CN1736580A - Method for preparing built-in nano pore silica absorbent for medicine separation and purification - Google Patents
Method for preparing built-in nano pore silica absorbent for medicine separation and purification Download PDFInfo
- Publication number
- CN1736580A CN1736580A CN 200510014455 CN200510014455A CN1736580A CN 1736580 A CN1736580 A CN 1736580A CN 200510014455 CN200510014455 CN 200510014455 CN 200510014455 A CN200510014455 A CN 200510014455A CN 1736580 A CN1736580 A CN 1736580A
- Authority
- CN
- China
- Prior art keywords
- solution
- xerogel
- compound
- medicine
- tetraethoxysilane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Steroid Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparation of inner- type nano pore silica sorbent used for separating and purifying medicine, belonging to the technique of synthesizing sorbent. The technique contains the following steps: dissolving medicine compound into solvent containing chloroform to prepare a solution, mixing the solution with organosilane with a molar ratio of medicine compound to organosilane, mixing around, and then removing the solvent to prepare predecessor material. Dissolving tetraethoxysilane into ethanol solution, adding the predecessor material, hydrolyzing, and gelling and aging to prepare xerogel. Grinding the xerogel and stripping medicine compound with chloroform- contained eluent to prepare built-in type nano pore silica sorbent. For molecular engram and identification of the material proceed in polar solvent, it can be used to separate and purify water-soluble medicine component. Adsorbance of the sorbent can reach up to 6mg/ g, and the selectivity ratio of absorption can reach up to 80%.
Description
Technical field
The present invention relates to the method that a kind of preparation is used for the internally-arranged type nano-hole silica adsorbent of medicine separation and purification.The technology that belongs to synthetic adsorbent.
Background technology
Along with the development of medicinal career and the enhancing of health of people consciousness, the quality standard of used medical medicine also improves thereupon.Present separating and purifying technology is difficult to the molecular separation that autonomic drug is similar with molecular structure in the synthetic drug, to reach the standard of a class medicine purity.At present, using more widely in industry, isolation and purification method mainly contains solvent extraction, resin adsorption method etc.Solvent extraction technology is fairly simple, but it is big to exist solvent-oil ratio, power consumption, and product impurity is many, shortcomings such as technological process length; The equipment of resin adsorption method is simple, and is easy to operate, with short production cycle, energy-conservation and cost is low etc., but but exists pre-treatment more complicated, single-minded poor selectivity, can only separate a compounds (as flavonoids, polysaccharide etc.), the similar single component of structure can not be separated effectively.No matter adsorption separation technology separates the extraction of medicine, still the Analysis and Identification that is used for traditional Chinese medicine fingerprint all is very effectively and practical, therefore development have efficient, selectivity is strong, stable, energy-conservation with inexpensive new adsorbent is used for directly extracting that to separate the single medicine composition be one of field of medicaments urgent problem.
Last century, the forties proposed the notion of molecular engram, and had synthesized the molecularly imprinted polymer material in the seventies first by Germany scientist Wulff.This technology is comprehensively developed after entering the eighties, is widely used in the fields such as separation, SPE, chemobionics sensor and mimetic enzyme catalysis of analysis, shape selective catalysis, isomers.Therefore, appear as preparation high selectivity, the high-performance adsorbent of molecular imprinting provide brand-new technological means.
At present, although aspect molecular imprinting, obtained significant progress both at home and abroad, but the monomer that is used for material preparation mainly is acrylic acid, methacrylic acid, methyl methacrylate, to Ethenylbenzene formic acid, 1-vinyl imidazole and 4-vinylpridine etc., kind is limited, adding the molecular engram and the identifying of such adsorbent all carries out in organic facies, the molecular engram process at aqueous phase that makes can not realize, thereby make the directly water miscible compound of adsorbing separation of this material; This material also exists bad mechanical strength simultaneously, and adsorption capacity is low, easy-formation not, and shortcomings such as resistance to acids and bases difference are further used it and are subjected to very big restriction.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing internally-arranged type nano-hole silica adsorbent, it is simple, easy to operate that this method has preparation technology.
