CN102617869A - Polyacrylic ester and polyacrylic ester copolymer material hydrophilic modification products and hydrophilic modification method of polyacrylic ester - Google Patents
Polyacrylic ester and polyacrylic ester copolymer material hydrophilic modification products and hydrophilic modification method of polyacrylic ester Download PDFInfo
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- CN102617869A CN102617869A CN201210091582XA CN201210091582A CN102617869A CN 102617869 A CN102617869 A CN 102617869A CN 201210091582X A CN201210091582X A CN 201210091582XA CN 201210091582 A CN201210091582 A CN 201210091582A CN 102617869 A CN102617869 A CN 102617869A
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Abstract
The invention discloses a method for hydrophilically modifying a polyacrylic ester or polyacrylic ester copolymer material and a product prepared with the method. The modification method comprises the following steps of: (1) performing swelling pretreatment on microspheres by using an organic solvent; (2) under the action of an alkaline catalyst, catalyzing ring opening of an epoxy group for reacting with hydroxy groups of polysaccharides to generate a stable ester bond, and chemically bonding hydrophilic polysaccharide molecules on the surfaces of the microspheres; and (3) under an alkaline condition, crosslinking and reinforcing the polysaccharide molecules bonded on the surfaces of the microspheres by using a bifunctional crosslinking agent. The method provided by the invention is easy and convenient to operate, and has mild reaction conditions; and an obtained hydrophilic material is stable, a coating is prevented from falling easily, and nonspecific adsorption of polymer microspheres on proteins is well suppressed. According to hydrophilically-modified polyacrylic ester microspheres, rich hydroxy groups contained in a hydrophilic layer can be further derived into other various functional groups; and the microspheres have great application prospects in the field of biotechnology, particularly in the field of biochemical separation.
Description
Technical field
The present invention relates to polymer materials modification field, relate in particular to a kind of method and product obtained by this method of surface of polymer material wetting abilityization, particularly to the surface hydrophilicityization of oversized hole polyacrylate(s) material.
Background technology
Polymer microballoon is as biochemical separating medium, and its advantage is that physical strength is high, chemical property is stable, acid-alkali-resistant degree is good, can under high pressure operate etc., therefore in the Application Areas as chromatographic media good prospect is arranged.But some feature limits of polymkeric substance itself its application aspect the biomacromolecule separation; Like polymethyl acrylic acid glycidyl ether and Vinylstyrene copolymerization (PGMA-DVB) microballoon; Its microsphere surface has a large amount of epoxy group(ing); Being easy to derive is various functional groups, but because its surface has hydrophobicity, therefore easily and between the protein molecular hydrophobic interaction takes place and cause proteic irreversible adsorption even sex change.
Research shows that this hydrophobic interaction is to cause major cause (the Journal of Colloid and Interface Science of albumen in material surface generation non-specific adsorption; 1989; 132:176-187), one of approach that addresses this problem increases the wetting ability of material surface exactly.The hydrophilic modification method of a kind of amphipathic molecule to polypropylene porous membrane surface disclosed like CN 101011645A; This method is that amphipathic molecule with block structure is as the hydrophilic modifying agent; Earlier polypropylene porous film impregnated in and carry out surface treatment in the swelling agent that is dissolved with amphipathic molecule, carry out surperficial deswelling with the method for vacuum extraction swelling agent at last; Employing has the close and distant water amphipathic molecule of block structure as surface treatment agent; Wherein hydrophobic segment and polyacrylic consistency are better; Be prone to provide the effect of " grappling " with the polypropylene molecule chain combination of surperficial swollen region; Hydrophilic segment is owing to being separated or the outside on film surface and the wetting ability of giving polypropylene porous membrane surface are stretched in the orientation effect.
The PGMA-DVB microballoon carries out surface chemical modification more easily as separating medium more traditional PS and Vinylstyrene (PSt-DVB) microballoon, and the hydrophobicity of its skeletal matrix than PSt matrix a little less than, so be more suitable for as biochemical separating medium.Mostly the PGMA-DVB microsphere surface hydrophilic modifying of bibliographical information is the epoxy group(ing) on surface is hydrolyzed two hydroxyls under acidity or alkaline condition; The polarity on strongthener surface is in the hope of obtaining wetting ability (Chem Commun preferably; 2007,4614-4616), shown in Fig. 1 a; Perhaps in the patented technology in early stage of this laboratory with material surface coupling wetting ability macromole polyoxyethylene glycol (PEG) (CN100487011C) shown in Fig. 1 b, the PGMA microballoon after the modification can be applied to the separation and purification of biomacromolecule under the hydrophobic interaction chromatograph pattern.
Summary of the invention
The objective of the invention is to develop a kind of method of surface of polymer material hydrophilization,, at surface of polymer material, utilize the hydroxyl that enriches on polysaccharide surface to carry out further chemically derived then its coating the mode of hydrophilic polysaccharide molecule with chemical coupling.Material surface after the modification and duct surface bond one deck hydroaropic substance; Thereby reduced material significantly to proteic non-specific adsorption; Surface after the modification can be applied to the separation and purification of biomacromolecule owing to can further be derivatized to various functional groups.
Can effectively reduce albumen in its surperficial non-specific adsorption behind polyacrylate(s) or its copolymer microsphere material surface hydrophilic modifying, very high value arranged in the biologic applications field; Oversized hole PGMA-DVB microballoon among the present invention is through behind the hydrophilic modifying; Can continue to keep original macroporous structure; Can tolerate higher pressure operation; Can further derive in hydrophilic surface simultaneously, can separate as the biochemistry under the various clastotypes and use medium, therefore in biochemical separation and purification field good application prospects and advantage arranged.
For reaching this purpose, the present invention adopted carries out the method for hydrophilic modifying to polyacrylate(s) or its copolymer material surface, comprises the steps:
1) with polyacrylate(s) or its copolymer material, carries out swelling treatment with organic solvent;
2) under the alkaline matter existence condition, the wetting ability polysaccharide molecule is chemically bonded to the material surface that step 1) is handled well through covalent linkage in the presence of solvent;
3) under the alkaline matter existence condition, with linking agent with step 2) the hydrophilic polysaccharide of resulting material surface carries out crosslinked reinforcing.
The polyacrylate(s) material can be materials such as polyacrylate modified product, derived products or graft copolymer.
As optimal technical scheme; Swelling treatment process described in the step 1) is following: polyacrylate(s) or its copolymer material are put into organic solvent seal vibration 1～4h; Treat that polyacrylate(s) or its copolymer material are in solvent after the complete swelling; Carry out suction filtration, and wash, the clean solvent of suction filtration with used solvent.
The swelling pretreatment step is important not omissible program in the preparation process, and what fully the microballoon after the swelling helped hydrophilic substance diffuses into microballoon inside fully, is beneficial to the surface that covers the material that is modified fully of hydrophilic substance.
As optimal technical scheme; Step 2) bonding process described in is: the bonding process step 2) is: polyacrylate(s) or its copolymer material that wetting ability polysaccharide, alkaline matter, swelling are crossed are put into reaction kettle; In solvent, fully mix; React 12～24h down at 30～80 ℃, reaction finishes the back and removes unreacted matters, obtains the material of surface bond hydrophilic substance.
Preferably, said reaction finishes the back and removes unreacting substance, and its program comprises carries out filtration under diminished pressure, filters and uses the deionized water of heat to wash simultaneously, and the temperature of the deionized water of said heat is preferably 40～80 ℃.
As optimal technical scheme; Crosslinked reinforcing process described in the step 3) is: to step 2) add linking agent in the material of gained, under alkaline condition, 20～50 ℃ hydrophilic coating carried out crosslinked 12～24h after; Cross-linking products obtains the hydrophilic modifying material through washing, drying.
Preferably, after crosslinking reaction finished, washing, the drying process of cross-linking products were following: decompress filter and water and ethanol elder generation after scouring three times, remove unreacted matters, 50 ℃ of following vacuum-drying 24h then.Calculate the coating amount of every gram microballoon with mass method, calculation formula is following:
As optimal technical scheme, described polyacrylate(s) or its copolymer material are polymethyl acrylic acid glycidyl ether microballoon or sheet material or polymethyl acrylic acid glycidyl ether and Vinylstyrene copolymerization microsphere or sheet material.
As optimal technical scheme, the organic solvent described in the step 1) is selected from one or several in dioxane, ethanol, DMSO 99.8MIN., the N.Used in the present invention swelling solvent is not limited to above several kinds, allly can carry out other miscible polar organic solvents with water and all can.
Preferably, said volume of organic solvent consumption is said 10～20 times by the swollen material quality.Be microspheres quality: solvent volume=1: 10～20 (g/mL).
As optimal technical scheme, step 2) in, described alkaline matter is selected from one or several in sodium hydroxide, ammoniacal liquor, triethylamine, the dimethyl aminopyridine, and preferably its consumption is 4～32% of a polysaccharide quality.
Preferably, described wetting ability polysaccharide is agarose or VISOSE; Preferred agarose weight average molecular weight range is 10～30W, and the VISOSE weight average molecular weight range is 5K～7W; Further preferred its quality consumption is polymethacrylate or copolymer material quality 1/3～3 times.
Preferably, described solvent is H
2O, DMSO or its mixture, preferred its mixture, further preferred DMSO and H
2O is with the mixed of 1: 10～1: 1 (v/v); The ratio of the quality of materials before the volumetric usage of special preferred solvent is untreated with step 1) is 30: 1～50: 1 (v/m).The adding of DMSO helps the swelling of polymer materials.
As optimal technical scheme, the alkaline matter described in the step 3) is a sodium hydroxide or/and Pottasium Hydroxide, and preferably its concentration range is 1～7mol/L;
Preferably, used solvent is H in the said alkaline substance solution
2The mixture of O and DMSO, preferred DMSO and H
2The volume ratio of O is 1: 10～1: 1 (v/v);
Preferably, described linking agent is selected from one or several in ethylene glycol diglycidylether, epoxy chloropropane, two polyethyleneglycol diglycidylethers; Preferred its consumption is to be crosslinked 1～10 times of quality of materials.
One of the object of the invention also is to provide a kind of hydrophilic modifying polyacrylate(s) or its copolymer material that makes according to preparation method provided by the present invention; Described material surface comprise the internal surface chemical coupling of microballoon duct one deck be rich in the wetting ability agarose or the dextran molecule of hydroxyl, can be used for further modification or derive.
As optimal technical scheme, described hydrophilic modifying polyacrylate(s) or its copolymer material are polymethyl acrylic acid glycidyl ether material or the polymethyl acrylic acid glycidyl ether and the divinyl benzene copolymer material of hydrophilic modifying.
For microballoon behind the check hydrophilic modifying to the inhibition effect of albumen non-specific adsorption; The microballoon of modification is packed in the stainless steel chromatogram column jecket; The column jecket specification is φ 4.6 * 50mm; The chromatographic column that fills is connected on the performance liquid chromatography non-specific adsorption of test microballoon to protein B SA, and concrete experimental technique is seen the embodiment part.The result shows that its BSA non-specific adsorption amount approaches 0.
The method of hydrophilic modifying material surface of the present invention is, the polyose molecular chemistry is coupled to the surface of the material that is modified, particularly to the surface-treated of oversized hole polymethyl acrylic acid Racemic glycidol ethers microballoon.
The technique effect that the present invention produced is; At the enough uniform bonding one deck wetting ability polysaccharide molecule of polymethyl acrylic acid Racemic glycidol ethers material surface energy; The wetting ability of the material surface after the modification improves greatly, can significantly reduce proteic non-specific adsorption amount.
Method of the present invention can be applied to surface-treated, the especially super large pore polymer microsphere of most polymers material, and the polymer microballoon behind the hydrophilic modifying can be applied to biotechnology and chromatographic separation field.
Description of drawings
Fig. 1 is a PGMA-DVB microballoon hydrophilization synoptic diagram.
Fig. 2 is the electronics surface sweeping microphotograph of the polymer microballoon modification front and back of embodiment two gained, and wherein A is the microballoon before the modification; B is the microballoon after the modification.
Fig. 3 is that modification post polymerization thing microballoon proteic adsorptive capacity is measured of embodiment three gained schemed, ● the chromatographic peak area when representing BSA not have absorption; Chromatographic peak area after ■ represents BSA through the hydrophilization microballoon.
Embodiment
Further specify technical scheme of the present invention below in conjunction with accompanying drawing and through embodiment.
Embodiment one
1) oversized hole PGMA-DVB microballoon pre-treatment in dioxane
Accurately take by weighing PGMA-DVB microballoon 1.0g and put into the Erlenmeyer flask of 50mL; Add dioxane 10mL then, behind the 2h that vibrates under the room temperature in the 120rpm vibration shaking table, carry out suction filtration; And wash with the dioxane of same volume, after the washing solvent suction filtration to microsphere surface there is not obvious solvent.
2) PGMA-DVB microsphere surface bonding agarose (Mw=13W)
Take by weighing 1.0g agarose (Mw=13W), 0.32g NaOH puts into the 100mL there-necked flask, then to wherein adding 50mL DMSO/H2O (1: 5; V/v) mixed solvent under the 120rpm mechanical stirring, adds the microballoon after the step 1) swelling treatment among the embodiment one; Be warming up to 70 ℃, under this temperature, keep reaction 24h, after reaction finishes while hot; Carry out decompress filter with the G4 sand core funnel, wash with 80 ℃ of hot water of 500mL simultaneously.
3) with the crosslinked reinforcing of EDGE PGMA-DVB microsphere surface bonding agarose
With step 2 in the case study on implementation one) microballoon that makes is transferred in three mouthfuls of reaction flasks of 100mL, adds 10g NaOH pressed powder to reaction flask then, under the 120rpm mechanical stirring, adds 50mL DMSO/H
2O (1: 5, v/v) mixed solvent slowly drips the EDGE of 3.5mL then with constant pressure funnel; The control rate of addition dropwises EDGE in 20 ℃ of following 4h, keeps reaction 12h; Reaction finishes; Carry out decompress filter with the G4 sand core funnel, and, remove unreacted matters with deionized water and ethanol elder generation after scouring three times.Microballoon after the washes clean to constant weight, characterizes coating with Fourier's ir spectra (FTIR) 50 ℃ of vacuum-dryings, is illustrated in 3432cm
-1The hydroxyl absorption peak at place is obviously strengthened, simultaneously at 1071cm
-1Near the stretching vibration peak of the C-O-C of agarose has also appearred, the appearance of these characteristic peaks shows that the successful coating of agarose is to the PGMA-DVB microballoon.Poidometer is counted in and is stated the modification microballoon that makes, and its agarose coating amount is 110mg/g.
Embodiment two
1) oversized hole PGMA-DVB microballoon pre-treatment in DMSO
Accurately take by weighing PGMA-DVB microballoon 1.0g and put into the Erlenmeyer flask of 50mL; Add DMSO20mL then, behind the 2h that vibrates under the room temperature in the 120rpm vibration shaking table, carry out suction filtration; And wash with the DMSO of same volume, after the washing solvent suction filtration to microsphere surface there is not obvious solvent.
2) PGMA-DVB microsphere surface bonding VISOSE (Mw=2W)
Take by weighing 1.0g VISOSE (Mw=2W), 0.32g NaOH puts into the 100mL there-necked flask, then to wherein adding 50mL DMSO/H
2O (1: 5, v/v) mixed solvent is under the 120rpm mechanical stirring; Add the microballoon after the step 1) swelling treatment among the embodiment two; Be warming up to 37 ℃, under this temperature, keep reaction 20h, after reaction finishes; Carry out decompress filter with the G4 sand core funnel while hot, wash with 40 ℃ of deionized waters of 500mL simultaneously.
3) with the crosslinked reinforcing of EPCl PGMA-DVB microsphere surface bonding VISOSE
With step 2 in the case study on implementation two) microballoon that makes is transferred in three mouthfuls of reaction flasks of 100mL, adds 10g NaOH pressed powder to reaction flask then, under the 120rpm mechanical stirring, adds 50mL DMSO/H
2O (1: 5, v/v) mixed solvent is warming up to 35 ℃ of EPCl that slowly drip 4.5mL with constant pressure funnel then; The control rate of addition in the 4h dropwises EPCl under the room temperature, keeps reaction 24h; Reaction finishes; Carry out decompress filter with the G4 sand core funnel, and, remove unreacted matters with deionized water and ethanol elder generation after scouring three times.Microballoon after the washes clean, to constant weight, with the microballoon before and after the scanning electron microscope observation modification, its pattern does not have considerable change, and is as shown in Figure 2 50 ℃ of vacuum-dryings, shows that the surface hydrophilic modification reaction does not destroy the original pore passage structure of microballoon.The coating amount of microballoon is 116mg/g after the above-mentioned modification.
