CN113292763A - Microwave preparation method of anthocyanin magnetic molecularly imprinted polymer - Google Patents
Microwave preparation method of anthocyanin magnetic molecularly imprinted polymer Download PDFInfo
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- 150000004636 anthocyanins Chemical class 0.000 title claims abstract description 47
- 229930002877 anthocyanin Natural products 0.000 title claims abstract description 45
- 235000010208 anthocyanin Nutrition 0.000 title claims abstract description 45
- 239000004410 anthocyanin Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 51
- VEVZSMAEJFVWIL-UHFFFAOYSA-O cyanidin cation Chemical compound [O+]=1C2=CC(O)=CC(O)=C2C=C(O)C=1C1=CC=C(O)C(O)=C1 VEVZSMAEJFVWIL-UHFFFAOYSA-O 0.000 claims abstract description 40
- 235000007336 cyanidin Nutrition 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 16
- 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 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000005855 radiation Effects 0.000 claims abstract description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract 4
- 229960002089 ferrous chloride Drugs 0.000 claims abstract 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract 4
- 239000000419 plant extract Substances 0.000 claims abstract 2
- 239000002861 polymer material Substances 0.000 claims abstract 2
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000696 magnetic material Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
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- 150000001452 anthocyanidin derivatives Chemical class 0.000 description 5
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- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
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- WCGUUGGRBIKTOS-GPOJBZKASA-N (3beta)-3-hydroxyurs-12-en-28-oic acid Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C WCGUUGGRBIKTOS-GPOJBZKASA-N 0.000 description 2
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- KZMACGJDUUWFCH-UHFFFAOYSA-O malvidin Chemical compound COC1=C(O)C(OC)=CC(C=2C(=CC=3C(O)=CC(O)=CC=3[O+]=2)O)=C1 KZMACGJDUUWFCH-UHFFFAOYSA-O 0.000 description 2
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- PSWFFKRAVBDQEG-YGQNSOCVSA-N thymopentin Chemical compound NC(N)=NCCC[C@H](N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@H](C(O)=O)CC1=CC=C(O)C=C1 PSWFFKRAVBDQEG-YGQNSOCVSA-N 0.000 description 2
- 229960004517 thymopentin Drugs 0.000 description 2
- 229940096998 ursolic acid Drugs 0.000 description 2
- PLSAJKYPRJGMHO-UHFFFAOYSA-N ursolic acid Natural products CC1CCC2(CCC3(C)C(C=CC4C5(C)CCC(O)C(C)(C)C5CCC34C)C2C1C)C(=O)O PLSAJKYPRJGMHO-UHFFFAOYSA-N 0.000 description 2
- ZJWIIMLSNZOCBP-KGDMUXNNSA-N (2s,3r,4s,5r,6r)-2-[5,7-dihydroxy-2-(3,4,5-trihydroxyphenyl)chromenylium-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol;chloride Chemical compound [Cl-].O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1OC1=CC2=C(O)C=C(O)C=C2[O+]=C1C1=CC(O)=C(O)C(O)=C1 ZJWIIMLSNZOCBP-KGDMUXNNSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RKWHWFONKJEUEF-GQUPQBGVSA-O Cyanidin 3-O-glucoside Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC2=C(O)C=C(O)C=C2[O+]=C1C1=CC=C(O)C(O)=C1 RKWHWFONKJEUEF-GQUPQBGVSA-O 0.000 description 1
- GCPYCNBGGPHOBD-UHFFFAOYSA-N Delphinidin Natural products OC1=Cc2c(O)cc(O)cc2OC1=C3C=C(O)C(=O)C(=C3)O GCPYCNBGGPHOBD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- RKWHWFONKJEUEF-WVXKDWSHSA-O Idaein Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1OC1=CC2=C(O)C=C(O)C=C2[O+]=C1C1=CC=C(O)C(O)=C1 RKWHWFONKJEUEF-WVXKDWSHSA-O 0.000 description 1
- 240000001549 Ipomoea eriocarpa Species 0.000 description 1
- 235000005146 Ipomoea eriocarpa Nutrition 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009830 antibody antigen interaction Effects 0.000 description 1
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- 238000013375 chromatographic separation Methods 0.000 description 1
- YTMNONATNXDQJF-UBNZBFALSA-N chrysanthemin Chemical compound [Cl-].O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC2=C(O)C=C(O)C=C2[O+]=C1C1=CC=C(O)C(O)=C1 YTMNONATNXDQJF-UBNZBFALSA-N 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- YTMNONATNXDQJF-QSLGVYCOSA-N cyanidin 3-O-beta-D-galactoside chloride Chemical compound [Cl-].O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1OC1=CC2=C(O)C=C(O)C=C2[O+]=C1C1=CC=C(O)C(O)=C1 YTMNONATNXDQJF-QSLGVYCOSA-N 0.000 description 1
- USNPULRDBDVJAO-FXCAAIILSA-N cyanidin 3-O-rutinoside betaine Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(=[O+]C3=CC(O)=CC([O-])=C3C=2)C=2C=C(O)C(O)=CC=2)O1 USNPULRDBDVJAO-FXCAAIILSA-N 0.000 description 1
- RDFLLVCQYHQOBU-ZOTFFYTFSA-O cyanin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=[O+]C1=CC(O)=C2)C=3C=C(O)C(O)=CC=3)=CC1=C2O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 RDFLLVCQYHQOBU-ZOTFFYTFSA-O 0.000 description 1
- 235000007242 delphinidin Nutrition 0.000 description 1
- JKHRCGUTYDNCLE-UHFFFAOYSA-O delphinidin Chemical compound [O+]=1C2=CC(O)=CC(O)=C2C=C(O)C=1C1=CC(O)=C(O)C(O)=C1 JKHRCGUTYDNCLE-UHFFFAOYSA-O 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000008131 glucosides Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000010829 isocratic elution Methods 0.000 description 1
- 229960001331 keracyanin Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 235000009584 malvidin Nutrition 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- HKUHOPQRJKPJCJ-UHFFFAOYSA-N pelargonidin Natural products OC1=Cc2c(O)cc(O)cc2OC1c1ccc(O)cc1 HKUHOPQRJKPJCJ-UHFFFAOYSA-N 0.000 description 1
- 235000006251 pelargonidin Nutrition 0.000 description 1
- XVFMGWDSJLBXDZ-UHFFFAOYSA-O pelargonidin Chemical compound C1=CC(O)=CC=C1C(C(=C1)O)=[O+]C2=C1C(O)=CC(O)=C2 XVFMGWDSJLBXDZ-UHFFFAOYSA-O 0.000 description 1
- 229930015721 peonidin Natural products 0.000 description 1
- 235000006404 peonidin Nutrition 0.000 description 1
- XFDQJKDGGOEYPI-UHFFFAOYSA-O peonidin Chemical compound C1=C(O)C(OC)=CC(C=2C(=CC=3C(O)=CC(O)=CC=3[O+]=2)O)=C1 XFDQJKDGGOEYPI-UHFFFAOYSA-O 0.000 description 1
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- 210000003934 vacuole Anatomy 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C08F122/00—Homopolymers 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
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
Abstract
The patent relates to a method for preparing anthocyanin magnetic molecularly imprinted polymer by a microwave method, belonging to the technical field of polymer material preparation and analytical chemistry; the method adopts a microwave synthesis method, and comprises the steps of synthesizing a certain amount of ferrous chloride, ferric chloride, tetraethyl orthosilicate, ethylene glycol dimethacrylate, azobisisobutyronitrile and cyanidin through microwave radiation, and obtaining the anthocyanin magnetic molecularly imprinted polymer through washing, methanol reflux extraction and room temperature freeze drying; the anthocyanin magnetic molecularly imprinted material provided by the invention can more accurately and sensitively capture various anthocyanin molecules in plant extract, can realize rapid separation of target substances in complex components through a control magnetic field, can avoid traditional procedures such as centrifugation and filtration, and can effectively solve the problem of high difficulty in effective extraction of anthocyanin in plants.
Description
Technical Field
The invention relates to chemical extraction and separation, in particular to a preparation method for preparing a anthocyanin magnetic molecularly imprinted material by using a microwave method.
Background
Anthocyanins (also called anthocyanidins) are water-soluble natural pigments widely present in plants in nature, and are colored aglycones obtained by hydrolyzing anthocyanins. The main color-producing substances in fruits, vegetables and flowers are mostly related to the plants. Under the condition of different pH values of plant cell vacuoles, the anthocyanin enables the petals to present colorful colors. More than 20 anthocyanidins are known, and 6 important foods are pelargonidin, cyanidin, delphinidin, peonidin, morning glory pigment and malvidin. The natural anthocyanin exists in a glucoside form, is called anthocyanin, and rarely exists in a free anthocyanin. Anthocyanins are mainly used for coloring food, and can also be used in dye, medicine, and cosmetic.
The anthocyanin molecule has a high molecular conjugation system, contains acidic and basic groups, and is easily dissolved in polar solvents such as water, methanol, ethanol, dilute alkali, dilute acid and the like. The method has certain technical bottlenecks in the aspects of extraction, detection and analysis, the existing extraction method cannot effectively extract anthocyanin in a targeted manner, and the yield and the purity are low. Meanwhile, the traditional extraction method can damage the anthocyanin structure, so that the activity of the anthocyanin is changed. A method for directionally and efficiently obtaining anthocyanin is urgently needed.
Molecular Imprinting Technology (MIT), a Technology for specifically recognizing an imprinted molecule (also called a template molecule) by using a Molecular Imprinting Polymer (MIPs) to mimic an enzyme-substrate or antibody-antigen interaction. Due to the characteristics of the presettability, the identification and the practicability of the technology, the technology is widely applied to many fields (such as chromatographic separation, solid phase extraction, biomimetic sensing, mimic enzyme catalysis, clinical drug analysis and the like). The method mainly adopted by the existing molecular imprinting material is as follows: (1) the imprinting molecules are combined with the functional monomers through covalent bonds or non-covalent bonds to form a host-guest complex; (2) and adding a cross-linking agent and an initiator into the complex, and initiating the polymerization reaction around the imprinted molecule-monomer complex by heat or light. In this process, the polymer chains "trap" the template molecules and monomer complexes into the polymer's stereo-structure by free radical polymerization; (3) and eluting the imprinting molecules in the polymer by a proper method to form binding sites for recognizing the imprinting molecules. The traditional method has multiple steps, the target substance loss is large in the preparation process, and the prepared molecularly imprinted material is generally weak in adsorption capacity to the target substance due to the limitation of heat radiation capacity. For example, the adsorption capacity of the molecular imprinting membrane prepared in the document 'phase transfer method for preparing ursolic acid molecular imprinting membrane' to ursolic acid is only 0.226 μmol/g, and the adsorption capacity is poor (written by Nature science edition, 2010(37), 2: 60-63, Yunzhi, et al, Hunan university). In addition, the molecular imprinting material prepared by the traditional preparation method has larger particle size, and the specific surface area is reduced. For example, the thymopentin molecule magnet prepared in the literature "preparation of thymopentin molecularly imprinted polymer magnetic microsphere and study of adsorption PropertyThe diameter of the sex-imprinted microsphere is about 40 μm (Lu Wan Ru, et al, college of chemical engineering of college 2015(29)), 3: 667-682). Microwave radiation has higher thermal efficiency than the traditional heating mode, and the principle is that the high-frequency changing magnetic field is mainly used for enabling molecules to be rearranged continuously, and the inside generates heat through rotational friction. Research shows that the microwave can realize rapid preparation and improve preparation efficiency. For example, the document "lithium ion battery cathode material LiFePO4The crystal crystallinity of the lithium iron phosphate prepared by microwave in the microwave synthesis and structure characterization is better, the particle size distribution is more uniform, and the crystal grains are more complete (Liyuhua, etc. the molecular science bulletin 2005,21(005): 14-18). Meanwhile, the traditional molecularly imprinted material needs complex steps such as centrifugation and filtration when in use.
Disclosure of Invention
The invention aims to provide a rapid anthocyanin magnetic molecular imprinting preparation method so as to overcome the defects of high cost and the like, which are caused by the fact that the anthocyanin structure is easy to change in anthocyanin extraction, separation and detection in the traditional separation method. Meanwhile, the defect that the synthesis steps in the traditional molecularly imprinted material are complicated is also overcome.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
s1: FeCl is added3And FeSO4Mixing the solutions according to the mol ratio of 2: 1-1: 2, adding a certain amount of ammonia water, stirring, putting into a microwave synthesizer, performing microwave radiation reaction for 10-20 min, wherein the microwave power is 1500-2500 MHz, and the input power is 300-500W. Adsorbing with magnet, separating, and filtering.
S2: and S1, adding tetraethyl orthosilicate solution into the material obtained in the step, wherein the molar ratio is 1: 1-1: 3, adding a proper amount of ammonia water, placing the mixture into a microwave synthesizer, and carrying out microwave radiation reaction for 15-25 min, wherein the microwave power is 1500-2500 MHz, and the input power is 300-500W. Adsorbing with magnet, filtering, and freeze drying.
S3: adding ethylene glycol dimethacrylate, azodiisobutyronitrile and cyanidin into the material obtained in the step S2, wherein the molar ratio is 1:2:1, the solvent is methanol, and the molar ratio of the methanol to the mixture is 2: 1. After mixing, the mixed solution is put into a microwave reactor, reacts for 20-30 min at 2500MHz and 500W, is adsorbed by a magnet, is filtered and is frozen and dried.
S4: placing the dried anthocyanin magnetic molecularly imprinted material into a Soxhlet extractor, performing reflux extraction by using methanol, washing off cyanidin in the material, wherein the extraction finishing standard is that no cyanidin is detected in a reflux liquid.
S5: the obtained anthocyanin magnetic molecularly imprinted material was subjected to particle size measurement using a particle size analyzer. The particle size is 200-300 nm.
S6: adding anthocyanin magnetic molecularly imprinted material into 0.001, 0.003, 0.005, 0.01 and 0.05mg/g cyanidin solution, treating for 10min, and magnetically separating.
S7: further, the material obtained in S5 was put into a soxhlet extractor, and methanol was refluxed and extracted for 10min, and the refluxed solution was concentrated to 1/5 of the original volume, and analyzed by high performance liquid chromatography-mass spectrometry.
S8: further, the material obtained in S5 is added into plant anthocyanin extract, the adding proportion is 50% and 60% of the extract, the processing time is 10min, and the magnetic separation is carried out.
S9: further, the material of S8 is placed into a Soxhlet extractor, methanol is refluxed and extracted for 10min, the reflux liquid is concentrated to 1/5 of the original volume, and high performance liquid chromatography-mass spectrometry is used for analysis.
Compared with the prior art, the invention has the beneficial effects that:
(1) the magnetic molecular imprinting material can more accurately and sensitively capture various anthocyanidins in the anthocyanidin extract, and the use precision reaches 0.003 mg/g.
(2) The material preparation process is simple and easy, the steps are few, the magnetic material and the molecularly imprinted material are coupled, and the anthocyanin magnetic molecularly imprinted material is prepared by microwave radiation, so that the preparation time is saved, and the use of organic reagents is reduced; the reaction time is short and the efficiency is high.
(3) The material of the invention contains magnetic material, can be recovered by the magnetic material and is convenient for the next repeated use.
(4) The material of the invention is not easy to decompose, the particle size of the material is small, the contact area is large, and the preparation process is environment-friendly.
Drawings
FIG. 1 particle size diagram of the material of example 1 of the present invention
FIG. 2 particle size diagram of the material of example 2 of the present invention
FIG. 3 particle size diagram of the material of example 3 of the present invention
FIG. 4 Effect of adsorption of different concentrations of cyanidin by the material of example 1 of the present invention
The specific implementation mode is as follows:
example 1:
FeCl is added3And FeSO4The solution is prepared by mixing the following components in a molar ratio of 2:1, adding a certain amount of ammonia water, stirring, placing into a microwave synthesizer, reacting for 25min at 1500MHz and 300W, adsorbing with a magnet, filtering, and freeze-drying to obtain a black magnetic material. Adding the obtained black magnetic material into tetraethyl orthosilicate solution with the molar ratio of 1:1, adding a proper amount of ammonia water, stirring by using a glass rod, placing into a microwave synthesizer, setting parameters at 1500MHz and 300W, reacting for 30min, cooling, adsorbing by using a magnet, filtering, washing by using ethanol, and freeze-drying. Adding the dried material into a mixed solution of ethylene glycol dimethacrylate, azobisisobutyronitrile and cyanidin at a molar ratio of 1:2:1, and diluting with methanol to 50% of the original volume. Placing the mixed solution into a microwave reactor, setting the parameters at 1500MHz and 300W, reacting for 30min, cooling, adsorbing with a magnet, filtering, washing with ethanol, and freeze-drying.
Placing the dried material into Soxhlet extractor, extracting with methanol under reflux until the reflux liquid contains no cyanidin, and detecting cyanidin by high performance liquid chromatography, as shown in figure 4. The detection conditions are as follows: c18 chromatographic column, mobile phase 80% methanol water, and detector evaporative light detector.
Example 2:
FeCl is added3And FeSO4Mixing the solutions at a molar ratio of 1:1, adding a certain amount of ammonia water, stirring, placing in a microwave synthesizer, reacting at 2000MHz and 400W for 15min, and mixingAdsorbing with magnet, filtering, and freeze drying to obtain black magnetic material. Adding the obtained black magnetic material into tetraethyl orthosilicate solution with the molar ratio of 1:2, adding a proper amount of ammonia water, stirring by using a glass rod, putting into a microwave synthesizer, setting parameters to be 2000MHz and 400W, reacting for 20min, cooling, adsorbing by using a magnet, filtering, washing by using ethanol, and freeze-drying. Adding the dried material into a mixed solution of ethylene glycol dimethacrylate, azobisisobutyronitrile and cyanidin at a molar ratio of 1:2:1, and diluting with methanol to 50% of the original volume. Placing the mixed solution into a microwave reactor, setting the parameters at 2000MHz and 300W, reacting for 25min, cooling, adsorbing with a magnet, filtering, washing with ethanol, and freeze-drying.
Placing the dried material into a Soxhlet extractor, and extracting with methanol under reflux until the reflux liquid does not contain cyanidin, wherein the detection of the cyanidin is carried out by high performance liquid chromatography. The detection conditions are as follows: c18 chromatographic column, mobile phase 80% methanol water, and detector evaporative light detector.
Example 3:
FeCl is added3And FeSO4Mixing the solutions according to a molar ratio of 1:2, adding a certain amount of ammonia water, stirring, placing into a microwave synthesizer, reacting for 10min at 2500MHz and 500W, adsorbing with a magnet, filtering, and freeze-drying to obtain a black magnetic material. Adding the obtained black magnetic material into tetraethyl orthosilicate solution with the molar ratio of 1:3, adding a proper amount of ammonia water, stirring by using a glass rod, placing into a microwave synthesizer with the set parameters of 2500MHz and 500W, reacting for 15min, cooling, adsorbing by using a magnet, filtering, washing by using ethanol, and freeze-drying. Adding the dried material into a mixed solution of ethylene glycol dimethacrylate, azobisisobutyronitrile and cyanidin at a molar ratio of 1:2:1, and diluting with methanol to 50% of the original volume. Placing the mixed solution into a microwave reactor, setting parameters at 2500MHz and 500W, reacting for 20min, cooling, adsorbing with a magnet, filtering, washing with ethanol, and freeze drying.
Placing the dried material into a Soxhlet extractor, and extracting with methanol under reflux until the reflux liquid does not contain cyanidin, wherein the detection of the cyanidin is carried out by high performance liquid chromatography. The detection conditions are as follows: c18 chromatographic column, mobile phase 80% methanol water, and detector evaporative light detector.
Example 4
And (4) evaluating the result:
(1) the prepared anthocyanin magnetic molecularly imprinted material has the particle size
And analyzing the particle size of the prepared material by using a particle size analyzer. The particle sizes of the materials obtained in the three embodiments are mainly distributed between 200 nm and 300nm, and the distribution is good, as shown in fig. 1, fig. 2 and fig. 3. Compared with the traditional method, the particle size is smaller.
TABLE 1 particle size of anthocyanidin magnetic molecularly imprinted material obtained in different examples
| Example 1 | Example 2 | Example 3 | Conventional methods (literature) | |
| Particle size (nm) | 300～250nm | 280～ |
250～220nm | 10000～400000nm |
| Is in percentage by weight | 76.17 | 80.36 | 85.54 |
(2) Anthocyanin recognition and adsorption capacity test
Adding anthocyanin magnetic molecularly imprinted material into 0.001, 0.003, 0.005, 0.01 and 0.05mg/g cyanidin solution, treating for 10min, magnetically separating, placing into a Soxhlet extractor, extracting with methanol under reflux for 10min, concentrating the reflux to 1/5 of the original volume, and analyzing by high performance liquid chromatography-mass spectrometry.
Chromatographic conditions are as follows: 50% methanol-water isocratic elution, C18 column (150 mm. times.4.6 μm).
Mass spectrum conditions: ESI ion source, ion source temperature 600 deg.C, carrier gas is high purity nitrogen gas, collision energy 70ev, and cone hole voltage 4500V.
TABLE 2 adsorption of anthocyanidin species by anthocyanidin magnetic molecularly imprinted material
| Serial number | Name of anthocyanidin | Mass to charge ratio |
| 1 | cyanidin-3-O-galactoside | 449.4 |
| 2 | cyanidin-3-O-glucoside | 449.4 |
| 3 | Cyanidin-3, 5-O-diglucoside | 611.6 |
| 4 | cyanidin-3-O-rutinoside | 595.5 |
| 5 | Paeonine-3-O-glucoside | 463.4 |
| 6 | delphinidin-3-O-galactoside | 465.4 |
Claims (8)
1. A anthocyanin magnetic molecularly imprinted polymer material is characterized in that the magnetic material comprises the following raw materials: ferrous chloride, ferric chloride, tetraethyl orthosilicate, ethylene glycol dimethacrylate, azobisisobutyronitrile, and cyanidin.
2. The anthocyanin magnetic molecularly imprinted material of claim 1, wherein the anthocyanin magnetic molecularly imprinted material has a particle size of 200-300 nm.
3. A preparation method of anthocyanin magnetic molecularly imprinted material comprises the following steps:
step 1: mixing ferrous chloride and ferric chloride according to a molar ratio of 2: 1-1: 2, adding a proper amount of ammonia water, and synthesizing in a microwave reactor by microwave radiation for 10-20 min, wherein the microwave power is 1500-2500 MHz, and the input power is 300-500W; magnet separation, namely continuously carrying out induced synthesis in a microwave reactor for 15-25 min on tetraethyl orthosilicate with a molar ratio of 1:2 in a solid phase, carrying out magnet separation, and washing with absolute ethyl alcohol to obtain a magnetic material;
step 2: adding ethylene glycol dimethacrylate, azodiisobutyronitrile and cyanidin (1:2:1) into the magnetic material obtained in the step (1) according to the molar ratio of 1: 1-3: 1, wherein the microwave radiation synthesis time is 20-30 min, the microwave power is 1500-2500 MHz, and the input power is 300-500W; and (3) separating by using a magnet, refluxing the magnetic material by using methanol until anthocyanin template molecules are not detected, and freeze-drying to obtain the anthocyanin magnetic molecularly imprinted material.
4. The method for preparing the anthocyanin magnetic molecularly imprinted material as claimed in claim 3, wherein the method comprises the following steps: the mol ratio of the ferrous chloride to the ferric chloride is 2:1, the microwave induction synthesis time is 15min, the microwave power is 2000MHz, and the input power is 500W.
5. The method for preparing the anthocyanin magnetic molecularly imprinted material of claim 3, further comprising: in the step 2, the molar ratio of the magnetic material, the ethylene glycol dimethacrylate, the azodiisobutyronitrile and the cyanidin is 1:2:2:1, the microwave induction synthesis time is 25min, the microwave power is 2000MHz, and the input power is 500W.
6. The method for preparing the anthocyanin magnetic molecularly imprinted material of claim 3, further comprising: methanol was used to reflux the magnetic material until no more template molecules were detected in the reflux.
7. The method for preparing the anthocyanin magnetic molecularly imprinted material as claimed in claim 2, wherein methanol is used for reflux extraction, template molecules are washed away until no more template molecules are detected, and the anthocyanin magnetic molecularly imprinted material is dried in vacuum at room temperature.
8. The anthocyanin magnetic molecularly imprinted material of any one of claims 1 to 3, wherein the anthocyanin magnetic molecularly imprinted material is applied to recognition, capture and separation of anthocyanin molecules in plant extracts. The method is characterized in that the minimum adsorption quantity of the anthocyanin magnetic molecularly imprinted material to the anthocyanin is 0.003mg/g, and the adsorption types are 5-6.
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