 7) in, the vacuum drying temperature is 50 ℃.
7, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1 is characterized in that, described template is chloromycetin; Described function monomer is styrene, acrylamide or methacrylic acid N, N-diethylamino ethyl ester.
8, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1 is characterized in that, described thinning agent is octanol: the mixed solvent of chloroform volume ratio=5: 1.
9, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1 is characterized in that, keeps nitrogen atmosphere in the course of reaction, and flow velocity is 0.5ml/min.
10, the preparation method of chloramphenicol molecularly imprinted polymeric microspheres according to claim 1 is characterized in that, described chloramphenicol molecularly imprinted polymeric microspheres, and average pore size is 40～120 μ m, on the molecular blotting polymer microsphere surface many apertures is arranged.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610023903 CN1811411A (en) | 2006-02-16 | 2006-02-16 | Process for producing chloromycetin molecular engram polymer microsphere |
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| CN 200610023903 CN1811411A (en) | 2006-02-16 | 2006-02-16 | Process for producing chloromycetin molecular engram polymer microsphere |
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| CN101507916B (en) * | 2009-02-16 | 2011-01-19 | 西北工业大学 | Preparation method of molecularly imprinted polymer microspheres of macrolide antibiotics |
| 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 |
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| CN101387617B (en) * | 2008-10-16 | 2012-07-04 | 上海交通大学 | Silk-screen printing electrode and method for synthesizing chloramphenicol molecular imprinting film |
| CN101507916B (en) * | 2009-02-16 | 2011-01-19 | 西北工业大学 | Preparation method of molecularly imprinted polymer microspheres of macrolide antibiotics |
| 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 |
| CN102336871A (en) * | 2010-07-16 | 2012-02-01 | 中国科学院过程工程研究所 | Chloramphenicol molecular imprinting polymer microballoon with uniformity in size as well as preparation method and application thereof |
| CN102336871B (en) * | 2010-07-16 | 2013-11-06 | 中国科学院过程工程研究所 | Chloramphenicol molecular imprinting polymer microballoon with uniformity in size as well as preparation method and application thereof |
| CN109232823A (en) * | 2018-08-14 | 2019-01-18 | 桂林理工大学 | A kind of preparation method of abietyl TDI type polyurethane molecular engram microsphere |
| CN109265727A (en) * | 2018-08-14 | 2019-01-25 | 桂林理工大学 | A kind of preparation method of abietyl HDI type polyurethane molecular engram microsphere |
| CN109369951A (en) * | 2018-08-14 | 2019-02-22 | 桂林理工大学 | A kind of preparation method of rosin-based IPDI type polyurethane molecularly imprinted microspheres |
| CN109369951B (en) * | 2018-08-14 | 2020-11-24 | 桂林理工大学 | A kind of preparation method of rosin-based IPDI type polyurethane molecularly imprinted microspheres |
| CN109265727B (en) * | 2018-08-14 | 2020-11-24 | 桂林理工大学 | A kind of preparation method of rosin-based HDI type polyurethane molecularly imprinted microspheres |
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