Embodiment three
1) oversized hole PGMA-DVB microballoon pre-treatment in DMF
Accurately take by weighing PGMA-DVB microballoon 1.0g and put into the Erlenmeyer flask of 50mL; Add DMF15mL then, behind the 2h that vibrates under the room temperature in the 120rpm vibration shaking table, carry out suction filtration; And wash with the DMF of same volume, after the washing solvent suction filtration to microsphere surface there is not obvious solvent.
2) PGMA-DVB microsphere surface bonding VISOSE (Mw=5W)
Take by weighing 1.0g VISOSE (Mw=5W), 0.32g NaOH puts into the 100mL there-necked flask, then to wherein add 50mL DMSO/H2O (1: 5, v/v) mixed solvent; Under the 120rpm mechanical stirring, add the microballoon after the step 1) swelling treatment among the embodiment three, be warming up to 47 ℃; Under this temperature, keep reaction 24h; Reaction is carried out decompress filter with the G4 sand core funnel while hot, and is washed with 50 ℃ of deionized waters of 500mL after finishing.
3) with the crosslinked reinforcing of EDGE PGMA-DVB microsphere surface bonding VISOSE (Mw=5W)
With step 2 in the case study on implementation three) microballoon that makes is transferred in three mouthfuls of reaction flasks of 100mL, adds 10g NaOH pressed powder to reaction flask then, under the 120rpm mechanical stirring, adds 50mL DMSO/H
2O (1: 5, v/v) mixed solvent is warming up to 40 ℃ then; Slowly drip the EDGE of 3.5mL with constant pressure funnel, the control rate of addition dropwises EDGE in 4h; Keep reaction 24h, after reaction finishes, carry out decompress filter with the G4 sand core funnel; And, remove unreacted matters with deionized water and ethanol elder generation after scouring three times.Microballoon after the washes clean, to constant weight, the coating amount is 120mg/g 50 ℃ of vacuum-dryings.Microballoon as model protein, is measured its albumen non-specific adsorption with bovine serum albumin (BSA) after the modification, shows that its BSA non-specific adsorption amount approaches 0, and measured value is 0.004mg/mL, and its test result is as shown in Figure 3.
Embodiment four
1) oversized hole PGMA-DVB microballoon pre-treatment in DMSO
Accurately take by weighing PGMA-DVB microballoon 1.0g and put into the Erlenmeyer flask of 50mL; Add DMSO15mL then, behind the 3h that vibrates under the room temperature in the 120rpm vibration shaking table, carry out suction filtration; And wash with the DMSO of same volume, after the washing solvent suction filtration to microsphere surface there is not obvious solvent.
2) PGMA-DVB microsphere surface bonding VISOSE (Mw=5W)
Take by weighing 1.0g VISOSE (Mw=5W), 0.32g DMAP puts into the 100mL there-necked flask, then to wherein add 50mL DMSO/H2O (1: 3, v/v) mixed solvent; Under the 120rpm mechanical stirring, add the microballoon after the step 1) swelling treatment among the embodiment four, be warming up to 37 ℃; Under this temperature, keep reaction 24h; Reaction is carried out decompress filter with the G4 sand core funnel after finishing while hot, washs with 40 ℃ of deionized waters of 500mL simultaneously.
3) with the crosslinked reinforcing of DEDGE PGMA-DVB microsphere surface bonding VISOSE (Mw=5W)
With step 2 in the case study on implementation four) microballoon that makes is transferred in three mouthfuls of reaction flasks of 100mL, adds 10g NaOH pressed powder to reaction flask then, under the 120rpm mechanical stirring, adds 50mL DMSO/H2O (1: 5; V/v) mixed solvent is warming up to 50 ℃ then, slowly drips the DEDGE of 3.5mL with constant pressure funnel; The control rate of addition dropwises DEDGE in 4h, keeps reaction 24h; Reaction finishes; Carry out decompress filter with the G4 sand core funnel, and, remove unreacted matters with deionized water and ethanol elder generation after scouring three times.Microballoon after the washes clean, 50 ℃ of vacuum-dryings to constant weight.The above-mentioned microballoon coating amount that makes is 116mg/g, and BSA non-specific adsorption amount is 0.01mg/mL.
Embodiment five
1) oversized hole PGMA-DVB microballoon pre-treatment in DMSO
Accurately take by weighing PGMA-DVB microballoon 1.0g and put into the Erlenmeyer flask of 50mL; Add DMSO15mL then, behind the 2h that vibrates under the room temperature in the 120rpm vibration shaking table, carry out suction filtration; And wash with the DMSO of same volume, after the washing solvent suction filtration to microsphere surface there is not obvious solvent.
