CN101381430A - Molecule brand polymer of curcumin, preparation method and application thereof - Google Patents
Molecule brand polymer of curcumin, preparation method and application thereof Download PDFInfo
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- CN101381430A CN101381430A CNA2008101215109A CN200810121510A CN101381430A CN 101381430 A CN101381430 A CN 101381430A CN A2008101215109 A CNA2008101215109 A CN A2008101215109A CN 200810121510 A CN200810121510 A CN 200810121510A CN 101381430 A CN101381430 A CN 101381430A
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Abstract
The invention discloses a molecular branding polymer of curcumin and a preparation method and application thereof. In the molecular branding polymer, a template molecule and a functional monomer are subjected to the polyreaction under the action of a cross linking agent, and the template molecule is extracted out by utilizing a solvent, and the molecular branding polymer is obtained; and the template molecule of the molecular branding polymer of the curcumin is one of compounds as shown in formulas of (I) to (III) or the combination of more than two of the compounds as shown in the formulas of (I ) to (III). The molecular branding polymer of the curcumin can be used as a solid phase extraction agent to separate and purify curcumin compounds. The curcumin obtained by the separation-purification method has the advantages of high purity, simple method, easy operation, little environmental pollution, low energy consumption and good application prospect.
Description
(1) technical field
The present invention relates to molecular brand polymer of a kind of curcumine and its production and application, especially as the application of solid extracting agent in separate and purify curcumin compounds.
(2) background technology
Molecular brand claims molecular imprinting, template again, tailors, and is meant that preparation has the process of the polymkeric substance of specific selectivity to specific molecular (template molecule).Prepared polymkeric substance is called molecular brand polymer.The preparation process of molecular brand polymer probably is divided into three steps: (1) at first is dissolved in specific molecular (template molecule) in the corresponding solvent and (claims pore-creating agent again), make the effect combination by covalently or non-covalently of template molecule and function monomer, form the mixture of Subjective and Objective.(2) in solution, add linking agent and initiator,, make and cross-linking polymerization takes place around the host-guest complex, produce highly cross-linked and have the polymkeric substance of good mechanical properties by light or thermal-initiated polymerization; (3) prepared polymkeric substance is pulverized, utilize appropriate solvent with the template molecule wash-out in the polymkeric substance, just stayed the hole that size and space structure with template molecule mate mutually like this in polymkeric substance, the special groups of function monomer also is distributed in inside, hole accurately simultaneously.So just, prepared the high molecular polymer that specific molecular is had special selectivity and affinity.
Solid-Phase Extraction is a physical extraction process that comprises liquid phase and solid phase.In the Solid-Phase Extraction process, greater than the sample mother liquor, when sample during by solid-phase extraction column, analyte is attracted to solid surface to solid phase to the adsorptive power of analyte, other component then with the sample mother liquor by pillar, with appropriate solvent analyte is eluted at last.Many problems of using solid phase extraction can avoid liquid-liquid extraction to bring, such as: be easy to emulsification, incomplete being separated, the lower quantitative analysis rate of recovery, expensive frangible glassware and a large amount of organic liquid wastes.
Though Solid-Phase Extraction has above-mentioned a lot of advantages, there is not stationary phase optionally but to limit the application of solid phase extraction techniques.Because the selectivity of molecular imprinting technique, can overcome this shortcoming as the stationary phase of Solid-Phase Extraction with molecular brand polymer.
Contain in the turmeric based on three kinds of slightly variant phenol monomers of the molecular structure of curcumine, be called curcumin chemical compounds, i.e. curcumine, demethoxycurcumin and bisdemethoxycurcumin, molecular formula is respectively C
21H
20O
6, C
20H
18O
5And C
19H
16O
4(Fig. 1), the ratio of three's content is about curcumine: demethoxycurcumin: bisdemethoxycurcumin=7:2:1.
1.curcumin： R
1＝R
2＝OMe
2.demethoxycurcumin： R
1＝H，R
2＝OMe
3.bisdemethyoxycurcumin：R
1＝R
2＝H
Curcumin chemical compounds is mainly derived from turmeric, curcuma zedoary, root tuber of aromatic turmeric rhizome, is main active ingredient wherein.Wherein curcumin chemical compounds is about 2-5% in the turmeric rhizome, and this composition is widely used in the food and medicine field.Now, existing people is used for curcumin chemical compounds AIDS patient and HIV the infected's treatment.Recently, domestic and international many documents have been reported the reducing blood-fat, anti-mutation of curcumin chemical compounds, anticancer, anti-oxidant, concern that the application of anticancer and anti-AIDS function in experimental study and clinical study that remove the physiological function and the mechanism of action, especially curcumines such as free radical more and more is subjected to the world in succession.
The method of traditional separation curcumine mainly is the volatile oil that at first extracts in the curcumine, utilizes the organic solvent extraction curcumine to re-use organic solvent extraction then.This method is loaded down with trivial details time-consuming, and the labor intensive material resources have increased cost.Molecular imprinting technique is a kind of a certain compounds of group all to be had the material of selective adsorption effect, and preparation is simple, and with low cost, good stability is reusable; Solid phase extraction techniques can be separated target product and impurity by the mode of Solid-Phase Extraction.At present there is not bibliographical information to utilize the molecular brand solid phase extraction techniques directly from the curcumine crude extract, to obtain pure curcumin chemical compounds as yet.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide a kind of molecular brand polymer of curcumine, be applied to the separation and purification of curcumin chemical compounds, utilize the molecular brand solid phase extraction techniques simply, separate and purify curcumin compounds from the curcumine crude extract efficiently.
Generally speaking, molecular brand polymer be by the template molecule of molecular brand polymer and function monomer behind polymerization reaction take place under the linking agent effect, obtain after falling described template molecule with solvent extraction again.
The template molecule of the molecular brand polymer of curcumine of the present invention is the combination of one or more in the compound shown in the formula (I)～(III);
The function monomer of the molecular brand polymer of described curcumine can be selected acid monomer for use, neutral monomer, the alkalescence monomer, specifically can select following one or more mixing for use: methacrylic acid, vinylformic acid, 2-methylacryoyloxyethyl phosphoric acid, methylene-succinic acid, trifluoromethyl acrylate, to vinyl benzoic acid, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid, 4-vinylpridine, the diethylaminoethyl-methacrylic ester, diformazan aminoethyl methacrylic ester, p-aminophenyl ethene, the 1-vinyl imidazole, the 4-vinyl imidazole, 2,6-bisacrylamind yl pyridines, acrylamide, Methacrylamide, N, the two methacryloyl ethylethanolamines of O-, N, N, N-trimethylammonium aminoethyl methacrylic acid ester hydrochloride, the 2-hydroxyethyl meth acrylate;
The linking agent of the molecular brand polymer of described curcumine is following one or more combination: Vinylstyrene, 1,3 di isopropenylbenzenes, Ethylene glycol dimethacrylate, tetramethylene dimethacrylate, dimethacrylate triglycol ester, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, N, N '-methylene-bisacrylamide, N, N '-vinyl bisacrylamide.
Further, described function monomer is preferably one of following: methacrylic acid, vinylformic acid, trifluoromethyl acrylate, 4-vinylpridine, p-aminophenyl ethene, 1-vinyl imidazole, 4-vinyl imidazole, acrylamide, Methacrylamide.
It is one of following that described linking agent is preferably: Vinylstyrene, 1,3 di isopropenylbenzene, Ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate.
Concrete, the preparation of the molecular brand polymer of curcumine of the present invention comprises the steps: in pore-creating agent, curcumin chemical compounds molecule, function monomer and linking agent mix, polymerization reaction take place, controlled temperature is fully obtaining the polymkeric substance crude product after the reaction between 50～80 ℃, and described polymkeric substance crude product falls the molecular brand polymer that obtains described curcumine behind wherein the curcumin chemical compounds molecule with solvent extraction.
Above-mentioned preparation can be implemented by any one method of preparation traditional polymer, comprises mass polymerization, suspension polymerization, emulsion polymerization, seed swelling polymerization etc.
In preparation, described pore-creating agent is recommended as following one or more combination: tetrahydrofuran (THF), toluene, chloroform, acetone, methylene dichloride, acetonitrile.
The ingredient proportion of described curcumin chemical compounds, function monomer and linking agent contains under the prerequisite of curcumine, function monomer, linking agent in guaranteeing polymers soln, and any ratio all is fine.But preferably, described curcumin chemical compounds, function monomer and linking agent feeds intake amount of substance than being 1:2～20:4～80.
Polyreaction of the present invention can adopt thermal initiation or light-initiated, and the initiator that uses is azo-compound or superoxide, for example Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) or other azo-compound and superoxide or their arbitrary combination.
The employed solvent of extracting curcumin chemical compounds molecule is generally selected the good solvent of curcumin chemical compounds, as selecting following one or more combination: methyl alcohol, ethanol, acetone, tetrahydrofuran (THF).
The present invention is in the preparation process of the molecular brand polymer of curcumine, when adopting mass polymerization, suspension polymerization or emulsion polymerization to be prepared, preferably the polymkeric substance crude product is ground back wet method mistake 〉=400 mesh sieves (as 400 purpose stainless steel sifts) in water, suction filtration, the particle diameter that obtains is used eluting solvent extracting curcumin chemical compounds wherein after less than the oven dry of 400 purpose curcumine molecular brand polymers again.
The molecular brand polymer of curcumine of the present invention is as the application of solid extracting agent in separate and purify curcumin compounds.
Described application is specific as follows: the molecular brand polymer with curcumine is a solid extracting agent, extraction obtains curcumin chemical compounds from the curcumine crude extract, and described Solid-Phase Extraction comprises the activation of molecular brand polymer, with sample, methanol aqueous solution drip washing, four steps of eluting solvent wash-out on the curcumine crude extract.The elutriant that contains curcumin chemical compounds that wash-out obtains promptly obtains the pure product of curcumin chemical compounds through aftertreatment.
Described curcumine crude extract is obtained through solvent extraction by Turmeric Root, described extraction solvent is one of following: the methanol solution of water, methyl alcohol, ethanol, acetone, alkali, the ethanolic soln of alkali, the acetone soln of alkali, alkali aqueous solution, the mass concentration of alkali is no more than 50% in the acetone soln of the methanol solution of described alkali, the ethanolic soln of alkali, alkali and the alkali aqueous solution, described alkali is oxyhydroxide or the salt that shows alkalescence, described oxyhydroxide comprises sodium hydroxide, calcium hydroxide, hydrated barta etc., the salt of described apparent alkalescence comprises yellow soda ash, sodium bicarbonate etc.Extracting method comprises heating reflux method, ultrasonic extraction, microwave-assisted extraction method, buck extraction etc.
Described elutriant aftertreatment can be taked following operation: with the elutriant concentrating under reduced pressure that contains curcumin chemical compounds that obtains in the Solid-Phase Extraction, vacuum-drying promptly obtains the curcumin chemical compounds behind the purifying.
Further, in the process of Solid-Phase Extraction, the drip washing solvent is preferably the methanol in water of volume fraction≤30%.
The good solvent of any curcumin chemical compounds all can be used as eluting solvent, as one or more the mixed solution in methyl alcohol, ethanol, the acetone, or the acetic acid solution of above-mentioned three kinds of solvents (wherein quality of acetic acid concentration is not more than 20%), be preferably methyl alcohol-acetic acid (9:1, V/V).
The molecular brand polymer that the present invention makes has single-minded selectivity to curcumin chemical compounds, and it is applied to the separation and purification of curcumin chemical compounds as solid extracting agent, and following advantage and effect are compared with prior art arranged:
A) compare with traditional Solid-Phase Extraction, the molecular brand Solid-Phase Extraction is because its filler is target molecule to be had the polymkeric substance of specific selectivity so seeks suitable drip washing solvent be easier to, and wash-out is easy;
B) compare with liquid-liquid extraction, Solid-Phase Extraction is more effective, reaches quantified extract easily, and quick and automatization has also reduced solvent load and working hour simultaneously;
C) use of minimizing organic solvent is free from environmental pollution, improves and analyzes quality, reduces the interference of background, has improved the rate of recovery.
D) the molecular brand Solid-Phase Extraction does not need a large amount of immiscible solvents, can not produce emulsion in the treating processes, the efficient height.
To sum up, curcumine purity height, method that this method obtains are easy, easy to operate, and environmental pollution is very little, and energy consumption is low, has the major application prospect.
(4) description of drawings
The crude extract that Fig. 1 obtains for embodiment 1 is the liquid chromatogram when 422.4nm and 206.16nm detection respectively;
Fig. 2 is the effluent liquid liquid chromatogram when 422.4nm and 206.16nm detect respectively during sample on the embodiment 1;
The leacheate that Fig. 3 obtains for embodiment 1 is the liquid chromatogram when 422.4nm and 206.16nm detection respectively;
The elutriant that Fig. 4 obtains for embodiment 1 is the liquid chromatogram when 422.4nm and 206.16nm detection respectively.
Ordinate zou is integral area unit (mAU) among the above-mentioned figure, and X-coordinate is retention time (min).
(5) embodiment
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment 1:
(1) mass polymerization prepares the molecular brand polymer of curcumine
The tetrahydrofuran (THF) of measuring 10mL in the 25mL test tube, with measured 0.36g curcumine, the 10.36g methacrylic acid glycol ester, 9.6g methacrylic acid, 0.02g Diisopropyl azodicarboxylate join in the Erlenmeyer flask successively, the sealing, ultrasonic dissolution 30min.With the polymers soln inflated with nitrogen deoxygenation 10min that mixes.Test tube is put into 65 ℃ water-bath, and heated polymerizable 4h is elevated to 68 ℃ with temperature after the polymerization, continues heating 2h, makes polymerization complete.The mass polymer that obtains is taken out, grind, sieve in water with 400 order stainless steel sift wet methods, suction filtration, the particle diameter that obtains is dried less than 400 purpose curcumine molecular brand polymers,, in extracting solution, detect less than till the curcumine with ethanol extracting curcumine wherein in apparatus,Soxhlet's, with the oven dry of molecular brand powder, standby then.
(2) preparation of solid phase extraction sample
Turmeric Root after 5.0g cleaned extracts 30min with the 25mL alcohol heating reflux, extracts the back suction filtration that finishes, and filtrate is concentrated into dried, uses the 25mL dissolve with methanol then, and lysate is done the HPLC analysis after with the 0.45um filtering with microporous membrane.Remaining crude extract is preserved standby.
(3) Solid-Phase Extraction of curcumine crude extract
Activate: the molecular brand polymer 500.0mg after finishing with extracting uses 20mL methyl alcohol drip washing pillar then with methyl alcohol wet method dress post, and remaining impurities in the wash-out polymkeric substance makes the abundant swelling of molecular brand polymer.
Last sample: after activation finished, the crude extract 0.2mL that extracts curcumine with syringe went up sample.In the process of last sample, the effluent liquid in the pillar is collected, be evaporated to driedly, use the dissolve with methanol of 2.0mL then, wait to be HPLC and detect.
Drip washing: after treating that sample immerses in the polymkeric substance fully, with methanol-water (3:7, leacheate 30mL drip washing pillar V/V).Collect leacheate, be evaporated to driedly, use the dissolve with methanol of 2mL then, wait to be HPLC and detect.
Wash-out: after drip washing finished, (9:1, the V/V) curcumine in the 20mL wash-out pillar were treated elutriant to be merged behind the effluent liquid water white transparency, are evaporated to driedly, obtain the curcumine sample behind the purifying with methyl alcohol-acetic acid.Sample is HPLC to be detected.
Embodiment 2:
(1) suspension polymerization prepares the molecular brand polymer of curcumine
The 1.0g gelatin is added 200mL water in 250mL single port flask, be placed in 80 ℃ the water bath with thermostatic control gelatin is dissolved fully.The tetrahydrofuran (THF) of measuring 10mL then is in the 25mL test tube, with measured 0.36g Demethoxycurcumin, 10.36g trimethylolpropane trimethacrylate, 9.6g vinylformic acid, 0.02g Diisopropyl azodicarboxylate joins in the Erlenmeyer flask successively, sealing, ultrasonic dissolution 30min.The polymers soln that mixes is poured in the single port flask that fills 200mL water inflated with nitrogen deoxygenation 10min.The single port flask is put into 65 ℃ water-bath, and heated and stirred 4h is elevated to 68 ℃ with temperature after the polymerization, continues heating 2h, makes polymerization complete.With the microballoon suction filtration that obtains, in 80 ℃ of oven dry, grind, sieve in water with 400 order stainless steel sift wet methods, suction filtration is dried the particle diameter that obtains less than the oven dry of 400 purpose curcumine molecular brand polymers, with ethanol extracting Demethoxycurcumin wherein in apparatus,Soxhlet's, in extracting solution, detect less than till the Demethoxycurcumin, with the oven dry of molecular brand powder, standby then.
(2) preparation of solid phase extraction sample
Turmeric Root after 5.0g cleaned extracts 30min with the 25mL alcohol heating reflux, extracts the back suction filtration that finishes, and filtrate is concentrated into dried, uses the 25mL dissolve with methanol then, and lysate is done the HPLC analysis after with the 0.45um filtering with microporous membrane.Remaining crude extract is preserved standby.
