CN1935342A - Glycosylated polyethylene affinity membrane preparing method and its use - Google Patents
Glycosylated polyethylene affinity membrane preparing method and its use Download PDFInfo
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- CN1935342A CN1935342A CN 200610053524 CN200610053524A CN1935342A CN 1935342 A CN1935342 A CN 1935342A CN 200610053524 CN200610053524 CN 200610053524 CN 200610053524 A CN200610053524 A CN 200610053524A CN 1935342 A CN1935342 A CN 1935342A
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Abstract
The present invention discloses a preparation method of glycosylated polypropylene affinity membrane and its application. It is characterized by that it uses polypropylene microfiltration membrane as carrier material, uses mixture of acetone and water as solvent, uses dibenzophenone and iron trichloride as photoinitiator, under the irradiation of UV light the hydroxyethyl methacry late can be grafted to obtain the hydroxylated polypropylene microfiltration membrane, then under the catalysis action of catalyst boron trifluoride ethyl ether complex compound the saccharide protected by acetyl group can be combined on the hydroxyl group of said membrane surface, then the glycosylated polypropylene microfiltration membrane protected by acetyl group be soaked in the sodium methoxide/methyl alcohol solution to remove acetyl group so as to obtain the invented glycosylated polypropylene affinity membrane. Said glycosylated polypropylene affinity membrane can be used for selectively separating and purifying protein.
Description
Technical field
The present invention relates to the method that membrane surface modification prepares affinity membrane, relate in particular to a kind of preparation method of glycosylated polyethylene affinity membrane.
Background technology
Effect between any material all starts from the surface, and the importance of surface property in application is that other performance institute is irreplaceable.At present, different materials is carried out surface modification, obtained paying close attention to widely and significant progress.Wherein, the separation membrane more and more wider to the application field, the employing process for modifying surface can be optimized the surface property of separation membrane and don't can destroy its bulk properties, widened the scope of application of separation membrane, improve the service efficiency of separation membrane, prolonged the service life of separation membrane.The method of separation membrane surface modification mainly comprise surface plasma handle (CN1539550, CN1546214), ultraviolet light irradiation graft modification (CN1618509), gamma-radiation radiation modification (CN1569934), ozone graft modification (CN1640533) and surfactant coated modification (CN1257747) etc.Through specific modifying process, separation membrane can be endowed different surfaces characteristic, possess such as functions such as hydrophily, compatibility, p hour response, temperature-responsive, biocompatibility, resistance tocrockings, be widely used in fields such as sewage disposal, printing and dyeing, bio-pharmaceuticals, fine chemistry industry.
Protein, nucleic acid and sugar are the chief components that constitutes organism, are bringing into play in vital movement and important biological function, and numerous physiology courses is had deep effect, therefore, their research and sign are become more and more important.At occurring in nature, sugar exists with forms such as glycopeptide, glycolipid, glycosaminoglycan, proteoglycans or other glycoconjugates, discover, sugar is except storage power and establishment structure, also wide participation many physiology courses in the vital movement, comprise virus intrusion, signal transmission, inflammation, cell-cell interaction, bacterium-host's interaction, fertilization, growth etc.In fact, sugar relates to every thing feelings of control from the embryonic development to the immune system, and the fine difference of sugared structure just may produce significant impact to biological function.Than protein and nucleic acid, sugar is the compound of polyhydroxy aldehyde or polyhydroxyketone, can straight chain or ring-like existence, by glycosidic bond or branch, perhaps be linear and link to each other, its possible structure is more complicated various, and irreplaceable effect is being brought into play in corresponding biological agent in life science.In unique status biologically, from late 1980s, glycobiology becomes another emerging front subject after genomics and protein science owing to sugared---and sugar group has obtained increasing concern and application.