For achieving the above object, the present invention is realized by following technical proposals.A kind of internally-arranged type nano-hole silica preparation of adsorbent method that is used for the medicine separation and purification is characterized in that comprising following concrete steps:
1, the compound that will have flavonoid glycoside, steroid drugs, anthrol and the anthrone class or a Coumarins of medicinal function is dissolved in and is mixed with the solution that concentration is 5～10mg/ml in oxolane, methyl-sulfoxide, pyridine or the chloroform, then by compound and chloropropyl triethoxysilane or aminopropyl triethoxysilane mol ratio 1～5, it is joined in the above-claimed cpd solution, stir 4～20h down in 70～130 ℃; After reaction finishes, solvent removed with rotary evaporator obtain the compound precursor thing.
2, tetraethoxysilane is dissolved in to be mixed with volumetric concentration in 20%～70% ethanolic solution be 40～80% solution, and be 0.2～1 to join in the tetraethoxysilane ethanolic solution according to predecessor and tetraethoxysilane volume ratio, stir 2～10h down at 40～60 ℃, carry out the synergetic hydrolysis of silane.
3, with the colloidal sol behind the above-mentioned synergetic hydrolysis, being placed on temperature is gel under 30～50 ℃ of conditions, treats to place 80～120 ℃ to wear out gel after whole gels, till jel product quality constant weight.
4, the xerogel grinding is screened into 40～100 orders, with 40%～70% ethanolic solution, oxolane, methyl-sulfoxide or chloroform as eluent, stir 5～24h down at 70～130 ℃, medicinal compound wash-out from xerogel is removed, make internally-arranged type nano-pore sorbing material.
The invention has the advantages that the employing molecular imprinting, make and have and corresponding, the orderly internally-arranged type nano-pore of compound space structure sorbing material.The organo-functional group of inner assembling can form ionic bond or covalent bond with the phenolic hydroxyl group or the carboxyl effect of medicinal compound molecule in the hole, and the discrimination bit of functional group is complementary with the compound space conformation on spatial distribution.The molecular engram that material carries out carries out with being identified in the polar solvent, can be used for water soluble drug component separation purifying.This siliceous sorbing material has nano grade pore, porosity is bigger, adsorbance height, stronger stability and resistance to acids and bases, advantage such as preparation technology is simple, easy to operate.
The specific embodiment
Embodiment one: the flavonoids medicine rutin of 100mg is dissolved in the 10ml pyridine, the chloropropyl triethoxysilane of 7ml is added above-mentioned pyridine solution, at 80 ℃ of following condensing refluxes, stir 4h; After reaction finishes, pyridine removed with rotary evaporator make rutin compound precursor thing.The tetraethoxysilane of 15ml is dissolved in 50% ethanolic solution, and adds the rutin compound precursor thing of above-mentioned preparation, carry out synergetic hydrolysis at 40 ℃ of following stirring 8h and prepare Ludox.Ludox is a gel under 40 ℃ of conditions in temperature, wears out down in 100 ℃, makes the siliceous xerogel that inside is inlaid with rutin.Xerogel is ground into 80 purpose fine particles, and at 80 ℃ of following condensing refluxes, stirring 6h removes rutin wash-out from xerogel with 50% ethanolic solution, makes rutin is had single-minded optionally internally-arranged type nano-pore sorbing material.Sorbing material carries out saturated absorption to the rutin simulated solution of 0.5mol/mL, and maximal absorptive capacity is 6.4mg/g, and reaching the adsorption equilibrium time is 3h, is 85.5% to the selection rate of rutin.
Embodiment two: the archen of 50mg is dissolved in the 6ml oxolane, the aminopropyl triethoxysilane of 10ml is joined above-mentioned tetrahydrofuran solution, at 70 ℃ of following condensing refluxes, stir 5h; After reaction finishes, oxolane sent out to remove with the rotation steaming device make archen compound precursor thing.The tetraethoxysilane of 20ml is dissolved in 60% ethanolic solution, and adds the archen compound precursor thing of above-mentioned preparation, carry out synergetic hydrolysis at 60 ℃ of following stirring 4h and prepare Ludox.Ludox is a gel under 50 ℃ of conditions in temperature, wears out down in 110 ℃, makes the siliceous xerogel that inside is inlaid with archen.It is 100 purpose fine particles that xerogel is ground, and at 70 ℃ of following condensing refluxes, stirs 7h with dimethyl sulfoxide solution, and archen wash-out from xerogel is removed, and makes archen is had single-minded optionally internally-arranged type nano-pore suction material.Sorbing material carries out saturated absorption to the archen simulated solution of 0.5mol/mL, and maximal absorptive capacity is 7.1mg/g, and reaching the adsorption equilibrium time is 4h, is 79% to the selection rate of archen.
