CN104548972B - A kind of preparation method of pharmaceutical bilobalide molecular engram polysulfones hybridized film - Google Patents

A kind of preparation method of pharmaceutical bilobalide molecular engram polysulfones hybridized film Download PDF

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CN104548972B
CN104548972B CN201410617850.6A CN201410617850A CN104548972B CN 104548972 B CN104548972 B CN 104548972B CN 201410617850 A CN201410617850 A CN 201410617850A CN 104548972 B CN104548972 B CN 104548972B
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bilobalide
molecular engram
film
polysulfones
benzoyl peroxide
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CN104548972A (en
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华文蔚
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Abstract

The invention discloses the preparation method of a kind of pharmaceutical bilobalide molecular engram polysulfones hybridized film, comprise the steps: (1), the polysulfone membrane prepared is contacted with the solution containing benzoyl peroxide, then dry, it is thus achieved that film surface-coated has the polysulfone membrane of initiator;(2) molecular engram coating liquid, is prepared: by bilobalide dissolution of crystals in organic solvent;It is subsequently adding polymer monomer, and cross-linking agent;(3), by step 2) the molecular engram coating liquid coating for preparing contains on the surface of benzoyl peroxide to polysulfone membrane, temperature 40 60 DEG C is reacted 30 60 minutes, it is then added to freezing film in the deionized water of 25 DEG C, by the glycerine water solution immersion treatment 10~20h that mass concentration is 20~50%, last again with methanol is soaked 24 hours, thoroughly remove bilobalide crystal, then clean with deionized water, obtain described bilobalide molecular engram polysulfones hybridized film.

Description

A kind of preparation method of pharmaceutical bilobalide molecular engram polysulfones hybridized film
Technical field
The present invention relates to the preparation method of a kind of bilobalide molecular engram polysulfones hybridized film.
Background technology
Lactone compound is widely present in plant kingdom, is one of important active ingredient of natural product, anti- The aspect such as viral, anticancer has significant effect, is widely used to clinic.Effective ingredient ratio in plant More complicated, at present the isolation and purification method that flavone compound is main there are macroreticular resin absorbing method, supercritical Fluid extraction etc., but these technology exist and the compound that structure is similar can not be carried out clean cut separation and set Standby investment is bigger waits deficiency.Membrane separation technique is the isolation technics that twentieth century is emerging, have energy-conservation, efficient, Can the feature such as seriality operation, be applied in the separation of lactone compound, purification research achieve preferably Progress.But the selectivity of membrance separation is carried out by molecular cut off at present, and lactone compound kind Many, molecular weight is close, and structure is similar, it is difficult to realize the high Selective Separation to single flavone compound Purification.
Molecular imprinting (Molecular Imprinting Technique) is to utilize molecularly imprinted polymer " memory " function with microsphere stereochemical structure and shape carries out a kind of technology of specific molecular identification, Therefore there is precordainment and identity, delivered relevant on " Nature " from Mosbach in 1993 etc. Can separate theophylline molecularly imprinted polymer report since, developed rapidly, become chemistry, biology, The crossing domain of the subject such as macromolecular material, medical science, at chromatographic stationary phases, Solid-Phase Extraction, membrance separation, exempts from The aspects such as epidemic disease analysis, antibodies mimic, imitative biosensor, catalyst and synzyme show good application Prospect.
Molecular engram film is a kind of new technique grown up on the basis of molecular imprinting, with dividing Sub-trace and the two-fold advantage of membrane technology.The basic ideas of molecular engram film preparation are to introduce in polymerisation medium Microsphere, removes microsphere after film forming, forms the network structure adapted with template molecule in film, And it is inlaid with the functional group interacted with template molecule, when separating the mixture containing template molecule, Template molecule can be gone out and efficiently separates out by Selective recognition.The preparation method of molecular engram film mainly has former Position polymerization, phase inversion, surface modification, electrochemical process etc..Situ aggregation method and phase inversion are molecules The preparation method of trace integral membrane.Situ aggregation method is that the polyreaction by free radical prepares molecular engram film, Gained membrane porosity is low, and flux is little.Phase inversion is without radical polymerization, and preparation process is simple, is current One of preparation method of more research.The trace point position that it is critical only that on control film that phase inversion prepares film is same Time create the film with good pore morphology, improve the transmission characteristic of film while optimizing molecular recognition performance. The molecular engram film prepared by phase inversion has good separating property in aqueous phase.But, although Phase inversion is very suitable for the preparation of molecular engram film, but owing to the optimum condition of imprinted sites formation may It not the formation condition of optimized membrane pore structure, so molecular engram film preparation process is subject to certain restrictions. It addition, the imprinted sites of molecular engram film is randomly dispersed in inside and the surface of polymer phase, seriality duct Formation there be difficulties involved when the separating property of film is all had a certain impact, make the separating property of film reduce, Property high Selective Separation effectively continuous to target molecule there be difficulties involved when.
Membrane science has become an independent science.The most most widely used is polymeric membrane for separation, belongs to high score The one of subfunction film.Separate film and effectively promote development and the raising of isolation technics.Its work of separation now Can from initial microporous filter separation solidliquid mixture develop into molecular level mixture separation, saltout, electricity The separation solving matter separates with transmission, gas and enrichment etc..Separate at present film biological engineering, desalinization, In medicament slow release, controlled release and chemical process, the field such as the separation of mixture and steam has reached practical. Separate film and there is the features such as energy-conservation, efficient, environmentally friendly.
In vegetable Chinese herbal medicine, extracting and developing active component is one of content of the modernization of Chinese medicine.The side extracted Fado is traditional solvent extraction, or organic solvent, or water, or mixed solvent, or super faces Boundary fluid CO2 etc..But no matter using which kind of solvent, that extracts isolated is crude extract, and its purification is many Use recrystallization.
Solution crystallization is the traditional method of material purifies and separates, is also an important chemical process.Solute from Solution crystallizes out and to experience two steps: nucleus generates and crystal growth.It is in supersaturation that nucleus generates Solution generates a number of nucleus;And on the basis of nucleus, grow into crystal, then it is crystal growth. The factor affecting whole crystallization process is a lot, such as the degree of supersaturation of solution, the existence of impurity, the speed of stirring And various physical fields etc..In industrial crystallization, pursue high crystal growth rate to improve equipment Production capacity, but actually rate of crystalline growth generally limiting by problems such as required specific product quality System, does not allow to use raising degree of supersaturation to improve growth rate, will seek under suitable degree of supersaturation Additive method is pushed to crystal growing process.The impact on crystallization kinetics of the such as sound field, Zhang Ximei etc. was once Have studied the sound field impact on solution nucleation, stability of solution and crystal growth system, and further investigated its Influencing Mechanism (Zhang Ximei, Qiu Taiqiu, Li Yuehua. the research [J] that solution crystallization kinetics is affected by sound field. Chemistry circular, 1997,1:44~46);The magnetic field impact on crystallization, bavin really respects to wait the most also to be had together Sample finds, and utilizes the action of a magnetic field, controls crystal growth, make crystal particle size reduction (Chai Chengjing. magnetization skill Art application in chemical separating field. chemical industry and engineering, 1999, (16) 4:245~249);Its His outfield facilitation to crystallizing also is effective.
Along with industrial expansion, efficient Crystallization Separation technology are at oil, chemical industry, biotechnology and ring The application in the fields such as border protection is more and more extensive, and the research of industrial crystallization technology and correlation theory is also pushed to newly Stage, domestic and international novel crystallization technology achieves greater advance, and wherein crystalization in supercritical fluid is a kind of new The method for crystallising of type.
Summary of the invention
It is an object of the invention to propose the preparation method of a kind of bilobalide molecular engram polysulfones hybridized film.
For reaching this purpose, the present invention by the following technical solutions:
The preparation method of a kind of bilobalide molecular engram polysulfones hybridized film, comprises the steps: (1), will make The polysulfone membrane got ready contacts with the solution containing benzoyl peroxide, then dries, it is thus achieved that film surface-coated has draws Send out the polysulfone membrane of agent;The mass percentage content of benzoyl peroxide is 0.05~1%;
(2) molecular engram coating liquid, is prepared: by bilobalide dissolution of crystals in organic solvent;Then add Enter polymer monomer, and cross-linking agent;Described bilobalide with the mass ratio of polymer monomer and cross-linking agent is: 1:1-3:2-8;Described organic solvent is N,N-dimethylacetamide or dimethylformamide or N-methyl -2-Pyrrolidone, solution temperature is 45~65 DEG C, carries out ultrasonic disperse simultaneously;Described polymer monomer For acrylamide;Described cross-linking agent is selected from ethylene glycol dimethacrylate or tetramethylene dimethyl allene Acid esters;
(3), by step 2) the molecular engram coating liquid coating for preparing contains benzoyl peroxidating to polysulfone membrane On the surface of thing, react 30-60 minute in temperature 40-60 DEG C, be then added in the deionized water of 25 DEG C Freezing film, by the glycerine water solution immersion treatment 10~20h that mass concentration is 20~50%, uses the most again Methanol soaks 24 hours, thoroughly removes bilobalide crystal, then cleans with deionized water, obtains described Semen Ginkgo Lactone molecule trace polysulfones hybridized film.
Detailed description of the invention
Embodiment 1
The preparation method of a kind of bilobalide molecular engram polysulfones hybridized film, comprises the steps: (1), will make The polysulfone membrane got ready contacts with the solution containing benzoyl peroxide, then dries, it is thus achieved that film surface-coated has draws Send out the polysulfone membrane of agent;The mass percentage content of benzoyl peroxide is 1%;
(2) molecular engram coating liquid, is prepared: by bilobalide dissolution of crystals in organic solvent;Then add Enter polymer monomer, and cross-linking agent;Described bilobalide with the mass ratio of polymer monomer and cross-linking agent is: 1:1:2;Described organic solvent is N,N-dimethylacetamide or dimethylformamide, and solution temperature is 45 DEG C, carry out ultrasonic disperse simultaneously;Described polymer monomer is acrylamide;Described cross-linking agent is selected from Ethylene glycol dimethacrylate
(3), by step 2) the molecular engram coating liquid coating for preparing contains benzoyl peroxidating to polysulfone membrane On the surface of thing, react 30 minutes in temperature 40 DEG C, be then added in the deionized water of 25 DEG C be frozen into Film, by glycerine water solution immersion treatment 10h that mass concentration is 20%, last again with methanol is soaked 24 hours, Thoroughly remove bilobalide crystal, then clean with deionized water, obtain described bilobalide molecular engram polysulfones Hybridized film.
Embodiment 2
The preparation method of a kind of bilobalide molecular engram polysulfones hybridized film, comprises the steps: (1), will make The polysulfone membrane got ready contacts with the solution containing benzoyl peroxide, then dries, it is thus achieved that film surface-coated has draws Send out the polysulfone membrane of agent;The mass percentage content of benzoyl peroxide is 0.05%;
(2) molecular engram coating liquid, is prepared: by bilobalide dissolution of crystals in organic solvent;Then add Enter polymer monomer, and cross-linking agent;Described bilobalide with the mass ratio of polymer monomer and cross-linking agent is: 1:3:8;Described organic solvent is dimethylformamide or METHYLPYRROLIDONE, and solution temperature is 65 DEG C, carry out ultrasonic disperse simultaneously;Described polymer monomer is acrylamide;Described cross-linking agent is selected from Tetramethylene dimethylacrylate;
(3), by step 2) the molecular engram coating liquid coating for preparing contains benzoyl peroxidating to polysulfone membrane On the surface of thing, react 60 minutes in temperature 60 C, be then added in the deionized water of 25 DEG C be frozen into Film, by glycerine water solution immersion treatment 20h that mass concentration is 50%, last again with methanol is soaked 24 hours, Thoroughly remove bilobalide crystal, then clean with deionized water, obtain described bilobalide molecular engram polysulfones Hybridized film.
Embodiment 3
The preparation method of a kind of bilobalide molecular engram polysulfones hybridized film, comprises the steps: (1), will make The polysulfone membrane got ready contacts with the solution containing benzoyl peroxide, then dries, it is thus achieved that film surface-coated has draws Send out the polysulfone membrane of agent;The mass percentage content of benzoyl peroxide is 0.5%;
(2) molecular engram coating liquid, is prepared: by bilobalide dissolution of crystals in organic solvent;Then add Enter polymer monomer, and cross-linking agent;Described bilobalide with the mass ratio of polymer monomer and cross-linking agent is: 1:2:6;Described organic solvent is N,N-dimethylacetamide, and solution temperature is 55 DEG C, carries out simultaneously Ultrasonic disperse;Described polymer monomer is acrylamide;Described cross-linking agent is selected from tetramethylene dimethyl Acrylate;
(3), by step 2) the molecular engram coating liquid coating for preparing contains benzoyl peroxidating to polysulfone membrane On the surface of thing, react 50 minutes in temperature 50 C, be then added in the deionized water of 25 DEG C be frozen into Film, by glycerine water solution immersion treatment 115h that mass concentration is 30%, it is little that last again with methanol soaks 24 Time, thoroughly remove bilobalide crystal, then clean with deionized water, obtain described bilobalide molecular engram Polysulfones hybridized film.