In recent years, glycosyl is introduced in the material, utilized the biocompatibility and the recognition reaction of sugar, obtained certain effect in fields such as food, medicine, clinical diagnosis, cosmetics, Separation of Proteins.CN1450907 has invented the method that a kind of signal of inducing by activin in the beta glycan increase cell conducts, and this method can be used for treating many pathologic conditions, comprises reproduction, reaction, skin, bone, liver, hematopoiesis and central nervous system disease.CN1417347 with parts such as sugar at a certain distance covalency be connected in stromal surface, be used to identify pathogeny microorganism and toxic protein thereof.CN1460524 has prepared the intraocular lens of α～pi-allyl glucoside finishing, the intraocular lens's optics portion of this ECCE and the outer surface of loop all have the molecular layer of α～pi-allyl glucoside monomer, improved intraocular lens's biocompatibility, and method for making science, medical transplanting are safe and reliable.The diethylamine ethyl glucan that CN1030005 will have acidic functionality is coated on the silica dioxide granule, from whey, optionally extract metalloprotein by absorption and wash-out, especially fixedly the metalloprotein of iron, for example lactotransferrin, lactoperoxidase and siderophillin.CN1130375 is carried on polysaccharide derivates (ester of polysaccharide or carbamate derivatives) on the silica gel particle of the useful silylating agent surface treated silanol that aralkyl arranged and makes separating agent for optical isomer, as the packing material of reversed-phase liquid chromatography, optical isomer is separated from racemic compound.CN1763126 is a raw material with tamarind gum or Artemisia Glue and shitosan, tri-iron tetroxide is a magnetic fluid, glutaraldehyde as cross linker, sulfanilic acid is the magnetic microsphere with certain magnetic responsiveness of aminating agent preparation, is the composite biopolysaccharide magnetic microsphere that a kind of swelling volume is little, acid resistance is better, cost is low.WO2004040308 provides the method that is used to solidify at least a carbohydrate molecule, comprise the surface is contacted the amino surface that has that plasma polymer bag quilt is provided with the plasma of at least a monomer, and with different natural polysaccharide solution such as hyaluronic acid, dermatan sulfate, chondroitin sulfate, heparin, Heparan sulfate or the keratan sulfates etc. of described polymer surfaces contact, with polysaccharide by the passive polymer surfaces that is adsorbed onto of electrostatic interaction, the polysaccharide that solidifies has sufficient bond strength on the surface, and has kept natural biologically active.This sugared mating surface can be used for aspects such as biology sensor, treatment carrier, cell cultivation, medical treatment device, affinity purification matrix and chip.
Summary of the invention
The present invention thinks that glycosyl introduces the surface of polypropylene micro-filtration membrane after through the test that studies for a long period of time, can make the good physical and chemical performance of the biological function of sugar and polypropylene become one.Because polypropylene micro-filtration membrane porosity height, specific area is big, has improved the binding capacity of glycosyl on the film surface greatly, and the collection cluster effect of sugar is easy to realize, has significantly strengthened the selective absorption of glycosyl to protein.Utilize the selectivity recognition reaction of different glycosyls to specified protein, glycosylated polyethylene affinity membrane can be separated protein adsorption respectively.This glycosylated polyethylene affinity membrane can be realized efficient, the separation fast of protein as the fixedly phase of high performance liquid chromatography, this is because there be not the quality transmission of solute at the granule interior hole in fixing phase, solute only has short diffusion distance at fixing phase surface, therefore to having low diffusible large biological molecule, can realize quality transmission fast, thereby shorten the holdup time, and be beneficial to high biologically active and the rate of recovery (LC～GC Int of maintenance large biological molecule, 1996,9 (10): 650; 9 (11): 741; JC hour ro mol atogr.A, 1995.705:3).Simultaneously, this glycosylated polyethylene affinity membrane is as the affine surface of a class, also can be used for mass spectrum Identifying micro-organisms (Anal.C hour e mol .2001,73:751～757), because the film surface has high specific area, the surface of the affine surface ratio gold of this film has higher microorganism and captures ability, and in addition, hydrophily that glycosyl is good and biocompatibility make that the pollution of film is controlled.The polypropylene micro-filtration membrane after glycosylation, can be used for different proteins and microorganism separation, concentrate and target is removed, have broad application prospects at aspects such as chromatographic isolation and mass spectrum identification of protein or microorganism, cell cultivation, medical treatment devices.
The preparation method and the application thereof that the purpose of this invention is to provide a kind of glycosylated polyethylene affinity membrane.
Method step is as follows:
1) the polypropylene micro-filtration membrane is immersed in the solution contain composite photoinitiator and hydroxyl acrylic ester monomer, logical nitrogen, after the ultraviolet light irradiation glycerol polymerization, washing, oven dry, obtain hydroxylating polypropylene micro-filtration membrane, percent grafting is 0～150 gram/square metre film;
2) above-mentioned film is immersed different in the monose or polysaccharide solution of acetylation protection, under nitrogen protection, add catalyst, and oscillating reactions 2 hours in ice-water bath, then reaction system is moved to and continue oscillating reactions 20 hours under the room temperature, obtain the polypropylene micro-filtration membrane of surface after washing, the oven dry in conjunction with glycosyl;
3) this film is immersed in the methanol solution of sodium methoxide, vibrate under the room temperature, slough the blocking group on the glycosyl, obtain the glycosylated polyethylene affinity membrane of deprotection, fixed rate is 0～45 gram/square metre film.
The invention has the advantages that:
1) sugar is not limited to and lists severally, and the sugar (monose, disaccharides, trisaccharide etc.) of any acetyl group protection all can use.Simultaneously, the blocking group on the glycosyl (acetyl group) can remove easily, and can calculate the glycosyl content of combination on the polypropylene micro-filtration membrane by gravimetric method fast.
2) by regulating ultraviolet irradiation glycerol polymerization condition, the percent grafting of the hydroxyethyl methacrylate of grafting can be regulated (0～150 gram/square metre film) on the polypropylene micro-filtration membrane in very wide scope; Utilize the polypropylene micro-filtration membrane of different hydroxyethyl methacrylate percent graftings, and then can obtain the polypropylene affinity membranes (0～45 gram/square metre film) of different glycosylation degree, can realize the collection cluster effect of film surface glycosyl, significantly strengthen the selective absorption of glycosyl protein; Simultaneously, the polypropylene affinity membranes of this different glycosylation degree is applicable to the separation of a series of protein solutions (0.1 grams per liter～20 grams per liters) from the low concentration to the high concentration and concentrate, and the scope of application is wide.
3) reaction is at room temperature carried out, and is simple to operate, economically feasible.
4) glycosylated polyethylene affinity membrane that adopts this method to obtain is by poly hydroxy ethyl acrylate glycosyl to be fixed on the film surface, little in adsorbed proteins time space steric hindrance, and glycosyl is easy to form multivalence with protein and combines, and the ability of polypropylene affinity membranes adsorbed proteins is improved.
5) adopt glycosylated polyethylene affinity membrane that this method obtains owing to be that chemical method is in conjunction with glycosyl, stable performance in use, glycosyl can not come off, be used for protein Selective Separation, concentrate or target when removing, can reuse by the endless form of absorption, wash-out, and can avoid the pollution of product, greatly reduce production cost.
6) glycosylated polyethylene affinity membrane that adopts this method to obtain has excellent mechanical intensity, excellent chemical stability and heat endurance and cheap cost thereof, and is applied widely.
Description of drawings
Fig. 1-Fig. 7 is respectively the schematic arrangement of glucose glycosylated polyethylene affinity membrane, galactolipin glycosylated polyethylene affinity membrane, mannose glycosylated polyethylene affinity membrane, fucose glycosylated polyethylene affinity membrane, maltose glycosylated polyethylene affinity membrane, lactose glycosylated polyethylene affinity membrane and sucrose glycosylated polyethylene affinity membrane.
The specific embodiment
The light trigger that adopts among the present invention is a composite photoinitiator, i.e. the compound of benzophenone and ferric trichloride, and its purpose is to improve the percent grafting of hydroxyethyl methacrylate on the polypropylene micro-filtration membrane;
Percent grafting adopts gravimetric method to calculate among the present invention;
Glycosylated polyethylene affinity membrane separates employing ultraviolet-visible spectrophotometer detection to absorption of proteins among the present invention.
Following example further specifies the present invention, but these examples are not used for limiting the present invention.
One, the preparation example of glycosylated polyethylene affinity membrane:
Example 1
Take by weighing an amount of ferric trichloride (FeCl
3) be dissolved in the mixed solvent (volume ratio is 3: 1) of acetone and water, be made into the photoinitiator solution of concentration 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 20% monomer solution; With diameter is that (aperture is 0.2 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 85%, 160 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 25 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 1.52 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of penta-acetyl glucose (penta-acetyl glucose is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with the acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the glucose modified polypropylene micro-filtration membrane of penta-acetyl.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of glucose, and the glycosylation rate is 0.65 gram/square metre film.
Example 2
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 20% monomer solution; With diameter is that (aperture is 2 microns for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 40%, 500 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 25 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 11.48 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of penta-acetyl glucose (penta-acetyl glucose is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with the acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the glucose modified polypropylene micro-filtration membrane of penta-acetyl.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of glucose, and the glycosylation rate is 3.05 gram/square metre films.
Example 3
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.033 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 20% monomer solution; (aperture is 0.1 micron with the polypropylene hollow fiber micro-filtration membrane, porosity is 45%, the film external diameter is 500 microns) put into 10 milliliters of these monomer solutions and soaked 1 hour, ultraviolet light (UV) irradiation 25 minutes, take out the polypropylene hollow fiber micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene hollow fiber micro-filtration membrane of 2.38 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene hollow fiber micro-filtration membrane inserts 20 milliliters of penta-acetyl glucose (penta-acetyl glucose is 20 times of equivalents of the HEMA of polypropylene hollow fiber micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with the acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the glucose modified polypropylene hollow fiber micro-filtration membrane of penta-acetyl.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of glucose, and the glycosylation rate is 0.72 gram/square metre film.
Example 4
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; (aperture is 0.1 micron with the polypropylene hollow fiber micro-filtration membrane, porosity is 60%, the film external diameter is 250 microns) put into 10 milliliters of these monomer solutions and soaked 1 hour, ultraviolet light (UV) irradiation 25 minutes, take out the polypropylene hollow fiber micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene hollow fiber micro-filtration membrane of 11.13 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene hollow fiber micro-filtration membrane inserts 20 milliliters of penta-acetyl glucose (penta-acetyl glucose is 20 times of equivalents of the HEMA of polypropylene hollow fiber micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with the acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the glucose modified polypropylene hollow fiber micro-filtration membrane of penta-acetyl.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of glucose, and the glycosylation rate is 2.87 gram/square metre films.
Example 5
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; With diameter is that (aperture is 0.2 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 75%, 160 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 60 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 31.54 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of penta-acetyl glucose (penta-acetyl glucose is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with the acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the glucose modified polypropylene micro-filtration membrane of penta-acetyl.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of glucose, and the glycosylation rate is 11.50 gram/square metre films.
Example 6
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; With diameter is that (aperture is 0.8 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 70%, 240 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 25 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 11.26 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of penta-acetyl glucose (penta-acetyl glucose is 5 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with the acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the glucose modified polypropylene micro-filtration membrane of penta-acetyl.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of glucose, and the glycosylation rate is 1.48 gram/square metre films.
Example 7
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; With diameter is that (aperture is 0.2 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 85%, 160 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 300 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 145.68 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of penta-acetyl glucose (penta-acetyl glucose is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with the acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the glucose modified polypropylene micro-filtration membrane of penta-acetyl.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of glucose, and the glycosylation rate is 42.79 gram/square metre films.
Example 8
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; With diameter is that (aperture is 0.2 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 85%, 160 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 60 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 32.35 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of mannose pentaacetates (the mannose pentaacetate is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the polypropylene micro-filtration membrane of mannose pentaacetate modification.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of mannose, and the glycosylation rate is 11.79 gram/square metre films.
Example 9
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; With diameter is that (aperture is 0.2 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 85%, 160 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 60 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 30.87 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of galactolipin pentaacetates (the galactolipin pentaacetate is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the polypropylene micro-filtration membrane of galactolipin pentaacetate modification.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of galactolipin, and the glycosylation rate is 11.26 gram/square metre films.
Example 10
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; With diameter is that (aperture is 0.2 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 85%, 160 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 60 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 30.14 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of fucose tetracetates (the fucose tetracetate is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the polypropylene micro-filtration membrane of fucose tetracetate modification.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of fucose, and the glycosylation rate is 10.23 gram/square metre films.
Example 11
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; With diameter is that (aperture is 0.2 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 85%, 160 microns of thickness) film is put into 10 milliliters of these monomer solutions immersions 1 hour, ultraviolet light (UV) irradiation 60 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 31.88 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of maltose octaacetates (the maltose octaacetate is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the polypropylene micro-filtration membrane of maltose octaacetate modification.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of maltose, and the glycosylation rate is 13.29 gram/square metre films.
Example 12
Take by weighing an amount of benzophenone (BP) and ferric trichloride (FeCl
3) be dissolved in the mixed solvent of the acetone that mixes with equal-volume and water, be made into concentration and be respectively the composite photoinitiator solution of 0.033 mol and 0.0007 mol, add hydroxyethyl methacrylate (HEMA) again, be made into volumetric concentration and be 5% monomer solution; With diameter is that (aperture is 0.2 micron for 4.2 centimetres the dull and stereotyped micro-filtration membrane of polypropylene, porosity is 85%, 160 microns of thickness) putting into 10 milliliters of these monomer solutions soaked 1 hour, ultraviolet light (UV) irradiation 60 minutes, take out the polypropylene micro-filtration membrane then, clean, put into 40 ℃ of baking ovens with acetone and a large amount of water, vacuum drying 24 hours, obtaining the HEMA percent grafting is the hydroxylating polypropylene micro-filtration membrane of 32.58 gram/square metre films.Get in the dichloromethane solution that above-mentioned hydroxylating polypropylene micro-filtration membrane inserts 20 milliliters of lactose octaacetates (the lactose octaacetate is 20 times of equivalents of the HEMA of polypropylene micro-filtration membrane surface grafting), and under blanket of nitrogen, add the boron trifluoride etherate of 100 times of equivalents, sealing, oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then; Stop reaction, with acetone washing, put into 40 ℃ of baking ovens, vacuum drying 24 hours obtains the polypropylene micro-filtration membrane of lactose octaacetate modification.This film is immersed in the methanol solution (concentration is 0.5 mol) of sodium methoxide; vibrate under the room temperature; slough the blocking group acetyl group on the glycosyl; wash with water; put into 40 ℃ of baking ovens; vacuum drying 24 hours obtains the glycosylated polypropylene affinity membranes of lactose, and the glycosylation rate is 13.58 gram/square metre films.
Two, the example of glycosylated polyethylene affinity membrane application:
1, the glucose glycosylated polyethylene affinity membrane is to the adsorbing separation of concanavalin (Con A)
Get 4 of glucose glycosylated polyethylene affinity membranes (the glycosylation rate is 2.87 gram/square metre films) that prepare in the above-mentioned example and immerse infiltration in advance in 10 milliliters of absolute ethyl alcohols, again with PBS (PBS, 0.01 mol, pH=7.36) clean, put into the PBS solution of 10 milliliters of concanavalin/peanut agglutinins (Con A/PNA), sealing, wherein, the concentration of Con A is 1 grams per liter, and the concentration of PNA is 1 grams per liter, CaCl in the solution
2Concentration be 0.1 mM/liter, MnCl
2Concentration be 0.1 mM/liter, the concentration of NaCl is 0.1 mol.At 25 ℃ of following constant temperature after 30 minutes, take out the glucose glycosylated polyethylene affinity membrane, and, can will be adsorbed on the concanavalin wash-out on the film, thereby realize purpose that concanavalin is separated from the mixed solution of protein with the flushing of the glucose phosphate salt buffer solution of 1 mol.
Get 4 of glucose glycosylated polyethylene affinity membranes (the glycosylation rate is 11.50 gram/square metre films) that prepare in the above-mentioned example and immerse infiltration in advance in 10 milliliters of absolute ethyl alcohols, again with PBS (PBS, 0.01 mol, pH=7.36) clean, put into the PBS solution of 10 milliliters of concanavalin/peanut agglutinins (Con A/PNA), sealing, wherein, the concentration of Con A is 5 grams per liters, and the concentration of PNA is 5 grams per liters, CaCl in the solution
2Concentration be 0.1 mM/liter, MnCl
2Concentration be 0.1 mM/liter, the concentration of NaCl is 0.1 mol.At 25 ℃ of following constant temperature after 30 minutes, take out the glucose glycosylated polyethylene affinity membrane, and, can will be adsorbed on the concanavalin wash-out on the film, thereby realize purpose that concanavalin is separated from the mixed solution of protein with the flushing of the glucose phosphate salt buffer solution of 1 mol.
Get 4 of glucose glycosylated polyethylene affinity membranes (the glycosylation rate is 42.79 gram/square metre films) making each in the above-mentioned example and immerse infiltration in advance in 10 milliliters of absolute ethyl alcohols, again with PBS (PBS, 0.01 mol, pH=7.36) clean, put into the PBS solution of 10 milliliters of concanavalin/peanut agglutinins (Con A/PNA), sealing, wherein, the concentration of Con A is 20 grams per liters, and the concentration of PNA is 20 grams per liters, CaCl in the solution
2Concentration be 0.1 mM/liter, MnCl
2Concentration be 0.1 mM/liter, the concentration of NaCl is 0.1 mol.At 25 ℃ of following constant temperature after 30 minutes, take out the glucose glycosylated polyethylene affinity membrane, and, can will be adsorbed on the concanavalin wash-out on the film, thereby realize purpose that concanavalin is separated from the mixed solution of protein with the flushing of the glucose phosphate salt buffer solution of 1 mol.
2, the mannose glycosylated polyethylene affinity membrane is to the adsorbing separation of concanavalin (Con A)
Get 4 of mannose glycosylated polyethylene affinity membranes that prepare in the above-mentioned example and immerse infiltration in advance in 10 milliliters of absolute ethyl alcohols, again with PBS (PBS, 0.01 mol, pH=7.36) clean, put into the PBS solution of 10 milliliters of concanavalin/peanut agglutinins (Con A/PNA), sealing, wherein, the concentration of Con A is 5 grams per liters, and the concentration of PNA is 5 grams per liters, CaCl in the solution
2Concentration be 0.1 mM/liter, MnCl
2Concentration be 0.1 mM/liter, the concentration of NaCl is 0.1 mol.At 25 ℃ of following constant temperature after 30 minutes, take out the mannose glycosylated polyethylene affinity membrane, and, can will be adsorbed on the concanavalin wash-out on the film, thereby realize purpose that concanavalin is separated from the mixed solution of protein with the flushing of the mannose PBS of 1 mol.
3, the galactolipin glycosylated polyethylene affinity membrane is to the adsorbing separation of peanut agglutinin (PNA)
Get 4 of galactolipin glycosylated polyethylene affinity membranes that prepare in the above-mentioned example and immerse infiltration in advance in 10 milliliters of absolute ethyl alcohols, again with PBS (PBS, 0.01 mol, pH=7.36) clean, put into the PBS solution of 10 milliliters of concanavalin/peanut agglutinins (Con A/PNA), sealing, wherein, the concentration of Con A is 5 grams per liters, and the concentration of PNA is 5 grams per liters, CaCl in the solution
2Concentration be 0.1 mM/liter, MnCl
2Concentration be 0.1 mM/liter, the concentration of NaCl is 0.1 mol.At 25 ℃ of following constant temperature after 30 minutes, take out the galactolipin glycosylated polyethylene affinity membrane, and, can will be adsorbed on the peanut agglutinin wash-out on the film, thereby realize purpose that peanut agglutinin is separated from the mixed solution of protein with the flushing of the galactolipin PBS of 1 mol.
