CN102532391B - Method for preparing 17beta-estradiol molecularly imprinted polymer by adopting mixed template - Google Patents
Method for preparing 17beta-estradiol molecularly imprinted polymer by adopting mixed template Download PDFInfo
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Abstract
The invention provides a method for preparing a 17beta-estradiol molecularly imprinted polymer by adopting a mixed template, comprising the steps of taking a mixture of 17beta-estradiol and 17alpha-estradiol as template molecules, selecting and using methacrylic acid or methyl methacrylate as functional monomers, subjecting to ultrasonic processing after mixing with a pore-forming agent, adding a cross-linking agent, standing for 1h, adding an initiator, introducing nitrogen to seal, carrying out bulk polymerization in a container by adopting a thermal initiation way, grinding and sieving the polymer, eluting the template molecule by using a Soxhlet extraction method, drying in vacuum and obtaining the 17beta-estradiol molecularly imprinted polymer. The method has the advantages that 17beta-estradiol can be high-efficiently gathered, therefore, the detection time can be shortened, the detection cost is reduced, and the method has wide application prospects.
Description
Technical field
The invention belongs to macromolecular material and food safety and check technical field, relate to a kind of method that adopts hybrid template to prepare 17 beta-estradiol molecular engram polymers.
Background technology
17 beta estradiols are a kind of natural estrogens, enter the normal endocrine system that can disturb human body after human body, cause human hormone's surplus, and endocrine system disorder has a strong impact on the mankind's health.In environment or all likely residual in animal food, people healthy had to potential harm, therefore be subject to extensive concern.The technology of the current main use of detection to 17 beta estradiols is fluorescent spectroscopy, mass spectroscopy, gas-chromatography, immunodetection and combined interpretation technique.But existing these methods have certain limitation, wherein chromatography needs the technician of expensive extensive instrument and specialty, and need to carry out pre-treatment to sample, the enriched with trace test substance, and often extraction efficiency is low; Immunodetection needs Dispersal risk, and preparation cycle is long, is difficult to suitability for industrialized production, and specificity and susceptibility need further raising.Therefore exploitation has the responsive sorbing material of specific recognition performance to component to be measured, is the guardian technique that solves the new detection method of research and development.
Along with scientific and technical development, molecular imprinting produces, and the material that has special adsorptivity for preparation provides technical support.Molecular imprinting is to take the target detect thing to be template, and is combined by the mode of covalent linkage or non covalent bond with function monomer, adds linking agent in certain solvent, to carry out polyreaction.After the template molecule wash-out, a large amount of holes in imprinted polymer, have been stayed, the shape in these holes and functional group and template molecule mate fully, and its action site and template molecule have complementary structure, template molecule are presented to the identity of predetermined selectivity and height.Molecularly imprinted polymer (MIP) synthesizes by molecular imprinting, target molecule (template molecule) and analog thereof is had to the polymkeric substance of specific recognition and selective adsorption.Be characterized in having precordainment, identity, practicality; Advantage is can anti-adverse environment, the selectivity of height, stability and long work-ing life.
Be applied to molecular imprinting in environment or significant in the detection of 17 beta estradiols in animal food.The article great majority of relevant 17 beta-estradiol molecular engram polymers that current Chinese scholars is delivered are all to adopt single template molecule, and synthetic polymkeric substance does not have high avidity like this.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts hybrid template to prepare 17 beta-estradiol molecular engram polymers, the molecularly imprinted polymer that adopts the method to prepare has higher avidity to 17 beta estradiols, and adsorption effect is better.
In order to achieve the above object, the present invention has adopted following technical scheme:
The mixture of 17 beta estradiols and 17 alpha-estradiols of take is template molecule, select methacrylic acid (MAA) or methyl methacrylate (MA) as function monomer, with carry out supersound process after pore-creating agent mixes, add again linking agent, after standing 1 hour, add initiator, logical nitrogen-sealed, in container, adopt the thermal initiation mode to carry out mass polymerization, again polymkeric substance is ground, sieves, with soxhlet extraction method wash-out template molecule, after vacuum-drying, make 17 beta-estradiol molecular engram polymers.
