CN1919843A - Preparation method of siliceous inorganic flavonoid molecular engram microsphere - Google Patents
Preparation method of siliceous inorganic flavonoid molecular engram microsphere Download PDFInfo
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- CN1919843A CN1919843A CN 200610015699 CN200610015699A CN1919843A CN 1919843 A CN1919843 A CN 1919843A CN 200610015699 CN200610015699 CN 200610015699 CN 200610015699 A CN200610015699 A CN 200610015699A CN 1919843 A CN1919843 A CN 1919843A
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Abstract
The invention discloses a preparing method of silicon inorganic flavone molecular imprinting microballoon in the separating purifying domain, which comprises the following steps: blending certain density mold agent solution and functional monomer according to rate; adding and refluxing to obtain former solution; blending ethyl silicate, alcohol, water and face activator evenly; adding ammonia to do catalytic reaction; adding former solution after reacting for a certain time; hydrolyzing for certain time continuously; filtering the hydrolytic product; drying in the sorbitic extractor; extracting through alcohol for a long time; drying again to obtain the product.
Description
Technical field
The present invention relates to a kind of preparation method who natural product flavonoid molecule is had the siliceous inorganic molecular engram microsphere of single-minded selection adsorptivity.The technology of preparing that belongs to the material of separating and purifying flavone class material.
Background technology
Flavonoid compound is the class natural product that occurring in nature extensively exists, and has document to estimate to have approximately in 20% the herbal medicine and contains flavonoid compound, and as seen its resource is abundant.There is research to show that flavonoid compound has multiple biological activity, the effects such as it is antibiotic except that utilizing, anti-inflammatory, anti-mutation, step-down, clearing heat and detoxicating, calm, diuresis, in anti-oxidant, anticancer, anti-cancer, suppress aspect such as lipase unusual effect is also arranged.Because these biological activitys of flavonoid compound make its research enter a new stage, started flavonoid compound research, development and use upsurge, impel it in industry such as makeup, medicine, food, to be widely used.The main traditional separation purification method of flavonoid compound has at present: separation such as organic solvent extraction, absorption method separation, supercritical extraction, capillary electrophoresis.Many natural products can adopt adsorption method of separation to separate, and often use sorbent materials such as silica gel, macroporous resin, separate in this way, and are simple to operation, and treatment capacity is big, but separating effect is relatively poor, and it is not high to obtain sample purity.Supercritical extraction is an isolation technique commonly used in recent years, has been used for the separation of materials such as flavones.Supercritical extraction has solvent-free remaining, can keep the advantages such as stability of product, but needs complex apparatus, and to working pressure and temperature requirement strictness, trace utilization cost is higher, and products obtained therefrom purity is also lower simultaneously.Some other method, though as resolving power height such as capillary electrophoresis, reverse-phase chromatographies, can only be used for the analysis of natural product, treatment capacity is few, is difficult to use in preparation in enormous quantities.
Molecular imprinting is the technology of the preparation high-selectivity adsorbing material that grows up over nearly 20 years, and it has imitated the action principle of the key and the lock of organic sphere, treats separated portion and can carry out selective separation from the molecule rank.But at present used function monomer of molecular imprinting and linking agent majority are organic compound such as acrylate, chitosan, Mierocrystalline cellulose etc., and the material that is prepared into also mostly is organic materials, and the preparation process complexity of organic materials meets the easy swelling of machine solvent.Also the someone passes through colloidal sol～gel method and has prepared silicon-dioxide inorganic molecule imprinted polymer at present, this stability of material is good, the selection adsorptive capacity is big, but because its out-of-shape, easily produce fragment in the adsorption process, if be used for chromatogram or separating column packing causes post to press problems such as unstable, that the moving phase flow distribution is inhomogeneous easily; Because specific surface area is less relatively, the size of loading capacity also is restricted simultaneously.