Embodiment three: the betamethasone of 80mg is dissolved in the 15ml methyl-sulfoxide, the chloropropyl triethoxysilane of 15ml is joined above-mentioned dimethyl sulfoxide solution, at 110 ℃ of following condensing refluxes, stir 16h; After reaction finishes, methyl-sulfoxide removed with rotary evaporator make betamethasone compound precursor thing.The tetraethoxysilane of 10ml is dissolved in 55% ethanolic solution, and adds the betamethasone compound precursor thing of above-mentioned preparation, carry out synergetic hydrolysis at 50 ℃ of following stirring 6h and prepare Ludox.Ludox is being gel under 40 ℃ of conditions, wears out down in 100 ℃, makes the siliceous xerogel that inside is inlaid with betamethasone.It is 60 purpose fine particles that xerogel is ground, and at 110 ℃ of following condensing refluxes, stirs 20h with dimethyl sulfoxide solution, and betamethasone wash-out from xerogel is removed, and makes betamethasone is had single-minded optionally internally-arranged type nano-pore sorbing material.Sorbing material carries out saturated absorption to the betamethasone simulated solution of 1mol/mL, and maximal absorptive capacity is 7.5mg/g, and reaching the adsorption equilibrium time is 6h, is 81.1% to the selection rate of betamethasone.
Claims (1)
1. internally-arranged type nano-hole silica preparation of adsorbent method that is used for the medicine separation and purification is characterized in that comprising following concrete steps:
(1) will have flavonoid glycoside, steroid drugs, anthrol and the anthrone class of medicinal function or coumarin kind compound is dissolved in oxolane, methyl-sulfoxide, pyridine or chloroform and is mixed with the solution that concentration is 5～10mg/ml, then by compound and chloropropyl triethoxysilane or aminopropyl triethoxysilane mol ratio 1～5, silane is joined in the above-claimed cpd solution, stir 4～20h down in 70～130 ℃; After reaction finishes, solvent removed with rotary evaporator obtain the compound precursor thing;
(2) tetraethoxysilane is dissolved in to be mixed with volumetric concentration in 20%～70% ethanolic solution be 40～80% solution, and according to being 0.2～1 predecessor to be joined in the tetraethoxysilane ethanolic solution with the tetraethoxysilane volume ratio, stir 2～10h down at 40～60 ℃, carry out the synergetic hydrolysis of silane;
(3) with the colloidal sol behind the above-mentioned synergetic hydrolysis, being placed on temperature is gel under 30～50 ℃ of conditions, treats to place 80～120 ℃ to wear out down gel after whole gels, to jel product quality constant weight;
(4) xerogel is ground into 40～100 orders, with 40%～70% ethanolic solution, oxolane, methyl-sulfoxide or chloroform as eluent, stir 5～24h down at 70～130 ℃, medicinal compound wash-out from xerogel is removed, make internally-arranged type nano-pore sorbing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510014455XA CN100335163C (en) | 2005-07-11 | 2005-07-11 | Method for preparing built-in nano pore silica absorbent for medicine separation and purification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510014455XA CN100335163C (en) | 2005-07-11 | 2005-07-11 | Method for preparing built-in nano pore silica absorbent for medicine separation and purification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1736580A true CN1736580A (en) | 2006-02-22 |
| CN100335163C CN100335163C (en) | 2007-09-05 |
Family
ID=36079649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510014455XA Expired - Fee Related CN100335163C (en) | 2005-07-11 | 2005-07-11 | Method for preparing built-in nano pore silica absorbent for medicine separation and purification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100335163C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358616C (en) * | 2006-05-30 | 2008-01-02 | 天津大学 | Process for preparing silicon separating films with specialized selectivity to natural products |
| 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 |
| CN104340984A (en) * | 2013-12-10 | 2015-02-11 | 沈阳药科大学 | Preparation method and application of nanopore silicon dioxide xerogel |