Specifically comprise the following steps:
(1) hybrid template preparation: 17 alpha-estradiols are dissolved in pore-creating agent with the template molecule obtained after 17 beta estradiols mix, 17 alpha-estradiols: the mol ratio of 17 beta estradiols=0.5～2: 1, in pore-creating agent, add function monomer to obtain mixture A again, in every 3～5mL pore-creating agent, add the 1mmol function monomer, the mol ratio of function monomer and template molecule is 1: 0.2～0.3, and mixture A is mixed by supersound process 3min;
(2) reaction system is set up: add linking agent ethylene glycol dimethacrylate (EGDMA) in the mixture A mixed, then by supersound process 3～5min, mix, after supersound process under room temperature standing 1 hour, then add initiator Diisopropyl azodicarboxylate (AIBN) to obtain mixture B, the mol ratio of linking agent and function monomer is 1: 1, and the mol ratio of initiator and function monomer is 0.12～0.16: 1;
(3) polyreaction: lead to N in mixture B
2After 5～10min, seal, then adopt the thermal initiation mode to carry out bulk polymerization and obtain bulk polymer, the temperature of polyreaction is 50～65 ℃, and the time of polyreaction is 16～36 hours;
(4) purifying, drying, constant weight: bulk polymer is broken, grind, sieve, then with the mixed solvent of methyl alcohol and acetic acid, adopt soxhlet extraction to remove template molecule, then use methanol extraction 1～2 time, remove remaining acetic acid, remove after acetic acid in 40 ℃ of vacuum-dryings molecularly imprinted polymer that spends the night to obtain.
Described pore-creating agent is acetonitrile, tetracol phenixin or chloroform.
Described function monomer is methacrylic acid (MAA) or methyl methacrylate (MA).
The volume ratio of described methyl alcohol and acetic acid is 9: 1.
The condition of described soxhlet extraction is extraction 3～5 times, each 8～12 hours.
The particle diameter of described molecularly imprinted polymer is 30～60 μ m.
The method that employing hybrid template of the present invention prepares 17 beta-estradiol molecular engram polymers is usingd the mixture of 17 alpha-estradiols and 17 beta estradiols as template molecule, and adopt precipitation polymerization process to make 17 beta-estradiol molecular engram polymers, the molecularly imprinted polymer that adopts the method to prepare has the ability of higher absorption 17 beta estradiols, filler using it as Solid-Phase Extraction can shorten detection time, reduce testing cost, therefore, have broad application prospects.
The accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of 17 beta-estradiol molecular engram polymers that make of the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
In the 100ml medical brine bottle, 0.1mmol 17 alpha-estradiols and 0.1mmol 17 beta estradiols are dissolved in the 3ml acetonitrile, in acetonitrile, add 1mmol methyl methacrylate (MA) again, after mixing, supersound process 3min adds 1mmol ethylene glycol dimethacrylate (EGDMA), supersound process 3min mixes it, then standing 1h under room temperature, add 20mg initiator Diisopropyl azodicarboxylate after standing, then logical N
2, sealing rapidly after 5min, after sealing, reacted 36 hours in 50 ℃ of water bath chaders, what after reaction finishes, generate is bulk polymer, by the bulk polymer fragmentation, grind, after sieving, obtain the particle of particle diameter at 30～60 μ m, with the mixed solution of 100ml methyl alcohol and acetic acid, adopt the method for soxhlet extraction to carry out wash-out particle, remove template molecule until in elutriant, do not contain template molecule, in mixed solution, the volume fraction of acetic acid is 10%, the condition of soxhlet extraction is extraction 5 times, each 8 hours, finally by methanol-eluted fractions, remove molecular acid 1 time, then the molecularly imprinted polymer that spends the night purely in 40 ℃ of vacuum-dryings.
Embodiment 2
In the 100ml medical brine bottle, 0.1mmol 17 alpha-estradiols and 0.15mmol 17 beta estradiols are dissolved in the 5ml acetonitrile, in acetonitrile, add again 1mmol methacrylic acid (MAA), after mixing, supersound process 3min adds again 1mmol EGDMA, supersound process 4min mixes it, then standing 1h under room temperature, add 20mg initiator Diisopropyl azodicarboxylate after standing, then logical N
2, sealing rapidly after 10min, after sealing, reacted 32 hours in 55 ℃ of water bath chaders, what after reaction finishes, generate is bulk polymer, by the bulk polymer fragmentation, grind, after sieving, obtain the particle of particle diameter at 30～60 μ m, with the mixed solution of 100ml methyl alcohol and acetic acid, adopt the method for soxhlet extraction to carry out wash-out particle, remove template molecule until in elutriant, do not contain template molecule, in mixed solution, the volume fraction of acetic acid is 10%, the condition of soxhlet extraction is extraction 4 times, each 10 hours, finally by methanol-eluted fractions, remove molecular acid 1 time, then the molecularly imprinted polymer that spends the night purely in 40 ℃ of vacuum-dryings.
Embodiment 3
In the 100ml medical brine bottle, 0.2mmol 17 alpha-estradiols and 0.1mmol 17 beta estradiols are dissolved in the 5ml chloroform, in chloroform, add 1mmol MAA again, after mixing, supersound process 3min adds 1mmol EGDMA, supersound process 5min mixes it, then standing 1h under room temperature, add 25mg initiator Diisopropyl azodicarboxylate after standing, then logical N
2, sealing rapidly after 8min, after sealing, reacted 16 hours in 65 ℃ of water bath chaders, what after reaction finishes, generate is bulk polymer, by the bulk polymer fragmentation, grind, after sieving, obtain the particle of particle diameter at 30～60 μ m, with the mixed solution of 100ml methyl alcohol and acetic acid, adopt the method for soxhlet extraction to carry out wash-out particle, remove template molecule until in elutriant, do not contain template molecule, in mixed solution, the volume fraction of acetic acid is 10%, the condition of soxhlet extraction is extraction 3 times, each 12 hours, finally by methanol-eluted fractions, remove molecular acid 2 times, then the molecularly imprinted polymer that spends the night purely in 40 ℃ of vacuum-dryings.
Embodiment 4
In the 100ml medical brine bottle, 0.1mmol 17 alpha-estradiols and 0.2mmol 17 beta estradiols are dissolved in the 4ml chloroform, in chloroform, add 1mmol methyl methacrylate (MA) again, after mixing, supersound process 3min adds 1mmol ethylene glycol dimethacrylate (EGDMA), supersound process 3min mixes it, then standing 1h under room temperature, add 0.16mmol initiator Diisopropyl azodicarboxylate after standing, then logical N
2, sealing rapidly after 6min, after sealing, reacted 20 hours in 60 ℃ of water bath chaders, what after reaction finishes, generate is bulk polymer, by the bulk polymer fragmentation, grind, after sieving, obtain the particle of particle diameter at 30～60 μ m, with the mixed solution of 100ml methyl alcohol and acetic acid, adopt the method for soxhlet extraction to carry out wash-out particle, remove template molecule until in elutriant, do not contain template molecule, in mixed solution, the volume fraction of acetic acid is 10%, the condition of soxhlet extraction is extraction 4 times, each 10 hours, finally by methanol-eluted fractions, remove molecular acid 2 times, then the molecularly imprinted polymer that spends the night purely in 40 ℃ of vacuum-dryings.
Embodiment 5
In the 100ml medical brine bottle, 0.15mmol 17 alpha-estradiols and 0.1mmol 17 beta estradiols are dissolved in the 4ml tetracol phenixin, in tetracol phenixin, add 1mmol methacrylic acid (MAA) again, after mixing, supersound process 3min adds again 1mmol EGDMA, supersound process 4min mixes it, then standing 1h under room temperature, add 0.12mmol initiator Diisopropyl azodicarboxylate after standing, then logical N
2, sealing rapidly after 10min, after sealing, reacted 30 hours in 55 ℃ of water bath chaders, what after reaction finishes, generate is bulk polymer, by the bulk polymer fragmentation, grind, after sieving, obtain the particle of particle diameter at 30～60 μ m, with the mixed solution of 100ml methyl alcohol and acetic acid, adopt the method for soxhlet extraction to carry out wash-out particle, remove template molecule until in elutriant, do not contain template molecule, in mixed solution, the volume fraction of acetic acid is 10%, the condition of soxhlet extraction is extraction 5 times, each 8 hours, finally by methanol-eluted fractions, remove molecular acid 2 times, then the molecularly imprinted polymer that spends the night purely in 40 ℃ of vacuum-dryings.
As shown in Figure 1, the hole size on this molecularly imprinted polymer particle is between 0.20 μ m～0.40 μ m as shown in Figure 1 for 17 beta-estradiol molecular engram polymers prepared by the present invention.
17 beta-estradiol molecular engram polymers that prepare are carried out to adsorption test, 17 beta-estradiol molecular engram polymers that prepare of the hybrid template of employing more as can be known 17 alpha-estradiols of result and 17 beta estradiols can more efficient enrichment 17 beta estradiols by experiment, adsorptive capacity to 17 beta estradiols reaches 3.84mg/g, be greater than the 3.61mg/g in existing document, simultaneously, this molecular imprinting polymerization also shows higher selectivity and adsorptive capacity to the same compounds of group of 17 beta estradiols, such as, adsorptive capacity to 17 alpha-estradiols reaches 2.97mg/g, the expansion of detected object scope is conducive to further shorten detection time, reduce testing cost.
Claims (4)
1. method that adopts hybrid template to prepare 17 beta-estradiol molecular engram polymers is characterized in that: comprise the following steps:
(1) hybrid template preparation: 17 alpha-estradiols are dissolved in pore-creating agent with the template molecule obtained after 17 beta estradiols mix, 17 alpha-estradiols: the mol ratio of 17 beta estradiols=0.5～2:1, in pore-creating agent, add function monomer to obtain mixture A again, in every 3～5mL pore-creating agent, add the 1mmol function monomer, the mol ratio of function monomer and template molecule is 1:0.2～0.3, and mixture A is mixed by supersound process 3min;
(2) reaction system is set up: add the linking agent ethylene glycol dimethacrylate in the mixture A mixed, then by supersound process 3～5min, mix, after supersound process under room temperature standing 1 hour, then add the initiator Diisopropyl azodicarboxylate to obtain mixture B, the mol ratio of linking agent and function monomer is 1:1, and the mol ratio of initiator and function monomer is 0.12～0.16:1;
(3) polyreaction: lead to N in mixture B
2After 5～10min, seal, then adopt the thermal initiation mode to carry out bulk polymerization and obtain bulk polymer, the temperature of polyreaction is 50～65 ℃, and the time of polyreaction is 16～36 hours;
(4) purifying, drying, constant weight: bulk polymer is broken, grind, sieve, then with the mixed solvent of methyl alcohol and acetic acid, adopt soxhlet extraction to remove template molecule, then use methanol extraction 1～2 time, remove remaining acetic acid, remove after acetic acid in 40 ℃ of vacuum-dryings molecularly imprinted polymer that spends the night to obtain;
Described pore-creating agent is acetonitrile, tetracol phenixin or chloroform;
Described function monomer is methacrylic acid or methyl methacrylate.
2. a kind of method that adopts hybrid template to prepare 17 beta-estradiol molecular engram polymers according to claim 1, it is characterized in that: the volume ratio of described methyl alcohol and acetic acid is 9:1.
3. according to a kind of described method that adopts hybrid template to prepare 17 beta-estradiol molecular engram polymers of claim 1 or 2, it is characterized in that: the condition of described soxhlet extraction is extraction 3～5 times, each 8～12 hours.
4. a kind of method that adopts hybrid template to prepare 17 beta-estradiol molecular engram polymers according to claim 1, it is characterized in that: the particle diameter of described molecularly imprinted polymer is 30～60 μ m.
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| CN103724656B (en) * | 2013-12-18 | 2016-01-20 | 陕西科技大学 | A kind of method adopting hybrid template to prepare ebormycine molecularly imprinted polymer |
| CN104130442A (en) * | 2014-07-22 | 2014-11-05 | 江西出入境检验检疫局检验检疫综合技术中心 | Preparation method of 17beta-estradiol molecular imprinting material |
| CN106215975B (en) * | 2016-07-07 | 2018-12-04 | 中北大学 | One-step synthesis carbon dots/poly- 1,4- diphenyl diacetylene hydridization catalysis material method |
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| CN101139421A (en) * | 2007-08-16 | 2008-03-12 | 江南大学 | Preparation method of 17beta-estradiol molecular engram polymer and use |
| CN101177499A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing estradiol molecular engram polymer |
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| CN101139421A (en) * | 2007-08-16 | 2008-03-12 | 江南大学 | Preparation method of 17beta-estradiol molecular engram polymer and use |
| CN101177499A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing estradiol molecular engram polymer |
Non-Patent Citations (2)
| Title |
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| 几种甾醇异构体在TFMAA-co- TI RM分子印迹聚合物中的热力学特征;朱秋劲等;《贵州科学》;20070531;第25卷(第S1期);第1-8页 * |
| 朱秋劲等.几种甾醇异构体在TFMAA-co- TI RM分子印迹聚合物中的热力学特征.《贵州科学》.2007,第25卷(第S1期),第1-8页. |
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