Summary of the invention
The objective of the invention is to be to provide a kind of preparation method of siliceous inorganic flavonoid molecular engram microsphere, specific natural product flavonoid molecule is had the high efficiency selected adsorptivity with the prepared trace microballoon of this method.
The present invention is realized by following technical proposals.A kind of preparation method of siliceous inorganic flavonoid molecular engram microsphere is characterized in that comprising following process:
1. the preparation of precursor: luteolin, puerarin or the agent of catechin natural flavonoid molecular template be dissolved in to be made into mass concentration in mass concentration 98% ethanol be 0.04%～0.2% solution, in solution, by the ratio of the amount of hydroxylated material in function monomer γ-An Bingjisanyiyangjiguiwan and the template is to add γ-An Bingjisanyiyangjiguiwan in 4: 1～10: 1,60～80 ℃ of reflux 8～12 hours, obtain precursor solution after the reaction.
2. the preparation of molecular engram microsphere: the volume with γ-An Bingjisanyiyangjiguiwan used in the step 1 is as the criterion, under 60～80 ℃ of water bath condition, being 1 by volume between γ-An Bingjisanyiyangjiguiwan, tetraethoxy, 98% ethanol, deionized water and the tensio-active agent: (2～5): (10～20): (10～30): (0.5～2), tetraethoxy, ethanol, deionized water and surfactant mixing and stirring are got emulsion, and adding ammoniacal liquor adjusting emulsion to pH value is 10 catalyzed reactions; Reaction carries out after 0.5～2 hour adding the precursor solution that makes in the step 1 reaction that is hydrolyzed, react 5～9 hours, the hydrolysate filtration, filter cake is put into 60～85 ℃ of dry products that get of baking oven.
3. the removal of template and surfactant: step 2 product is added in the apparatus,Soxhlet's, after extracting 8～12 hours with mass concentration 85%～98% alcohol heating reflux, again product is put into 75～85 ℃ of dryings of baking oven, obtained the siliceous inorganic molecular engram microsphere of several microns to tens microns of particle diameters.
The invention has the advantages that preparation process is simple, prepared siliceous inorganic molecular engram microsphere physical strength height, good physical and chemical properties, anti-swelling, Static Adsorption partition ratio to target flavonoid molecule under 20～75 ℃ of temperature reaches 100～250, on the molecule rank, realize selective adsorption, even in strong polar water～alcohol mixeding liquid, target molecule is still had good selection fractionation by adsorption ability to the target substance molecule.
Embodiment
Embodiment one: under 70 ℃ of water bath condition, the luteolin of 0.03g is joined in the there-necked flask of 250mL, use the 50mL dissolve with ethanol; Then the 3mL aminopropyl triethoxysilane is joined in the flask, back flow reaction gets solution a after 8 hours; Under 70 ℃ of water bath condition, with 9mL tetraethoxy, 50mL98% ethanol, 50mL deionized water and class of 2mL department 20 mixing and stirring, and add ammoniacal liquor adjusting pH value to 10 catalyzed reactions equally, reaction is carried out adding solution a after 1 hour, continues reaction 5 hours; With hydrolysate filter paper suction filtration, filter cake was put into 85 ℃ of dryings of baking oven 48 hours, get the 3g product; The 3g product is added in the apparatus,Soxhlet's, extracted 10 hours with the 300mL98% alcohol heating reflux, to remove tensio-active agent and template; At last, product is promptly got siliceous molecular engram microsphere after 85 ℃ of dryings.
Carry out adsorption experiment with the microballoon that makes, experimentation is: accurately the luteolin ethanolic soln of the 0.5mg/mL of preparation and microballoon that 1g makes with aforesaid method are put into Erlenmeyer flask and are sealed with preservative film with 30mL, under 25 ℃, vibrated 0～8 hour at shaking table, afterwards with solution centrifugal, get the membrane filtration of supernatant liquor with 0.45 μ m, and detect strength of solution with HPLC, calculate before and after the absorption loading capacity that luteolin loss in the solution obtains this microballoon.The result shows that this trace microballoon was only had an appointment 60 minutes to the luteolin adsorption equilibrium time, Static Adsorption partition ratio (K
D=substrate is in the concentration of the concentration/substrate on the polymkeric substance in solution) reach 152.25; And experiment as a comparison, under similarity condition, this trace microballoon is joined in the solution of same concentration of puerarin of structural similitude and carry out Static Adsorption, the Static Adsorption that obtains distributes adsorption index then only to have 32.49, and separation factor (α=template partition ratio/comparison partition ratio) has obtained 4.69.