| CN104587968A (en) * | 2015-01-12 | 2015-05-06 | 南京工业大学 | Organic-inorganic hybridization light response adsorbent, preparation method and application of organic-inorganic hybridization light response adsorbent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6310110B1 (en) * | 1999-07-30 | 2001-10-30 | Michael A. Markowitz | Molecularly-imprinted material made by template-directed synthesis |
| CN1340552A (en) * | 2000-08-30 | 2002-03-20 | 中国科学院大连化学物理研究所 | Process for preparing chiral separation fixed phase of molecular brand polymer |
| US6709597B1 (en) * | 2002-11-29 | 2004-03-23 | Council Of Scientific And Industrial Research | Process for the separation of racemic mixtures |
-
2005
- 2005-07-11 CN CNB200510014455XA patent/CN100335163C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358616C (en) * | 2006-05-30 | 2008-01-02 | 天津大学 | Process for preparing silicon separating films with specialized selectivity to natural products |
| 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 |
| CN104340984A (en) * | 2013-12-10 | 2015-02-11 | 沈阳药科大学 | Preparation method and application of nanopore silicon dioxide xerogel |
| CN104587968A (en) * | 2015-01-12 | 2015-05-06 | 南京工业大学 | Organic-inorganic hybridization light response adsorbent, preparation method and application of organic-inorganic hybridization light response adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100335163C (en) | 2007-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Adsorption of alkaloids on ordered mesoporous carbon | |
| CN100335163C (en) | Method for preparing built-in nano pore silica absorbent for medicine separation and purification | |
| Li et al. | Hypercrosslinked poly (styrene-co-divinylbenzene) resin as a specific polymeric adsorbent for purification of berberine hydrochloride from aqueous solutions | |
| CN106040182A (en) | Method for preparing carbon foam adsorbents modified by phenylboronic acid type metal organic framework materials | |
| Liu et al. | Boric acid modified macroporous adsorption resin and its adsorption properties for catechol compounds | |
| Wang et al. | Zirconium metal-organic framework assisted miniaturized solid phase extraction of phenylurea herbicides in natural products by ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry | |
| CN101864021A (en) | Preparation method of nanometer silicon gel surface gastrodin molecular engram polymers | |
| Geng et al. | High selective purification of flavonoids from natural plants based on polymeric adsorbent with hydrogen-bonding interaction | |
| CN104418761A (en) | Method for separating kukoamine | |
| CN103992321A (en) | Preparation method of theophylline | |
| CN1919843A (en) | Preparation method of siliceous inorganic flavonoid molecular engram microsphere | |
| CN104829666A (en) | Method for preparing high purity baicalin from radix scutellariae | |
| CN101619062B (en) | Natural fibrauretine crystal and macroporous adsorbent resin preparation method thereof | |
| CN102060693B (en) | Method for enriching and purifying ferulic acid in cimicifugae foetidae | |
| CN1171857C (en) | Process for enriching and purifying capsaicin with macroporous adsorption resin | |
| CN102093328A (en) | Method for enriching and purifying procyanidin in pine bark | |
| CN102078357A (en) | Preparation method of Gynura bicolor total flavone extract | |
| CN102093345B (en) | Method for separating out dehydrogenized turkey corn by applying silicagel column chromatography | |
| CN103254226B (en) | A kind of method of ADSORPTION IN A FIXED BED method separation and purification Yelkin TTS | |
| CN103304562A (en) | Phellodendrine monomer and preparation method of salt thereof | |
| CN101831076A (en) | Silica gel particle surface artemisinin molecularly imprinted polymer and preparation and application method thereof | |
| CN106117191B (en) | A method of efficiently separating puerarin purification | |
| CN102491946A (en) | Method for separating and purifying huperzine by molecular imprinting technology | |
| CN111072851B (en) | Preparation method of hydroxyl iron surface initiated boron affinity imprinted polymer and application of hydroxyl iron surface initiated boron affinity imprinted polymer in extraction of shikimic acid | |
| CN102641347A (en) | Red paeony root extract, as well as preparation and application methods thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |