CN108047483A - Preparation method of luteolin molecularly imprinted polymer microspheres and application of luteolin molecularly imprinted polymer microspheres in solid-phase extraction, separation and purification - Google Patents
Preparation method of luteolin molecularly imprinted polymer microspheres and application of luteolin molecularly imprinted polymer microspheres in solid-phase extraction, separation and purification Download PDFInfo
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- CN108047483A CN108047483A CN201711076286.1A CN201711076286A CN108047483A CN 108047483 A CN108047483 A CN 108047483A CN 201711076286 A CN201711076286 A CN 201711076286A CN 108047483 A CN108047483 A CN 108047483A
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- cyanidenon
- methanol
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- 239000004005 microsphere Substances 0.000 title claims abstract description 33
- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 16
- 238000000746 purification Methods 0.000 title claims abstract description 4
- 238000000926 separation method Methods 0.000 title abstract description 8
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 title abstract description 4
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 title abstract description 4
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 title abstract description 4
- 235000009498 luteolin Nutrition 0.000 title abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 162
- 229920000642 polymer Polymers 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 23
- 241001553178 Arachis glabrata Species 0.000 claims description 23
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 23
- 235000018262 Arachis monticola Nutrition 0.000 claims description 23
- 235000020232 peanut Nutrition 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000287 crude extract Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 230000010355 oscillation Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010828 elution Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000523 sample Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000012673 precipitation polymerization Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- -1 azo Nitrile Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000284 extract Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001727 in vivo Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000012453 solvate Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XFZJEEAOWLFHDH-UHFFFAOYSA-N (2R,2'R,3R,3'R,4R)-3,3',4',5,7-Pentahydroxyflavan(48)-3,3',4',5,7-pentahydroxyflavan Natural products C=12OC(C=3C=C(O)C(O)=CC=3)C(O)CC2=C(O)C=C(O)C=1C(C1=C(O)C=C(O)C=C1O1)C(O)C1C1=CC=C(O)C(O)=C1 XFZJEEAOWLFHDH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CWEZAWNPTYBADX-UHFFFAOYSA-N Procyanidin Natural products OC1C(OC2C(O)C(Oc3c2c(O)cc(O)c3C4C(O)C(Oc5cc(O)cc(O)c45)c6ccc(O)c(O)c6)c7ccc(O)c(O)c7)c8c(O)cc(O)cc8OC1c9ccc(O)c(O)c9 CWEZAWNPTYBADX-UHFFFAOYSA-N 0.000 description 1
- MOJZMWJRUKIQGL-FWCKPOPSSA-N Procyanidin C2 Natural products O[C@@H]1[C@@H](c2cc(O)c(O)cc2)Oc2c([C@H]3[C@H](O)[C@@H](c4cc(O)c(O)cc4)Oc4c3c(O)cc(O)c4)c(O)cc(O)c2[C@@H]1c1c(O)cc(O)c2c1O[C@@H]([C@H](O)C2)c1cc(O)c(O)cc1 MOJZMWJRUKIQGL-FWCKPOPSSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HGVVOUNEGQIPMS-UHFFFAOYSA-N procyanidin Chemical compound O1C2=CC(O)=CC(O)=C2C(O)C(O)C1(C=1C=C(O)C(O)=CC=1)OC1CC2=C(O)C=C(O)C=C2OC1C1=CC=C(O)C(O)=C1 HGVVOUNEGQIPMS-UHFFFAOYSA-N 0.000 description 1
- 229920002414 procyanidin Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
the invention discloses a preparation method of luteolin molecularly imprinted polymer microspheres and application thereof in solid phase extraction, separation and purification.
Description
Technical field
The present invention relates to the preparing technical fields of molecular engram microsphere, are printed more particularly, to a kind of cyanidenon molecule
The preparation method of mark polymer microballoon and its application in terms of Solid phase extraction separation purifying.
Background technology
Luteolin from Peanut content is higher, is one of ideal source of cyanidenon, develops in peanut shell
Cyanidenon can improve the comprehensive utilization value of peanut.Cyanidenon has dual in terms of human health care and plant stress-resistance
Application value causes the extensive attention of domestic and international researcher.Then natural drug extract component is complex, has many knots
The component that structure is similar, chemical property is similar, therefore conventional separation means purity is relatively low, the rate of recovery is not high, and product quality is difficult to
Ensure.Molecular engram is to be gathered by synthesizing with the trace with target molecule specific adsorption effect with Solid phase extraction separation technology
Object is closed, to there is high selectivity by binding molecule, is very suitable for the separation system of complicated component.But currently for peanut shell
In contained cyanidenon, have no cyanidenon molecular blotting polymer microsphere prepare with Solid phase extraction separation purifying method and answer
Correlative study is reported.
The content of the invention
The technical problem to be solved by the present invention is to be directed to the technology of existing cyanidenon separating-purifying molecular engram microsphere
Deficiency provides a kind of preparation method of cyanidenon molecular blotting polymer microsphere.
A present invention also technical problems to be solved are to provide the cyanidenon molecular blotting polymer microsphere in solid phase
Application in terms of extraction separation purification cyanidenon.
The purpose of the present invention is achieved by the following technical programs：
A kind of preparation method of cyanidenon molecular blotting polymer microsphere is provided, is using cyanidenon standard items as template
Molecule, α-methacrylic acid is as function monomer, and ethylene glycol dimethacrylate is as crosslinking agent, azodiisobutyronitrile conduct
Initiator, methanol are prepared as pore-foaming agent using precipitation polymerization method.
Preferably, the template molecule：Function monomer：The molar ratio of crosslinking agent is 1:(6~10):(28~32).
Preferably, the initiator amount is according to template molecule：The ratio of initiator is 0.2mmol：0.1g is determined.
It is highly preferred that the template molecule, function monomer, the dosage of crosslinking agent and initiator are according to template molecule dosage
For 0.2mmol, function monomer dosage is 1.6mmol, dosage of crosslinking agent 6mmol, and initiator amount determines for 0.1g.
Preferably, the dosage of the methanol is according to template molecule：The ratio of methanol is 0.2mmol：The amount of 30mL determines.
Preferably, the preparation method of cyanidenon molecular blotting polymer microsphere of the present invention comprises the following steps：
S01. template molecule cyanidenon standard items are dissolved in methanol, add in function monomer, sonic oscillation is to complete
Dissolving；
S02. crosslinking agent and initiator are added in into the dissolved systems of step S01, ultrasound degassing 5min is filled with nitrogen guarantor
5min is protected, polymerization is vibrated in sealing in water bath with thermostatic control；
S03. the system after polymerizeing will be vibrated to filter, filter residue and drying is taken, extracted through mixed organic solvents solution, again with methanol
Elution removes acetic acid, dry, obtains molecularly imprinted polymer.
Preferably, step S01 is the ultrasonic cyclotron oscillation 1h under 60 DEG C of water bath conditions.
Preferably, the time of ultrasound degassing is 5min described in step S02, and the time for being filled with nitrogen protection is 5min；
The polymerization is that vibration polymerize for 24 hours under the conditions of 60 DEG C of waters bath with thermostatic control.
Preferably, extraction is carried out in apparatus,Soxhlet's described in step S03；The mixed solvent is methanol)：Acetic acid is pressed
It is 8 according to volume ratio：2 mixing gained.The time of the extraction is 6~7 days.The time of the drying is for 24 hours.
Cyanidenon methanol solution can will be added in molecularly imprinted polymer obtained by step S03, adsorbed, centrifugation takes supernatant
Liquid measures its peak area in high performance liquid chromatography, calculates the variable quantity Q of solution concentration before and after absorption.Preferably, the suction
Attached to be adsorbed using cyclotron oscillation, the time of absorption is for 24 hours.
Present invention simultaneously provides the cyanidenon molecular blotting polymer microsphere in procyanidin peanut shell institute
Application in terms of containing cyanidenon.
The method of the application comprises the following steps：
S11. build solid-phase extraction column, tubulose extraction column tube bottom tile cotton, by molecular engram produced by the present invention
Polymer is with dry pack in the filtering material that on filtering material, tiles in pipe at the top of the pillar filled；It is slowly added to first
Alcohol activating adsorbent, adds in water balance solid phase extraction column, and vacuum drains compacting pillar, discards efflux；
S12. crushed toward peanut shell in gained powder and add in ethyl alcohol, extracted, filtered, the filtrate that will be obtained, rotary evaporation is extremely
Paste, with the aqueous dissolution of methanol, centrifugation takes clear liquid to obtain peanut shell crude extract；
S13. using peanut shell crude extract obtained by step S12 as the sample solution of solid-phase extraction column described in step S11, take out true
Idling is depressed, and sample liquid is made to enter cylinder, absorption；
S14. the extraction column after absorption is eluted using the aqueous solution of methanol, methanol and formic acid mixing is added in after draining
Solution is eluted, and collects efflux, and evaporation and concentration obtains cyanidenon product paste liquid.
Preferably, the pillar height of bed about 2.5cm described in step S11, bed volume are about 5cm3.The addition of the methanol is
10mL, the addition of the water is 10mL.
Wherein step S11 can also use tetrafluoro piston chromatographic column, be let the liquid out using pressurizing ball pressurization.It is preferred that
Ground, the column length of tetrafluoro piston chromatographic column described in step S21:24cm, column mouth outer diameter:3cm, bed volume：64cm3。
Preferably, the concentration of volume percent of ethyl alcohol described in step S12 is 80%.The dosage of ethyl alcohol is according to its volume and flower
The ratio of the quality of raw shell powder is 20mL：1g is determined.
Preferably, extraction is carried out in 80 DEG C of constant temperature oscillation bain-marie described in step S12, and the time of the extraction is
3h.The concentration of the methanol/water solution is 50%.
Preferably, absorption is to adsorb 20min under gravity described in step S13.
Preferably, absorption described in step S13 can also be by setting pressue device pressurization to make the smooth stream of the in vivo liquid of column
Go out.Method that is most simple and practicable and ensureing adsorption effect is to set device for storing liquid on cylinder top, is given and stored up by pressue device
Fluid pressure is transferred to liquid in cylinder in liquid device so that the in vivo liquid of column combs outflow.
Preferably, the concentration of the aqueous solution of the methanol of elution described in step S14 is 35%.It is described elution coutroi velocity be
1.5 seconds/drop.The elution is eluted using 80% methanol/formic acid solution.The wherein mixed volume ratio of methanol and formic acid
Example is 20mL：5mL.
Preferably, gradient elution may be employed in step S14, use concentration of volume percent for 35% successively, 60%,
80%th, 100% methanol aqueous solution carries out gradient elution, collects efflux in batches；And by 60% methanol solution stream of the second component
Go out liquid, 80% methanol solution efflux enrichment method of third component, obtain relative purity and reach more than 95% cyanidenon product,
It can reach health product raw material production requirement.4th component, 100% methanol solution efflux rotary evaporation is concentrated, filter paper filtering
Afterwards, cyanidenon crystal can be obtained by petroleum ether recrystallization, color is more single, and purity is higher.
Beneficial effects of the present invention are as follows：
Cyanidenon molecular blotting polymer microsphere is prepared using precipitation party method in the present invention.Using cyanidenon as
Template molecule, α-methacrylic acid (MAA) are used as function monomer, and ethylene glycol dimethacrylate (EGDMA) is used as crosslinking agent
Polymerisation is carried out in methanol solvate for azodiisobutyronitrile (AIBN) with initiator, the microballoon is made.The present invention is to polymerization
The ratio of template molecule, function monomer and crosslinking agent is furtherd investigate in raw material, with reference to solvent dosage, polymerization time and temperature
Deng other key factors, summary draws cyanidenon:α-methacrylic acid:The molar ratio of ethylene glycol dimethacrylate is 1:
8:30, when methanol solvate is 30mL, its adsorbance of microballoon obtained is 42.56 μm of ol/g, α 1.25, has the selection of height
Adsorptivity, grain size small specific surface product is big, is outstanding solid phase extraction adsorbents.
The present invention provides the application technology scheme of the microballoon, with cyanidenon molecular blotting polymer microsphere obtained
As the adsorption stuffing of SPE solid-phase extraction columns, good effect is obtained.
In the application, the present invention further refines and optimizes concrete operation step, the operating process of Solid Phase Extraction, passes through
Optimize Solid Phase Extraction experiment condition, draw collection with reference to microballoon of the present invention as molecularly imprinted polymer, with 35% methanol of 15mL
For solution as eluent, 80% methanol/formic acid solution eluent of 25mL is optimal as 0.3000gMIPs solid phase extraction columns
SPE condition.After being extracted, the purity of cyanidenon is increased to compared with crude extract by original 51.9%
94.2%, the rate of recovery reaches 90.6%.
On the basis of aforementioned schemes, the present invention is also amplified solid phase extraction column experiment, increases imprinted polymer
Amount of fill, improve peanut shell crude extract sample size, simulate the process that actual back yard industry produces, pass through the side of gradient elution
Formula obtains the higher cyanidenon product of a large amount of purity and cyanidenon crystal.
Description of the drawings
Fig. 1 cyanidenon canonical plottings.
Fig. 2 Solid Phase Extraction column experiment device structure diagrams.
Fig. 3 SPE solid phase extraction column structure diagrams.
Fig. 4 peanut shell crude extract HPLC testing results.
Fig. 5 Solid Phase Extraction eluent HPLC testing results.
Fig. 6 cyanidenon standard specimen HPLC testing results.
The SEM scanning figures of Fig. 7 molecularly imprinted polymers (microballoon).
Specific embodiment
It is further illustrated the present invention with reference to specific embodiment.Following embodiments are only for illustration, it is impossible to manage
It solves as limitation of the present invention.Unless stated otherwise, the reagent used in following embodiments is that conventional purchased in market or commercial sources obtain
The reagent obtained, unless stated otherwise, the method and apparatus used in following embodiments is method commonly used in the art and sets
It is standby.
1. experiment reagent
2. laboratory apparatus
Embodiment 1
The present embodiment provides a kind of device isolated and purified suitable for cyanidenon, as shown in Fig. 2, including chromatographic column 1, storage
Liquid device 2 receives container 3, fixed frame 4, pressue device 5, and device for storing liquid 2 and chromatographic column 1 are individually fixed in fixed frame 4；Liquid storage
2 top of device is equipped with opening 21, and lower part is equipped with outlet 22, and its upper part opening 21 connects pressue device 5, device for storing liquid when in use
The outlet 22 of 2 lower part connects chromatographic column 1；The upper end of the chromatographic column is provided with opening 11, and the bottom of chromatographic column is provided with out
Mouth 12, the exit of chromatographic column are provided with control switch 13, and 12 lower section of outlet of chromatographic column 1 sets reception container 3.
The reception container 3 can be beaker or other similar containers.
As shown in figure 3, cyanidenon molecular blotting polymer microsphere pillar 15 and filter material are filled in the chromatographic column
Material.The filtering material is respectively arranged at the top 16 of cyanidenon molecular blotting polymer microsphere pillar and lower part 14.It is described
The filtering material on the top 16 of cyanidenon molecular blotting polymer microsphere pillar is arranged at as cotton or filter paper, it can be fine
Ground avoids the impact to cyanidenon molecular blotting polymer microsphere pillar.It is preferred that using cotton.It is described to be arranged at cyanidenon
The filtering material 14 of the lower part of molecular blotting polymer microsphere pillar is cotton or quartz sand, for cyanidenon molecule is avoided to print
Mark polymer microballoon is missed.It is preferred that cotton.The top for being arranged at cyanidenon molecular blotting polymer microsphere pillar is under
The filtering material in portion can use cotton, and cost is relatively low, and it is convenient to replace.The thickness of elaborating of cotton is 0.2cm.
The filling height of the cyanidenon molecular blotting polymer microsphere is 9cm, admission space 64cm3。
Tetrafluoro piston chromatographic column may be employed in the chromatographic column 1.Based on fundamental design idea of the present invention, can also be put
Big experiment by the use of tetrafluoro piston chromatographic column as cylinder, adds the amount of fill of imprinted polymer, improves peanut shell crude extract
Sample size simulates the process of actual back yard industry production.
Piston may be employed in control switch at the chromatographic column lower part outlet, simple and convenient.
As shown in Figure 1, pressue device 5 of the present invention includes pressurization sphere 51 and connecting tube 52, the connecting tube 52
One end connection pressurization sphere 51, the other end connect the opening 21 that 2 top of device for storing liquid is equipped with.The present invention sets pressue device
Pressurization makes the smooth outflow of the in vivo liquid of column.Most simple and practicablely, pressurizing ball is connected in liquid storage ball upper, open end 21, by right
The extruding of pressurization sphere 51 causes the in vivo liquid of column to comb outflow.
Liquid storage ball 2 and chromatographic column 1 are individually fixed in fixed frame 4, and the two can pass through activity in the fixed position of fixed frame 4
Folder is adjusted.
Embodiment 2
The present embodiment provides a kind of preparation methods of cyanidenon molecular blotting polymer microsphere, are with cyanidenon standard
Product are template molecule, and α-methacrylic acid is as function monomer, and for ethylene glycol dimethacrylate as crosslinking agent, azo two is different
Butyronitrile is prepared as initiator, methanol as pore-foaming agent using precipitation polymerization method.Comprise the following steps：
S01. 0.2mmol template molecule cyanidenon standard items are accurately weighed, are dissolved in 30mL methanol solvates, are added in
1.6mmol α-methacrylic acid function monomers, sonic oscillation is to being completely dissolved.At 60 DEG C, water-bath cyclotron oscillation 1h；
S02. addition 6mmol ethylene glycol dimethacrylates crosslinking agent and 0.1g initiator A IBN, ultrasound degassing 5min,
Nitrogen protection 5min is filled with, sealing vibrates polymerization for 24 hours in 60 DEG C of waters bath with thermostatic control.
S03. polymerizate obtained by step S02 is filtered in cloth funnel, it is dry, it is put into apparatus,Soxhlet's, and adds in
200mL V (methanol)：V (acetic acid)=8：2 solution extract a week, and again with methanol elution removes acetic acid, and drying for 24 hours, obtains institute
State molecular blotting polymer microsphere.
The made molecularly imprinted polymers of 0.0300g are weighed in 10mL centrifuge tubes, add in the cyanidenon first of 1mmol/L
Alcoholic solution 10mL.Cyclotron oscillation adsorbs for 24 hours, and centrifugation takes supernatant in high performance liquid chromatography, measures its peak area.
Linear regression is carried out according to concentration c (μ g/mL) and peak area A (mAU), calculates to obtain regression equation：Y=
72.802x+6.3075 coefficient R2=0.9996.
1 cyanidenon concentration of table (μ g/mL) and peak area relation
| Concentration c (μ g/mL) | 2 | 4 | 8 | 12 |
| Peak area A (mAU) | 185.23 | 304.08 | 592.12 | 862.22 |
| Concentration c (μ g/mL) | 16 | 20 | 28 | 40 |
| Peak area A (mAU) | 1153.23 | 1447.93 | 2032.67 | 2943.52 |
Standard curve as shown in Figure 1, the variable quantity Q that can calculate solution concentration before and after adsorbing are 42.56 μm of ol/g.
Embodiment 3
The present embodiment provides a kind of preparation methods of cyanidenon molecular blotting polymer microsphere, are with cyanidenon standard
Product are template molecule, and α-methacrylic acid is as function monomer, and for ethylene glycol dimethacrylate as crosslinking agent, azo two is different
Butyronitrile is prepared as initiator, methanol as pore-foaming agent using precipitation polymerization method.Comprise the following steps：
S01. 0.2mmol template molecule cyanidenon standard items are accurately weighed, are dissolved in 30mL methanol solvates, are added in
1.6mmol α-methacrylic acid function monomers, sonic oscillation is to being completely dissolved.At 60 DEG C, water-bath cyclotron oscillation 1h；
S02. addition 6mmol ethylene glycol dimethacrylates crosslinking agent and 0.1g initiator A IBN, ultrasound degassing 5min,
Nitrogen protection 5min is filled with, sealing vibrates polymerization for 24 hours in 60 DEG C of waters bath with thermostatic control.
S03. polymerizate obtained by step S02 is filtered in cloth funnel, it is dry, it is put into apparatus,Soxhlet's, and adds in
200mL V (methanol)：V (acetic acid)=8：2 solution extract a week, and again with methanol elution removes acetic acid, and drying for 24 hours, obtains institute
State molecular blotting polymer microsphere.
The made molecularly imprinted polymers of 0.0300g are weighed in 10mL centrifuge tubes, add in the cyanidenon first of 1mmol/L
Alcoholic solution 10mL.Cyclotron oscillation adsorbs for 24 hours, and centrifugation takes supernatant in high performance liquid chromatography, measures its peak area.By Fig. 1 institutes
The standard curve shown, the variable quantity Q that can calculate solution concentration before and after adsorbing are 42.56 μm of ol/g.By above-described embodiment 1 or
2 gained molecularly imprinted polymers (microballoon) carry out SEM figure scannings, as shown in Figure 7.
Cyanidenon isolates and purifies in the application molecularly imprinted polymer of embodiment 4 (microballoon) realization Extracts from Peanut Hulls
Based on the structure described in embodiment 1, the cyanidenon molecular blotting polymer microsphere that embodiment 2 or 3 synthesizes is weighed
0.3000g, dry pack is in 10mL solid phase extraction columns, and a fritter cotton of tiling at the top of the pillar filled, the height of bed is about
2.5cm, bed volume are about 5cm3；10mL methanol activating adsorbents, 10mL water balance solid phase extraction columns are slowly added to, vacuum is taken out
Dry-pressing reality pillar, discards efflux；
S12. accurately claim 8g peanut shells powder with electronic balance in the beaker of 500mL, 160mL volume integrals are added in toward beaker
Number is 80% ethyl alcohol, is placed on after being sealed with tinfoil in 80 DEG C of constant temperature oscillation bain-marie and extracts 3h, the filtrate filtered,
Rotary Evaporators are steamed to paste, are dissolved with 40mL50% methanol/water solutions, and centrifugal filtering liquid obtains peanut shell crude extract；Profit
It is detected with high performance liquid chromatograph, testing result is as shown in Figure 4；
S13. using peanut shell crude extract as the sample solution of the present embodiment solid-phase extraction column, vacuumize under negative pressure, make sample
Liquid is entered cylinder, and 20min is adsorbed under gravity；
S14. solid-phase extraction column is eluted using 15mL35% methanol/water solutions, coutroi velocity is 1.5 seconds/drop, is taken out
It is dry.It is slowly added to 25mL80% methanol/formic acid solution to be eluted, collects efflux, evaporation and concentration obtains cyanidenon product
Paste liquid.Using efficient liquid phase chromatographic analysis, the results are shown in Figure 5, and impurity is substantially eliminated in peanut shell crude extract, with
Cyanidenon standard specimen high-efficient liquid phase chromatogram is close.As shown in Figure 6.The purity of cyanidenon is by original crude extract 51.9%
94.2% is increased to, the rate of recovery reaches 90.6%.
Cyanidenon isolates and purifies in the application molecularly imprinted polymer of embodiment 5 (microballoon) realization Extracts from Peanut Hulls
S11. based on embodiment 1 described in structure, weigh embodiment 2 or 3 synthesis cyanidenon molecularly imprinted polymer
Microballoon 6.000g molecularly imprinted polymers (MIPs) are added in 50mL methanol solutions, are loaded imprinted polymer using wet method dress post
In tetrafluoro piston chromatographic column, gravity natural subsidence is let the liquid out using pressurizing ball pressurization.
S12. 40mL methanol activating adsorbents, 40mL water are slowly added to successively to tetrafluoro piston chromatographic column described in step S11
Solid phase extraction column is balanced, pressurization drains compacting pillar, discards efflux；
S13. peanut shell crude extract is slowly added into tetrafluoro piston chromatographic column described in step S12, and (preparation method is the same as real
Applying example 4) 20mL makes sample enter adsorbent using pressurization, and 20min is adsorbed, is drained；
S14. tetrafluoro piston chromatographic column described in step S13 is used into 35%, 60%, 80%, 100% methanol/waters of 50mL successively
Solution carries out gradient elution, collects efflux in batches.
By 60% methanol solution efflux of the second component, 80% methanol solution efflux enrichment method of third component, obtain
Relative purity reaches more than 95% cyanidenon product, reaches health product raw material production requirement.
4th component, 100% methanol solution efflux rotary evaporation is concentrated, after filter paper filtering, is recrystallized by petroleum ether
Cyanidenon crystal can be obtained, color is more single, and purity is higher.
Using efficient liquid phase chromatographic analysis the present embodiment products obtained therefrom, the results are shown in Figure 5, in peanut shell crude extract
Impurity is substantially eliminated, close with cyanidenon standard specimen high-efficient liquid phase chromatogram.As shown in Figure 6.The purity of cyanidenon is by original
The crude extract 51.9% come is increased to 95%, and the purity of cyanidenon crystal reaches more than 95%, and the rate of recovery reaches 90.6%.
Claims (10)
1. a kind of preparation method of cyanidenon molecular blotting polymer microsphere, which is characterized in that be with cyanidenon standard items
For template molecule, α-methacrylic acid is as function monomer, and ethylene glycol dimethacrylate is as crosslinking agent, two isobutyl of azo
Nitrile is prepared as initiator, methanol as pore-foaming agent using precipitation polymerization method.
2. the preparation method of cyanidenon molecular blotting polymer microsphere according to claim 1, which is characterized in that the mould
Plate molecule：Function monomer：The molar ratio of crosslinking agent is 1:(6~10):(28~32).
3. the preparation method of cyanidenon molecular blotting polymer microsphere according to claim 1, which is characterized in that described to draw
Agent dosage is sent out according to template molecule：The ratio of initiator is 0.2mmol：0.1g is determined.
4. the preparation method of cyanidenon molecular blotting polymer microsphere according to claim 1, which is characterized in that the first
The dosage of alcohol is according to template molecule：The ratio of methanol is 0.2mmol：The amount of 30mL determines.
5. according to the preparation method of any one of Claims 1-4 cyanidenon molecular blotting polymer microsphere, feature exists
In comprising the following steps：
S01. template molecule cyanidenon standard items are dissolved in methanol, add in function monomer, sonic oscillation is to being completely dissolved；
S02. crosslinking agent and initiator are added in into the dissolved systems of step S01, ultrasound degassing 5min is filled with nitrogen protection
Polymerization is vibrated in 5min, sealing in water bath with thermostatic control；
S03. the system after polymerizeing will be vibrated to filter, take filter residue, it is dry, it is extracted through mixed organic solvents solution, again with methanol is washed
Acetic acid is removed in removing, dry, obtains molecularly imprinted polymer.
6. the preparation method of cyanidenon molecular blotting polymer microsphere according to claim 5, which is characterized in that step
S01 is the ultrasonic cyclotron oscillation 1h under 60 DEG C of water bath conditions；Polymerization is shaken under the conditions of 60 DEG C of waters bath with thermostatic control described in step S02
Swing polymerization for 24 hours；
The time of ultrasound degassing is 5min described in step S02, and the time for being filled with nitrogen protection is 5min；Described in step S03
Extraction mixed solvent is methanol：Acetic acid is 8 according to volume ratio：2 mixing gained.
7. the cyanidenon molecular blotting polymer microsphere that any one of claim 1 to 6 preparation method is prepared is solid
Application in phase abstraction purification peanut shell in terms of contained cyanidenon.
8. application according to claim 7, which is characterized in that the method for the application comprises the following steps：
S11. solid-phase extraction column is built, in the tube bottom tiling cotton of tubulose extraction column, molecular engram produced by the present invention is polymerize
Object is with dry pack in the filtering material that on filtering material, tiles in pipe at the top of the pillar filled；It is slowly added to methanol work
Change adsorbent, add in water balance solid phase extraction column, vacuum drains compacting pillar, discards efflux；
S12. crushed toward peanut shell in gained powder and add in ethyl alcohol, extracted, filtered, the filtrate that will be obtained, rotary evaporation to paste,
With the aqueous dissolution of methanol, centrifugation takes clear liquid to obtain peanut shell crude extract；
S13. using peanut shell crude extract obtained by step S12 as the sample solution of solid-phase extraction column described in step S11, vacuumize negative
Pressure makes sample liquid enter cylinder, absorption；
S14. the extraction column after absorption is eluted using the aqueous solution of methanol, methanol and formic acid mixed solution is added in after draining
It is eluted, collects efflux, evaporation and concentration obtains cyanidenon product paste liquid.
9. application according to claim 8, which is characterized in that pillar height of bed 2.5cm, bed volume are described in step S11
5cm3；
Alternatively, solid-phase extraction column described in step S11 uses tetrafluoro piston chromatographic column；The column length of the tetrafluoro piston chromatographic column:
24cm, column mouth outer diameter:3cm, bed volume：64cm3。
10. application according to claim 8, which is characterized in that step S14 uses gradient elution, successively using volume hundred
The methanol aqueous solution that specific concentration is 35%, 60%, 80%, 100% is divided to carry out gradient elution, collects efflux in batches；By second
60% methanol solution efflux of component, 80% methanol solution efflux enrichment method of third component, obtain cyanidenon product；It will
4th component, 100% methanol solution efflux rotary evaporation concentrates, and after filtering, cyanidenon crystalline substance is recrystallized to give by petroleum ether
Body.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659982A (en) * | 2012-05-24 | 2012-09-12 | 国际竹藤中心 | Flavone magnetic molecularly imprinted polymer, preparation of flavone magnetic molecularly imprinted polymer, and application of flavone magnetic molecularly imprinted polymer to bamboo-leaf flavone separation |
| CN104558409A (en) * | 2013-10-22 | 2015-04-29 | 北京林业大学 | Surface molecular imprinting polymer made from nanoflower material, and preparation and application of surface molecular imprinting polymer |
-
2017
- 2017-11-03 CN CN201711076286.1A patent/CN108047483A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659982A (en) * | 2012-05-24 | 2012-09-12 | 国际竹藤中心 | Flavone magnetic molecularly imprinted polymer, preparation of flavone magnetic molecularly imprinted polymer, and application of flavone magnetic molecularly imprinted polymer to bamboo-leaf flavone separation |
| CN104558409A (en) * | 2013-10-22 | 2015-04-29 | 北京林业大学 | Surface molecular imprinting polymer made from nanoflower material, and preparation and application of surface molecular imprinting polymer |
Non-Patent Citations (9)
| Title |
|---|
| ，武汉大学化学与分子科学学院实验中心编著: "《基础有机化学实验》", 31 July 2014, 武汉大学出版社 * |
| 仝海娟等: "木犀草素分子印迹聚合物的制备及吸附性能研究", 《食品研究与开发》 * |
| 吴梧桐主编: "《生物制药工艺学》", 31 August 2015, 中国医药科技出版社 * |
| 彭松，林辉主编: "《有机化学实验》", 31 January 2013, 中国中医药出版社 * |
| 潘浪胜，曹红梅，高文姬，丁桂峰: "花生壳中黄酮类成分的识别分离与结构确定", 《应用化工》 * |
| 王洪存，孙树英编: "《层析技术及其在医药学上的应用》", 31 July 1985, 泰山医学院 * |
| 邓远雄，李晓宇主编: "《体内药物分析》", 31 July 2016, 中南大学出版社 * |
| 郭力，康文艺主编: "《中药化学实验》", 31 July 2015, 中国医药科技出版社 * |
| 陈安之主编: "《作业环境空气检测技术》", 31 August 1991, 北京经济学院出版社 * |
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