CN102936316B - Preparation method of molecularly imprinted polymer capable of enriching gallic acid - Google Patents
Preparation method of molecularly imprinted polymer capable of enriching gallic acid Download PDFInfo
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- CN102936316B CN102936316B CN201210483605.1A CN201210483605A CN102936316B CN 102936316 B CN102936316 B CN 102936316B CN 201210483605 A CN201210483605 A CN 201210483605A CN 102936316 B CN102936316 B CN 102936316B
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Abstract
The invention relates to a preparation method of a molecularly imprinted polymer capable of enriching gallic acid, which comprises the following steps: by using gallic acid as a template molecule, a tetrahydrofuran-isooctane mixed solvent as a pore-forming agent, 4-vinylpyridine as a functional monomer, ethylene glycol dimethyl acrylate as a crosslinking agent and azodiisobutyronitrile as an initiator, evenly mixing, carrying nitrogen-blowing deoxidization, carrying out thermostatic water bath reaction, carrying out Soxhlet extraction, and drying to obtain the molecularly imprinted polymer. The preparation method has the advantages of simple technique and low cost, and is easy to implement; and the prepared molecularly imprinted polymer can be used for separating and extracting gallic acid from natural products, has the advantage of long service life, and especially can implement quick enrichment and purification for some natural products with very low gallic acid content.
Description
Technical field
The present invention relates to molecularly imprinted polymer, particularly a kind of preparation method of molecularly imprinted polymer that can enrichment gallic acid.
Background technology
Gallic acid (gallic acid, GA), chemical name Gallic Acid, is a kind of polyphenolic compound that nature exists.Gallic acid and derivative thereof demonstrate effect in the diseases such as treatment coronary heart disease, cerebral thrombosis, stomach ulcer, have stronger trypanocidia, anti-inflammatory, the effect such as antibacterial; Gallic acid also shows prevention and restraining effect, the restraining effect to HIV-1 intergrase and the effect of hepatitis B virus resisting to swollen neoplastic each stage simultaneously.Due to the various biological activity of gallic acid, it is had broad application prospects at the aspect such as food, medical science.Therefore the natural resource that, further exploitation contains gallic acid have important practical significance.
Molecular imprinting is taking target molecule as template molecule, the high molecular polymer that preparation is mated on space structure and binding site completely with template molecule.1972, Wulff G. research group successfully prepared molecularly imprinted polymer first, makes molecular imprinting have breakthrough.1993, Mosbach etc. promoted this technology widespread use about the report of theophylline molecularly imprinted polymer.Nowadays, molecular imprinting is with its remarkable identity and selectivity, all represent good application prospect in fields such as chiral drug separation, Solid-Phase Extraction, clinical medicine analysis, membrane separation technique, mimetic enzyme catalysis, Biomimic sensors, and become one of emerging field of chemistry and biology intersection.
Summary of the invention
The object of the invention is for above-mentioned technical Analysis, a kind of preparation method of molecularly imprinted polymer that can enrichment gallic acid is provided, the characteristic of utilizing this molecularly imprinted polymer and template molecule to mate completely at space structure and binding site, directly separation, enrichment gallic acid from natural product, set up a kind of gallic acid extraction and separation method that can be quick, safe, easy.
Technical scheme of the present invention:
A kind of preparation method of molecularly imprinted polymer that can enrichment gallic acid, taking gallic acid as template molecule, taking the mixed solvent of tetrahydrofuran (THF) and octane-iso as pore-creating agent, taking 4-vinylpyridine as function monomer, taking ethylene glycol dimethacrylate as linking agent, taking Diisopropyl azodicarboxylate as initiator, step is as follows:
1) template molecule gallic acid and function monomer 4-vinylpyridine are dissolved in the mixed solvent of pore-creating agent tetrahydrofuran (THF) and octane-iso, mix and stir 3h;
2) add linking agent ethylene glycol dimethacrylate, mix and stir 30min;
3) add again initiator Diisopropyl azodicarboxylate, mix and stir 20min, obtain mixed solution;
4), by above-mentioned mixed solution nitrogen flushing deoxidation 4min, water-bath 48h at 60 DEG C of constant temperature, obtains bulk polymer;
5) above-mentioned bulk polymer is ground, screens and retain 60 order-100 purpose polymers particles with sizing screen, then by polymer beads by the extracting of Soxhlet extract to remove unreacted reactant, the extracting time is 48h, obtains molecularly imprinted polymer;
6) be dry at 60 DEG C by above-mentioned molecularly imprinted polymer in temperature, can make can enrichment gallic acid molecularly imprinted polymer.
In described pore-creating agent, the volume ratio of tetrahydrofuran (THF) and octane-iso is 4:1.
The mol ratio of described template molecule, function monomer and linking agent is 1:5:12.
The add-on of described initiator Diisopropyl azodicarboxylate is 0.4% of pore-creating agent, function monomer and linking agent total mass.
Described Soxhlet extract is that volume ratio is the methyl alcohol of 9:1 and the mixed solution of acetic acid.
Prepared by aforesaid method can enrichment gallic acid the application of molecularly imprinted polymer, for separating from pilose antler bacterium, enrichment to be to extract gallic acid.
Advantage of the present invention and positively effect are: this preparation method's technique is simple, cost is low, easy to implement, the molecularly imprinted polymer of preparation can be used for separation and Extraction gallic acid and long service life from natural product, particularly, for the very low natural product of some gallic acid contents, can realize fast enriching purifying.