Embodiment two: under 70 ℃ of water bath condition, the puerarin of 0.05g is joined in the there-necked flask of 250mL, use the 50mL dissolve with ethanol; Then the 3mL aminopropyl triethoxysilane is joined in the flask, back flow reaction gets solution a after 8 hours; Under 70 ℃ of water bath condition,, add ammoniacal liquor and regulate pH value to 10 catalyzed reaction equally 9mL tetraethoxy, 50mL98% ethanol, 50mL water and class of 2mL department 20 mixing and stirring; Reaction is carried out adding solution a after 1 hour, continues reaction and stops after 5 hours; With hydrolysate filter paper suction filtration, put into 85 ℃ of dryings of baking oven 48 hours, get the 3g molecular engram microsphere; Get the dried material of 3g then and pack in the apparatus,Soxhlet's, extracted 10 hours with the 300mL98% alcohol heating reflux, to remove tensio-active agent and template.At last, product is promptly got siliceous molecular engram microsphere.The result who carries out adsorption experiment with this material shows, this trace microballoon has the adsorption equilibrium time to template molecule (puerarin) only had an appointment 80 minutes, and the Static Adsorption partition ratio reaches 115.68; And experiment as a comparison, under similarity condition, this trace microballoon distributes adsorption index that 41.96mg/g is then only arranged to the Static Adsorption of the luteolin of structural similitude, and separation factor has reached 2.76.
Embodiment three: under 70 ℃ of water bath condition, the catechin of 0.03g is joined in the there-necked flask of 250mL, use the 50mL dissolve with ethanol; Then the 3mL aminopropyl triethoxysilane is joined in the flask, back flow reaction gets solution a after 8 hours; Under 70 ℃ of water bath condition,, add ammoniacal liquor and regulate pH value to 10 catalyzed reaction equally 9mL tetraethoxy, 50mL98% ethanol, 50mL water and class of 2mL department 20 mixing and stirring; Reaction is carried out adding solution a after 1 hour, continues reaction and stops in 5 hours.With hydrolysate filter paper suction filtration, put into 85 ℃ of dryings of baking oven 48 hours, the 3g product, this 3g product is packed in the apparatus,Soxhlet's, extracted 10 hours with the 300mL alcohol heating reflux, to remove tensio-active agent and template.At last, siliceous molecular engram microsphere will promptly be got after the product.The result who carries out adsorption experiment identical among the embodiment one with this trace shows, this trace microballoon can reach adsorption equilibrium in 45 minutes to template molecule (catechin), the Static Adsorption partition ratio reaches 186.37mg/g, and experiment as a comparison, this trace microballoon distributes adsorption index then only to have 39.29 to the Static Adsorption of the puerarin of structural similitude, and separation factor has reached 4.74.
Claims (1)
1. the preparation method of a siliceous inorganic flavonoid molecular engram microsphere is characterized in that comprising following process:
1). the preparation of precursor: luteolin, puerarin or the agent of catechin natural flavonoid molecular template be dissolved in to be made into mass concentration in mass concentration 98% ethanol be 0.04%～0.2% solution, in solution, by the ratio of the amount of hydroxylated material in function monomer γ-An Bingjisanyiyangjiguiwan and the template is to add γ-An Bingjisanyiyangjiguiwan in 4: 1～10: 1,60～80 ℃ of reflux 8～12 hours, obtain precursor solution after the reaction;
2). the preparation of molecular engram microsphere: the volume with γ-An Bingjisanyiyangjiguiwan used in the step 1) is as the criterion, under 60～80 ℃ of water bath condition, being 1 by volume between γ-An Bingjisanyiyangjiguiwan, tetraethoxy, 98% ethanol, deionized water and the tensio-active agent: (2～5): (10～20): (10～30): (0.5～2), tetraethoxy, ethanol, deionized water and surfactant mixing and stirring are got emulsion, and adding ammoniacal liquor adjusting emulsion to pH value is 10 catalyzed reactions; Reaction carries out after 0.5～2 hour adding the precursor solution that makes in the step 1) reaction that is hydrolyzed, react 5～9 hours, the hydrolysate filtration, filter cake is put into 60～85 ℃ of dry products that get of baking oven;
3). the removal of template and surfactant: with step 2) product adds in the apparatus,Soxhlet's, after extracting 8～12 hours with mass concentration 85%～98% alcohol heating reflux, again product is put into 75～85 ℃ of dryings of baking oven, obtained the siliceous inorganic molecular engram microsphere of several microns to tens microns of particle diameters.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831076A (en) * | 2010-04-23 | 2010-09-15 | 华东理工大学 | Silica gel particle surface artemisinin molecularly imprinted polymer and preparation and application method thereof |
| CN101914189A (en) * | 2010-08-04 | 2010-12-15 | 上海交通大学 | Preparation method and application of molecular imprinted polymer on silica surface for specifically adsorbing patulin |
| CN101091911B (en) * | 2007-04-16 | 2010-12-15 | 天津科技大学 | Method for synthesizing adsorption functional material for number one Sudan red |
| CN101712669B (en) * | 2009-02-13 | 2012-01-18 | 河北理工大学 | Method for separating and purifying luteolin |
| CN102463102A (en) * | 2010-11-16 | 2012-05-23 | 中国科学院成都生物研究所 | Surface-bonded baicalin magnetic nano-particle, and preparation method and application thereof |
| CN103319743A (en) * | 2013-06-03 | 2013-09-25 | 江南大学 | Molecularly imprinted polymer template molecule elution method |
| CN104945655A (en) * | 2015-03-31 | 2015-09-30 | 南京大学 | Synthesis method and application of molecularly imprinted mesoporous material |
| CN107400240A (en) * | 2017-07-06 | 2017-11-28 | 南京师范大学 | A kind of solid phase extraction concentration material for bisphenol-A detection and its preparation method and application |
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2006
- 2006-09-19 CN CN 200610015699 patent/CN1919843A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091911B (en) * | 2007-04-16 | 2010-12-15 | 天津科技大学 | Method for synthesizing adsorption functional material for number one Sudan red |
| CN101712669B (en) * | 2009-02-13 | 2012-01-18 | 河北理工大学 | Method for separating and purifying luteolin |
| CN101831076A (en) * | 2010-04-23 | 2010-09-15 | 华东理工大学 | Silica gel particle surface artemisinin molecularly imprinted polymer and preparation and application method thereof |
| CN101914189A (en) * | 2010-08-04 | 2010-12-15 | 上海交通大学 | Preparation method and application of molecular imprinted polymer on silica surface for specifically adsorbing patulin |
| CN102463102A (en) * | 2010-11-16 | 2012-05-23 | 中国科学院成都生物研究所 | Surface-bonded baicalin magnetic nano-particle, and preparation method and application thereof |
| CN103319743A (en) * | 2013-06-03 | 2013-09-25 | 江南大学 | Molecularly imprinted polymer template molecule elution method |
| CN104945655A (en) * | 2015-03-31 | 2015-09-30 | 南京大学 | Synthesis method and application of molecularly imprinted mesoporous material |
| CN107400240A (en) * | 2017-07-06 | 2017-11-28 | 南京师范大学 | A kind of solid phase extraction concentration material for bisphenol-A detection and its preparation method and application |
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