Claims (1)

1. the preparation method of a pharmaceutical bilobalide molecular engram polysulfones hybridized film, it is characterised in that Comprise the steps: (1), the polysulfone membrane prepared contacted with the solution containing benzoyl peroxide, then Dry, it is thus achieved that film surface-coated has the polysulfone membrane of initiator;The mass percentage content of benzoyl peroxide It is 0.05~1%;
(2) molecular engram coating liquid, is prepared: by bilobalide dissolution of crystals in organic solvent;Then add Enter polymer monomer and cross-linking agent;Described bilobalide with the mass ratio of polymer monomer and cross-linking agent is 1:1-3:2-8;Described organic solvent is N,N-dimethylacetamide or dimethylformamide or N-first Base-2-Pyrrolidone, solution temperature is 45~65 DEG C, carries out ultrasonic disperse simultaneously;Described polymer list Body is acrylamide;Described cross-linking agent is selected from ethylene glycol dimethacrylate or tetramethylene dimethyl propylene Olefin(e) acid ester;
(3), by step 2) poly-to containing benzoyl peroxide of the molecular engram coating liquid coating for preparing On sulfone film surface, react 30-60 minute in temperature 40-60 DEG C, be then added in the deionized water of 25 DEG C Freezing film, by the glycerine water solution immersion treatment 10~20h that mass concentration is 20~50%, uses the most again Methanol soaks 24 hours, thoroughly removes bilobalide crystal, then cleans with deionized water, obtains described silver Fructus Pruni lactone molecule trace polysulfones hybridized film.
CN201410617850.6A 2014-11-05 A kind of preparation method of pharmaceutical bilobalide molecular engram polysulfones hybridized film Active CN104548972B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0931583A1 (en) * 1998-01-26 1999-07-28 Kurita Water Industries Ltd. Spiral wound type membrane module
CN1772356A (en) * 2005-11-02 2006-05-17 华东理工大学 Composite fiber membrane with chiral molecular imprint and its prepn and application
CN101406813A (en) * 2008-11-20 2009-04-15 天津大学 Method for producing polysulfones hybrid membrane with separated pore passages formed by LUM particles
CN102512993A (en) * 2011-11-18 2012-06-27 天津工业大学 Boron-removed polysulphone modified affinitive membrane as well as preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0931583A1 (en) * 1998-01-26 1999-07-28 Kurita Water Industries Ltd. Spiral wound type membrane module
CN1772356A (en) * 2005-11-02 2006-05-17 华东理工大学 Composite fiber membrane with chiral molecular imprint and its prepn and application
CN101406813A (en) * 2008-11-20 2009-04-15 天津大学 Method for producing polysulfones hybrid membrane with separated pore passages formed by LUM particles
CN102512993A (en) * 2011-11-18 2012-06-27 天津工业大学 Boron-removed polysulphone modified affinitive membrane as well as preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
中药制剂分离与纯化新技术应用进展;陈秦娥等;《江西中医药》;20120630;第43卷(第354期);第72-76页 *

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