2) PGMA-DVB microsphere surface bonding VISOSE (Mw=1W)
Take by weighing 2.0g VISOSE (Mw=1W), the 0.24g triethylamine is put into the 100mL there-necked flask, then to wherein add 50mL DMSO/H2O (1: 3, v/v) mixed solvent; Under the 120rpm mechanical stirring, add the microballoon after the step 1) swelling treatment among the embodiment five, be warming up to 60 ℃; Under this temperature, keep reaction 24h; Reaction is carried out decompress filter with the G4 sand core funnel after finishing while hot, washs with 70 ℃ of deionized waters of 500mL simultaneously.
3) with the crosslinked reinforcing of EDGE PGMA-DVB microsphere surface bonding VISOSE (Mw=1W)
With step 2 among the embodiment five) microballoon that makes is transferred in three mouthfuls of reaction flasks of 100mL, adds 14g NaOH pressed powder to reaction flask then, under the 120rpm mechanical stirring, adds 50mL DMSO/H2O (1: 10; V/v) mixed solvent is warming up to 35 ℃ then and slowly drips the EDGE of 6.5mL, the control rate of addition with constant pressure funnel; In 4h, EDGE is dropwised; Keep reaction 24h, reaction finishes, and carries out decompress filter with the G4 sand core funnel; And, remove unreacted matters with deionized water and ethanol elder generation after scouring three times.Microballoon after the washes clean, to constant weight, the coating amount is 126mg/g 50 ℃ of vacuum-dryings, and BSA non-specific adsorption amount is the 0.02mg/mL microballoon, and its non-specific adsorption amount also approaches 0.
Embodiment six
1) oversized hole PGMA-DVB microballoon pre-treatment in DMSO
Accurately take by weighing PGMA-DVB microballoon 1.0g and put into the Erlenmeyer flask of 50mL; Add DMSO15mL then, behind the 2h that vibrates under the room temperature in the 120rpm vibration shaking table, carry out suction filtration; And wash with the DMSO of same volume, after the washing solvent suction filtration to microsphere surface there is not obvious solvent.
2) PGMA-DVB microsphere surface bonding VISOSE (Mw=4W)
Take by weighing 2.0g VISOSE (Mw=4W), 0.24g DMAP puts into the 100mL there-necked flask, then to wherein adding 50mL DMSO/H
2O (1: 4, v/v) mixed solvent is under the 120rpm mechanical stirring; Add the microballoon after the step 1) swelling treatment among the embodiment six; Be warming up to 47 ℃, under this temperature, keep reaction 24h, after reaction finishes; Carry out decompress filter with the G4 sand core funnel while hot, wash with 50 ℃ of deionized waters of 500mL simultaneously.
3) with the crosslinked reinforcing of DEDGE PGMA-DVB microsphere surface bonding VISOSE (Mw=4W)
With step 2 among the embodiment six) microballoon that makes is transferred in three mouthfuls of reaction flasks of 100mL, adds 14g KOH pressed powder to reaction flask then, under the 120rpm mechanical stirring, adds 50mL DMSO/H
2O (1: 10, v/v) mixed solvent slowly drips the DEDGE of 10mL then with constant pressure funnel; The control rate of addition in the 4h dropwises EDGE under the room temperature, keeps reaction 24h; Reaction finishes; Carry out decompress filter with the G4 sand core funnel, and, remove unreacted matters with deionized water and ethanol elder generation after scouring three times.Microballoon after the washes clean, to constant weight, the coating amount is 123mg/g 50 ℃ of vacuum-dryings, BSA non-specific adsorption amount approaches 0.
The non-specific adsorption flow measurement
1) microballoon after the filling modification
Microballoon after the 1.0g modification is put in 20mL 50% aqueous ethanolic solution, behind the ultra-sonic dispersion 30min, is put in the homogenizer of packing column machine, with 10MPa pressure dress post, time length 1h, the column jecket specification is φ 4.6 * 50mm.