(3) Solid-Phase Extraction of curcumine crude extract
Activate: the molecular brand polymer 500.0mg after finishing with extracting uses 20mL methyl alcohol drip washing pillar then with methyl alcohol wet method dress post, and remaining impurities in the wash-out polymkeric substance makes the abundant swelling of molecular brand polymer.
Last sample: after activation finished, the crude extract 0.2mL that extracts curcumine with syringe went up sample.In the process of last sample, the effluent liquid in the pillar is collected, be evaporated to driedly, use the dissolve with methanol of 2.0mL then, wait to be HPLC and detect.
Drip washing: after treating that sample immerses in the polymkeric substance fully, with methanol-water (3:7, leacheate 30mL drip washing pillar V/V).Collect leacheate, be evaporated to driedly, use the dissolve with methanol of 2mL then, wait to be HPLC and detect.
Wash-out: after drip washing finished, (9:1, the V/V) curcumine in the 20mL wash-out pillar were treated elutriant to be merged behind the effluent liquid water white transparency, are evaporated to driedly, obtain the curcumine sample behind the purifying with methyl alcohol-acetic acid.Sample is HPLC to be detected.
Embodiment 3:
(1) emulsion polymerization prepares the molecular brand polymer of curcumine
In the polyreaction bottle of 500mL belt stirrer, reflux exchanger, nitrogen inlet, thermometer and charging opening, add deionized water, compound emulsifying agent (sodium lauryl sulphate/alkylphenol polyethylene oxide condensation compound) successively, stirring heating, logical nitrogen is to remove oxygen.When temperature rises to 40 ℃, add ammonium persulphate, when stirring, be warming up to 50 ℃.Drip the polymerization single polymerization monomer trifluoromethyl acrylate, the two Demethoxycurcumins of template molecule, initiator Diisopropyl azodicarboxylate, linking agent pentaerythritol triacrylate and Na
2SO
3Solution, and keep temperature of reaction between 50～60 ℃, about 2h drip off whole polymeric constituents and reductive agent temperature of reaction are risen to 70 ℃, and keep certain hour in 70～75 ℃ of scopes, and emulsion is cooled to the room temperature discharging, leaches condensation product.With the curcumine molecular brand polymer suction filtration that obtains, in 80 ℃ of oven dry, grind, sieve in water with 400 order stainless steel sift wet methods, suction filtration is dried the particle diameter that obtains less than 400 purpose curcumine molecular brand polymers, with ethanol extracting two Demethoxycurcumins wherein in apparatus,Soxhlet's, in extracting solution, detect less than till two Demethoxycurcumins, with the oven dry of molecular brand powder, standby then.
(2) preparation of solid phase extraction sample
Turmeric Root after 5.0g cleaned extracts 30min with the 25mL alcohol heating reflux, extracts the back suction filtration that finishes, and filtrate is concentrated into dried, uses the 25mL dissolve with methanol then, and lysate is done the HPLC analysis after with the 0.45um filtering with microporous membrane.Remaining crude extract is preserved standby.
(3) Solid-Phase Extraction of curcumine crude extract
Activate: the molecular brand polymer 500.0mg after finishing with extracting uses 20mL methyl alcohol drip washing pillar then with methyl alcohol wet method dress post, and remaining impurities in the wash-out polymkeric substance makes the abundant swelling of molecular brand polymer.
Last sample: after activation finished, the crude extract 0.2mL that extracts curcumine with syringe went up sample.In the process of last sample, the effluent liquid in the pillar is collected, be evaporated to driedly, use the dissolve with methanol of 2.0mL then, wait to be HPLC and detect.
Drip washing: after treating that sample immerses in the polymkeric substance fully, with methanol-water (3:7, leacheate 30mL drip washing pillar V/V).Collect leacheate, be evaporated to driedly, use the dissolve with methanol of 2mL then, wait to be HPLC and detect.
Wash-out: after drip washing finished, (9:1, the V/V) curcumine in the 20mL wash-out pillar were treated elutriant to be merged behind the effluent liquid water white transparency, are evaporated to driedly, obtain the curcumine sample behind the purifying with methyl alcohol-acetic acid.Sample is HPLC to be detected.
Embodiment 4:
(1) the seed swelling polymerization prepares the molecular brand polymer of curcumine
Synthesizing of polystyrene seed: 10mL vinylbenzene, 90mL distilled water, 10mL dehydrated alcohol are added in the there-necked flask ultra-sonic oscillation, logical N
2Deoxidation adds the 0.10g Potassium Persulfate, then at N
2Protection under, be warmed up to 65 ℃ with induction stirring, isothermal reaction 20h obtains polystyrene seed emulsion.
The thermosol polymerization of expanding prepares the molecular brand polymer of curcumine: get a certain amount of seed emulsion, add the 0.6mL dibutyl phthalate (DBP), 0.375g Diisopropyl azodicarboxylate, 1mL toluene, 5mL water, 0.13g polyvinyl alcohol in flask, induction stirring 2h.Get 4mL toluene simultaneously, the 1.4g4-vinyl pyridine, the 0.2g curcumine mixes back ultra-sonic oscillation 20min, joins in the methacrylic acid glycol ester solution of 100mLw=3.6%PVA, with mixed solution induction stirring 2h.After above-mentioned two kinds of mixed solutions mixing, room temperature swelling 20h under induction stirring is warming up to 70 ℃ of swelling 24h again.
The wash-out of template molecule is handled: the gained emulsion is filtered, filter cake boils 2 times with each 500mL boiling water, boil 15min removing polyvinyl alcohol, the reusable heat water washing after the filtration places filter cake the 250mL flask at every turn, add 150mL methyl alcohol ultra-sonic oscillation 30min, filter back 200mL methyl alcohol: acetate (9:1, v/v) mixing solutions Soxhlet extractor extracting, flush away template molecule curcumine, product vacuum-drying 24h promptly obtains curcumine molecular brand microballoon, and it is standby to put moisture eliminator.
(2) preparation of solid phase extraction sample
Turmeric Root after 5.0g cleaned extracts 30min with the 25mL alcohol heating reflux, extracts the back suction filtration that finishes, and filtrate is concentrated into dried, uses the 25mL dissolve with methanol then, and lysate is done the HPLC analysis after with the 0.45um filtering with microporous membrane.Remaining crude extract is preserved standby.
(3) Solid-Phase Extraction of curcumine crude extract
Activate: the molecular brand polymer 500.0mg after finishing with extracting uses 20mL methyl alcohol drip washing pillar then with methyl alcohol wet method dress post, and remaining impurities in the wash-out polymkeric substance makes the abundant swelling of molecular brand polymer.
Last sample: after activation finished, the crude extract 0.2mL that extracts curcumine with syringe went up sample.In the process of last sample, the effluent liquid in the pillar is collected, be evaporated to driedly, use the dissolve with methanol of 2.0mL then, wait to be HPLC and detect.
Drip washing: after treating that sample immerses in the polymkeric substance fully, with methanol-water (3:7, leacheate 30mL drip washing pillar V/V).Collect leacheate, be evaporated to driedly, use the dissolve with methanol of 2mL then, wait to be HPLC and detect.
Wash-out: after drip washing finished, (9:1, the V/V) curcumine in the 20mL wash-out pillar were treated elutriant to be merged behind the effluent liquid water white transparency, are evaporated to driedly, obtain the curcumine sample behind the purifying with methyl alcohol-acetic acid.Sample is HPLC to be detected.
Embodiment 5:
(1) preparation of silica gel keys mould assembly curcumine molecular brand polymer
The activation of silica gel: the porous silica gel of 10g is placed round-bottomed flask, add rare nitric acid of 150mL 5%, induction stirring backflow 24h, product is washed till neutrality with distilled water, 150 ℃ of vacuum-drying 24h.
The derivatize of silica gel: the 10g activated silica gel is placed there-necked flask, vacuumize the air of removing in the silica gel hole, decompression adds 7.5g γ-(methacryloxypropyl) propyl trimethoxy silicane, 2mL triethylamine, 100mL exsiccant toluene down.N
2At 95～100 ℃ of reaction 24h, after the cooling, product is used toluene, acetone, ether, methanol wash successively, then at 120 ℃ of following vacuum-drying 24h down in protection.
The preparation of curcumine molecular brand polymer: add 0.36g curcumine and a certain amount of Methacrylamide in the 5mL chloroform, fully transfer in the 50mL ampere bottle behind the reaction 2h, add a certain amount of linking agent Vinylstyrene, 15mL tetrahydrofuran (THF), 0.5g silanized silica gel, 20mg initiator Diisopropyl azodicarboxylate.Mixture is ultrasonic repeatedly, fill N
2Gas is removed O
2Gas, vacuum sealing tube under the ice bath.The ampere bottle is placed on the gyroscope, slowly rotate 60 ℃ of water-bath thermal-initiated polymerization 24h.After reaction finishes, open after the ampere bottle left standstill for some time, the upper solution of inclining, a careful and bottle wall adhesive separately with methyl alcohol sedimentation repeatedly, is not damaged the MIP on silica gel surface to remove the MIP in the solution with the MIP particle in the bottle.With ethanol curcumine in the extracting brand polymer in apparatus,Soxhlet's, in extracting solution, detect less than till the curcumine, with the oven dry of molecular brand powder, standby then.
(2) preparation of solid phase extraction sample
Turmeric Root after 5.0g cleaned extracts 30min with the 25mL alcohol heating reflux, extracts the back suction filtration that finishes, and filtrate is concentrated into dried, uses the 25mL dissolve with methanol then, and lysate is done the HPLC analysis after with the 0.45um filtering with microporous membrane.Remaining crude extract is preserved standby.
(3) Solid-Phase Extraction of curcumine crude extract
Activate: the molecular brand polymer 500.0mg after finishing with extracting uses 20mL methyl alcohol drip washing pillar then with methyl alcohol wet method dress post, and remaining impurities in the wash-out polymkeric substance makes the abundant swelling of molecular brand polymer.
Last sample: after activation finished, the crude extract 0.2mL that extracts curcumine with syringe went up sample.In the process of last sample, the effluent liquid in the pillar is collected, be evaporated to driedly, use the dissolve with methanol of 2.0mL then, wait to be HPLC and detect.
Drip washing: after treating that sample immerses in the polymkeric substance fully, with methanol-water (3:7, leacheate 30mL drip washing pillar V/V).Collect leacheate, be evaporated to driedly, use the dissolve with methanol of 2mL then, wait to be HPLC and detect.
Wash-out: after drip washing finished, (9:1, the V/V) curcumine in the 20mL wash-out pillar were treated elutriant to be merged behind the effluent liquid water white transparency, are evaporated to driedly, obtain the curcumine sample behind the purifying with methyl alcohol-acetic acid.Sample is HPLC to be detected.
Claims (14)
1, a kind of molecular brand polymer of curcumine, described molecular brand polymer by the template molecule of molecular brand polymer and function monomer behind polymerization reaction take place under the linking agent effect, obtain after falling described template molecule with solvent extraction again, it is characterized in that:
The template molecule of the molecular brand polymer of described curcumine is the combination of one or more in the compound shown in the formula (I)～(III);
The function monomer of the molecular brand polymer of described curcumine is following one or more mixing: methacrylic acid, vinylformic acid, 2-methylacryoyloxyethyl phosphoric acid, methylene-succinic acid, trifluoromethyl acrylate, to vinyl benzoic acid, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid, 4-vinylpridine, the diethylaminoethyl-methacrylic ester, diformazan aminoethyl methacrylic ester, p-aminophenyl ethene, the 1-vinyl imidazole, the 4-vinyl imidazole, 2,6-bisacrylamind yl pyridines, acrylamide, Methacrylamide, N, the two methacryloyl ethylethanolamines of O-, N, N, N-trimethylammonium aminoethyl methacrylic acid ester hydrochloride, the 2-hydroxyethyl meth acrylate;
The linking agent of the molecular brand polymer of described curcumine is following one or more combination: Vinylstyrene, 1,3 di isopropenylbenzenes, Ethylene glycol dimethacrylate, tetramethylene dimethacrylate, dimethacrylate triglycol ester, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, N, N '-methylene-bisacrylamide, N, N '-vinyl bisacrylamide;
2, the molecular brand polymer of curcumine as claimed in claim 1 is characterized in that described function monomer is one of following: methacrylic acid, vinylformic acid, trifluoromethyl acrylate, 4-vinylpridine, p-aminophenyl ethene, 1-vinyl imidazole, 4-vinyl imidazole, acrylamide, Methacrylamide.
3, the molecular brand polymer of curcumine as claimed in claim 1, it is characterized in that described linking agent is one of following: Vinylstyrene, 1,3 di isopropenylbenzene, Ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate.