Brief description of the drawings
Accompanying drawing is the test pattern that this molecularly imprinted polymer of application separates the gallic acid in pilose antler bacterium crude extract.
In figure: the test value that peak A is gallic acid, the test value that peak B is Protocatechuic Acid; Curve (1) is the test value of pilose antler bacterium crude extract, the test value that curve (2) is the elutriant that obtains through gallic acid molecular imprinting column separating purification.
Embodiment
Embodiment:
A preparation method for molecularly imprinted polymer that can enrichment gallic acid, step is as follows:
1) 170mg gallic acid and 536 μ L 4-vinylpyridines are dissolved in the mixed solvent of 4mL tetrahydrofuran (THF) and 1mL octane-iso, mix and stir 3h;
2) add 2263 μ L ethylene glycol dimethacrylates, mix and stir 30min;
3) add again 30mg Diisopropyl azodicarboxylate, mix and stir 20min, obtain mixed solution;
4), by above-mentioned mixed solution nitrogen flushing deoxidation 4min, sealing is placed in thermostat water bath and reacts after 48h at 60 DEG C, obtains bulk polymer;
5) above-mentioned bulk polymer is ground with mortar, screen and retain 60 order-100 purpose polymers particles with sizing screen, then polymer beads is used the extracting of 250mL Soxhlet extract to remove unreacted reactant, Soxhlet extract is that volume ratio is the methyl alcohol of 9:1 and the mixed solution of acetic acid, the extracting time is 48h, obtains molecularly imprinted polymer;
6) be dry at 60 DEG C by above-mentioned molecularly imprinted polymer in temperature, can make can enrichment gallic acid molecularly imprinted polymer.
By this can enrichment gallic acid molecularly imprinted polymer for separating from pilose antler bacterium, enrichment to be to extract gallic acid, experimental technique and effect are as follows:
Place pad at the SPE of 4mL blank pipe two ends, load uniformly therein this prepared molecularly imprinted polymer of 150mg.The SPE 10mL10% methyl alcohol balance of molecularly imprinted polymer will be filled with; By 300ml methyl alcohol and 30ml 0.2molL-1 hydrochloric acid extraction three times for 10g pilose antler bacterium, after united extraction liquid, utilize rotary evaporation to remove solvent, the extract obtaining is dissolved in to 200ml water, with equal-volume ethyl acetate extraction three times.Combined ethyl acetate phase, and remove solvent by rotary evaporation, finally obtain pilose antler bacterium crude extract.The pilose antler bacterium crude extract obtaining is dissolved in to the methanol solution of 150mL 10%; 150mL sample solution is crossed to the SPE post that molecularly imprinted polymer is housed, at this moment gallic acid is just attracted on enrichment material.Then wash assorted with 4mL 65% methyl alcohol, wash away the material of non-specific adsorption on pillar, the methyl alcohol that is 9:1 by 20mL volume ratio and acetic acid mixed solution wash-out, the elutriant obtaining utilizes Rotary Evaporators to remove solvent, finally use 2ml dissolve with methanol extract, be by the gallic acid of molecular blotting column specific adsorption.
Detected result as shown in drawings, in figure, show: the existence of gallic acid in pilose antler bacterium crude extract, do not detected, and after molecular blotting column concentration and separation, gallic acid has obtained enrichment, due to the Protocatechuic Acid analog that is gallic acid, molecular blotting column also has certain adsorption to it, and the content of other components in pilose antler bacterium crude extract all decreases.As can be seen here, the gallic acid molecularly imprinted polymer of preparation can adsorb and enriched sample in gallic acid, thereby reach the object of enriching and purifying.
Claims (1)
- One kind can enrichment gallic acid the application of molecularly imprinted polymer, the preparation method of described molecularly imprinted polymer is, taking gallic acid as template molecule, taking the mixed solvent of tetrahydrofuran (THF) and octane-iso as pore-creating agent, taking 4-vinylpyridine as function monomer, taking ethylene glycol dimethacrylate as linking agent, taking Diisopropyl azodicarboxylate as initiator, step is as follows:1) template molecule gallic acid and function monomer 4-vinylpyridine are dissolved in the mixed solvent of pore-creating agent tetrahydrofuran (THF) and octane-iso, mix and stir 3 h;2) add linking agent ethylene glycol dimethacrylate, mix and stir 30 min;3) add again initiator Diisopropyl azodicarboxylate, mix and stir 20 min, obtain mixed solution;4), by above-mentioned mixed solution nitrogen flushing deoxidation 4 min, water-bath 48 h at 60 DEG C of constant temperature, obtain bulk polymer;5) above-mentioned bulk polymer is ground, screens and retain 60 order-100 purpose polymers particles with sizing screen, then by polymer beads by the extracting of Soxhlet extract to remove unreacted reactant, the extracting time is 48 h, obtains molecularly imprinted polymer;6) be dry at 60 DEG C by above-mentioned molecularly imprinted polymer in temperature, can make can enrichment gallic acid molecularly imprinted polymer;In described pore-creating agent, the volume ratio of tetrahydrofuran (THF) and octane-iso is 4:1;The mol ratio of described template molecule, function monomer and linking agent is 1:5:12;The add-on of described initiator Diisopropyl azodicarboxylate is 0.4% of pore-creating agent, function monomer and linking agent total mass;Described Soxhlet extract is that volume ratio is the methyl alcohol of 9:1 and the mixed solution of acetic acid;It is characterized in that: for from pilose antler bacterium separate, enrichment with extract gallic acid.
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