The preparation condition and the result of above-mentioned example 1～12 glycosylated polyethylene affinity membrane are as shown in table 1; The separating effect of 4,5,7,8 and 9 pairs of concanavalin/peanut agglutinin mixed solutions of example is as shown in table 2; Different glycosyls and as shown in table 3 with the protein table of comparisons of its identification.
Table 1
A: reference substance is the molal quantity of the HEMA of grafting on the polypropylene micro-filtration membrane.
Table 2
| Example | HEMA percent grafting (gram/square metre film) | Glycosylation rate (gram/square metre film) | Concanavalin concentration (grams per liter) | Peanut agglutinin concentration (grams per liter) | ||
| Before the absorption | After the absorption | Before the absorption | After the absorption | |||
| 4 | 11.13 | 2.87 | 1 | 0 | 1 | 0.96 |
| 5 | 31.54 | 11.50 | 5 | 0 | 5 | 4.89 |
| 7 | 145.68 | 42.79 | 20 | 0 | 20 | 19.83 |
| 8 | 32.35 | 11.79 | 5 | 0 | 5 | 4.94 |
| 9 | 30.87 | 11.26 | 5 | 4.93 | 5 | 0 |
Table 3
| The glycosyl type | The agglutinin of specific recognition | ||
| Title | Abbreviation | The source | |
| D-glucose | Concanavalin (Concanavalin A) | Con A | Sword bean |
| LCA (Lens culinaris agglutinin) | LCA | French beans | |
| Wheat bacterium agglutinin (Wheat germ agglutinin) | WGA | Wheat | |
| STL element (Solanum tubrosum agglutinin) | STA | Potato | |
| The D-mannose | Pisum sativum agglutinin (Pisum sativum agglutinin) | PSA | Pea |
| Concanavalin (Concanavalin A) | Con A | Sword bean | |
| LCA (Lens culinaris agglutinin) | LCA | French beans | |
| Snow bell flower agglutinin (Galanthus nivalus agglutinin) | GNA | Snow bell flower | |
| Kuhseng agglutinin (Sophora flavescens agglutinin) | SFA | Kuh-seng | |
| The D-galactolipin | Ricinus agglutinin (Ricinus communis agglutinin) | RCA | Castor-oil plant |
| Peanut agglutinin (Peanut agglutinin) | PNA | Peanut | |
| Soybean agglutinin (Soybean agglutinin) | SBA | Soybean | |
| Sophora bud agglutinin (Sophora japonica agglutinin) | SJA | The sophora bud | |
| Bandeiraea simplicifolia agglutinin | BSA | ～ | |
| The L-fucose | UEA (Ulex europeaus agglutinin) | UEA | The chaste tree beans |
Claims (10)
1, a kind of preparation method of glycosylated polyethylene affinity membrane, its feature is as follows:
1) under the light trigger effect, polypropylene micro-filtration membrane surface is arrived in hydroxyl acrylic ester monomer ultraviolet irradiation glycerol polymerization;
2) under catalyst action, sugar monomer is attached on the hydroxyl on above-mentioned polypropylene micro-filtration membrane surface;
3) slough blocking group on the glycosyl, obtain glycosylated polyethylene affinity membrane.
2, by the preparation method of the described glycosylated polyethylene affinity membrane of claim 1, it is characterized in that:
1) the polypropylene micro-filtration membrane is immersed in the solution contain composite photoinitiator and hydroxyl acrylic ester monomer, wherein photoinitiator concentration is 0～0.033 mol, and the percentage by volume of monomer in solution is 5～30%; Lead to nitrogen after 10 minutes, the ultraviolet light irradiation glycerol polymerization, the ultraviolet light irradiation time is 10～300 minutes: film is taken out and washs, dry, obtain hydroxylating polypropylene micro-filtration membrane, percent grafting is 0～150 gram/square metre film;
2) above-mentioned film is immersed in the sugar monomer solution, add catalyst under nitrogen protection, catalyst concn is 5 times of sugar; Oscillating reactions is 2 hours in ice-water bath, reaction system is moved to continue oscillating reactions 20 hours under the room temperature then, obtains the fixedly polypropylene micro-filtration membrane of glycosyl of surface after washing, the oven dry;
3) this film immersion is sloughed in the reagent of glycosyl blocking group, vibrate under the room temperature, slough the blocking group on the glycosyl, obtain the glycosylated polyethylene affinity membrane of deprotection, fixed rate is 0～45 gram/square metre film.
3, press the preparation method of the described glycosylated polyethylene affinity membrane of claim 1, it is characterized in that: said polypropylene micro-filtration membrane is that average pore size is that 0.1～2 micron, porosity are 40～85%, thickness is 15～200 microns flat sheet membrane or hollow-fibre membrane, and wherein the external diameter of hollow-fibre membrane is 250～500 microns.
4, by the preparation method of the described glycosylated polyethylene affinity membrane of claim 1, it is characterized in that: said light trigger is a composite photoinitiator, i.e. the compound of ferric trichloride and benzophenone, and its ratio is 0～1.
5, by the preparation method of the described glycosylated polyethylene affinity membrane of claim 1, it is characterized in that: said hydroxyl acrylic ester monomer is a hydroxyethyl methacrylate.
6, by the preparation method of the described glycosylated polyethylene affinity membrane of claim 1, it is characterized in that: the solvent of said ultraviolet light irradiation glycerol polymerization is the mixture of acetone and water, and ratio is 0.25～4.
7, press the preparation method of the described glycosylated polyethylene affinity membrane of claim 1, it is characterized in that: said sugar is alpha-glucose pentaacetate, the mannose pentaacetate, the galactolipin pentaacetate, the fucose tetracetate, the maltose octaacetate, the lactose octaacetate, one or more in the sucrose octaacetate: the solvent of sugar is a carrene.
8, by the preparation method of the described glycosylated polyethylene affinity membrane of claim 1, it is characterized in that: said catalyst is a boron trifluoride etherate.
9, by the preparation method of the described glycosylated polyethylene affinity membrane of claim 1, it is characterized in that: the said reagent of sloughing the blocking group on the glycosyl is the methanol solution of sodium methoxide, and its concentration is 0.5 mol, and the group of sloughing is an acetyl group.
10, the application of the described glycosylated polyethylene affinity membrane of claim 1 utilizes glycosylated polyethylene affinity membrane to have the selectivity of protein is discerned, as the separation of protein, concentrated or target removing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101301590B (en) * | 2008-01-16 | 2010-12-08 | 浙江大学 | Sugar-containing polymer compound film with blocked pore and preparation thereof |
| CN101544776B (en) * | 2009-04-30 | 2012-04-25 | 浙江大学 | Preparation method and use of high-density glycosylated polypropylene affinity membranes |
| CN104530460A (en) * | 2014-12-19 | 2015-04-22 | 大连理工大学 | Glycosylated high polymer material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101301590B (en) * | 2008-01-16 | 2010-12-08 | 浙江大学 | Sugar-containing polymer compound film with blocked pore and preparation thereof |
| CN101544776B (en) * | 2009-04-30 | 2012-04-25 | 浙江大学 | Preparation method and use of high-density glycosylated polypropylene affinity membranes |
| CN104530460A (en) * | 2014-12-19 | 2015-04-22 | 大连理工大学 | Glycosylated high polymer material and preparation method thereof |
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