4, the molecular brand polymer of curcumine as claimed in claim 1, the preparation that it is characterized in that the molecular brand polymer of described curcumine comprises the steps: in pore-creating agent, curcumin chemical compounds molecule, function monomer and linking agent mix, polymerization reaction take place, controlled temperature is fully obtaining the polymkeric substance crude product after the reaction between 50～80 ℃, and described polymkeric substance crude product falls the molecular brand polymer that obtains described curcumine behind wherein the curcumin chemical compounds molecule with solvent extraction.
5, the molecular brand polymer of curcumine as claimed in claim 4 is characterized in that described pore-creating agent is following one or more combination: tetrahydrofuran (THF), toluene, chloroform, acetone, methylene dichloride, acetonitrile.
6, the molecular brand polymer of curcumine as claimed in claim 4, what it is characterized in that described curcumin chemical compounds, function monomer and linking agent feeds intake amount of substance than being 1:2～20:4～80.
7, the molecular brand polymer of curcumine as claimed in claim 4 is characterized in that described polyreaction adopts thermal initiation or light-initiated, and the initiator that uses is azo-compound or superoxide.
8, the molecular brand polymer of curcumine as claimed in claim 4 is characterized in that the employed solvent of extracting curcumin chemical compounds molecule is following one or more combination: methyl alcohol, ethanol, acetone, tetrahydrofuran (THF).
9,, it is characterized in that described molecular brand polymer adopts one of following method to be prepared: mass polymerization, suspension polymerization, emulsion polymerization, seed swelling polymerization as the molecular brand polymer of the described curcumine of one of claim 1～8.
10, the molecular brand polymer of curcumine as claimed in claim 9, when it is characterized in that described molecular brand polymer adopts mass polymerization, suspension polymerization or emulsion polymerization to be prepared, the polymkeric substance crude product grinds back wet method mistake 〉=400 mesh sieves in water, uses eluting solvent extracting curcumin chemical compounds wherein again after suction filtration, the oven dry.
11, the molecular brand polymer of curcumine as claimed in claim 1 is as the application of solid extracting agent in separate and purify curcumin compounds.
12, application as claimed in claim 11, it is characterized in that described application is specific as follows: the molecular brand polymer with curcumine is a solid extracting agent, extraction obtains curcumin chemical compounds from the curcumine crude extract, described Solid-Phase Extraction comprises the activation of molecular brand polymer, with sample, methanol aqueous solution drip washing, four steps of eluting solvent wash-out on the curcumine crude extract, the elutriant that contains curcumin chemical compounds that wash-out obtains promptly obtains the pure product of curcumin chemical compounds through aftertreatment; Described curcumine crude extract is obtained through solvent-extraction process by Turmeric Root, described extraction solvent is one of following: the methanol solution of water, methyl alcohol, ethanol, acetone, alkali, the ethanolic soln of alkali, the acetone soln of alkali, alkali aqueous solution, the mass concentration of alkali is no more than 50% in the acetone soln of the methanol solution of described alkali, the ethanolic soln of alkali, alkali and the alkali aqueous solution, and described alkali is oxyhydroxide or the salt that shows alkalescence; Described eluting solvent is the good solvent of curcumin chemical compounds.
13, application as claimed in claim 12 is characterized in that in the process of Solid-Phase Extraction the drip washing solvent is the methanol in water of volume fraction≤30%.
14, application as claimed in claim 12, it is characterized in that in the process of Solid-Phase Extraction, eluting solvent is the combination of one or more arbitrary proportions in methyl alcohol, ethanol, the acetone, perhaps eluting solvent is the acetic acid solution of methyl alcohol, ethanol or acetone, and wherein quality of acetic acid concentration is not more than 20%.
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| CNA2008101215109A CN101381430A (en) | 2008-10-09 | 2008-10-09 | Molecule brand polymer of curcumin, preparation method and application thereof |
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| CNA2008101215109A CN101381430A (en) | 2008-10-09 | 2008-10-09 | Molecule brand polymer of curcumin, preparation method and application thereof |
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| CN105198717A (en) * | 2015-10-14 | 2015-12-30 | 中山大学 | Method for selectively extracting and separating curcumin |
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| CN114874484A (en) * | 2022-04-28 | 2022-08-09 | 重庆迈德凯医药有限公司 | Preparation method of molecular imprinting polymer based on curcumin, electrochemical sensor and application of electrochemical sensor |
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