2) with the non-specific adsorption of microballoon after the BSA test modification
A is with among the embodiment seven, and the chromatographic column that step 1) is loaded is connected on the liquid chromatograph, and chromatographic condition is following: the BSA solution of sample concentration 2mg/mL; Applied sample amount 200 μ L; Flow velocity 1mL/min; Mobile phase A pH=7.0,50mM phosphate buffer solution, the B 1M NaOH aqueous solution; Gradient condition 0-10minA phase; 10.01-20min B phase; 20.01-30A phase; Repeat sample introduction 5 times, record goes out peak area A1 at every turn; B replaces chromatographic column with connecting joint, same chromatographic process test, and record goes out peak area A at every turn
2C calculates the adsorptive capacity of BSA on chromatographic column, and formula is following:
Q
BSA: the quality of every milliliter of microballoon BSA adsorption (mg/mL);
V: the volume of microballoon (mL) in the chromatographic column.
The prepared hydrophilic modifying microballoon of above embodiment 1-6, test b SA non-specific adsorption amount is all used the testing method of above-mentioned specific adsorption flow measurement, and Fig. 3 is three test results of embodiment.
Claims (10)
1. one kind is carried out the method for hydrophilic modifying to polyacrylate(s) or its copolymer material surface, comprises the steps:
1) with polyacrylate(s) or its copolymer material, carries out swelling treatment with organic solvent;
2) under the alkaline matter existence condition, the wetting ability polysaccharide molecule is chemically bonded to the material surface that step 1) is handled well through covalent linkage in the presence of solvent;
3) under the alkaline matter existence condition, with linking agent with step 2) the hydrophilic polysaccharide of resulting material surface carries out crosslinked reinforcing.
2. method according to claim 1; It is characterized in that; Swelling treatment process described in the step 1) is following: polyacrylate(s) or its copolymer material are put into organic solvent seal vibration 1～4h, treat that polyacrylate(s) or its copolymer material after the complete swelling, carry out suction filtration in solvent; And wash the clean solvent of suction filtration with used solvent.
3. method according to claim 1 and 2; It is characterized in that; Step 2) bonding process described in is: polyacrylate(s) or its copolymer material that wetting ability polysaccharide, alkaline matter, swelling are crossed are put into reaction kettle, in solvent, fully mix, react 12～24h down at 30～80 ℃; Reaction finishes the back and removes unreacted matters, obtains the material of surface bond hydrophilic substance;
Preferably, said reaction finishes the back and removes unreacting substance, and its program comprises carries out filtration under diminished pressure, filters and uses the deionized water of heat to wash simultaneously, and the temperature of the deionized water of said heat is preferably 40～80 ℃.
4. according to each described method of claim 1～3; It is characterized in that; Crosslinked reinforcing process described in the step 3) is: to step 2) add linking agent in the material of gained, under alkaline condition, 20～50 ℃ hydrophilic coating carried out crosslinked 12～24h after; Cross-linking products obtains the hydrophilic modifying material through washing, drying;
Preferably, after crosslinking reaction finished, washing, the drying process of cross-linking products were following: decompress filter and water and ethanol elder generation after scouring three times, remove unreacted matters, 50 ℃ of following vacuum-drying 24h then.
5. according to each described method of claim 1～4; It is characterized in that described polyacrylate(s) or its copolymer material are polymethyl acrylic acid glycidyl ether microballoon or sheet material or polymethyl acrylic acid glycidyl ether and Vinylstyrene copolymerization microsphere or sheet material.
6. according to each described method of claim 1～5, it is characterized in that the organic solvent described in the step 1) is selected from one or several in dioxane, ethanol, DMSO 99.8MIN., the N;
Preferably, said volume of organic solvent consumption is said 10～20 times by the swollen material quality.
7. according to each described method of claim 1～6, it is characterized in that step 2) in, described alkaline matter is selected from one or several in sodium hydroxide, ammoniacal liquor, triethylamine, the dimethyl aminopyridine, and preferably its consumption is 4～32% of a polysaccharide quality;
Preferably, described wetting ability polysaccharide is agarose or VISOSE; Preferred agarose weight average molecular weight range is 10～30W, and the VISOSE weight average molecular weight range is 5K～7W; Further preferred its quality consumption is polymethacrylate or copolymer material quality 1/3～3 times;
Preferably, described solvent is H
2O, DMSO or its mixture, preferred its mixture, further preferred DMSO and H
2O is with the mixed of 1: 10～1: 1 (v/v); The ratio of the quality of materials before the volumetric usage of special preferred solvent is untreated with step 1) is 30: 1～50: 1 (v/m).
8. according to each described method of claim 1～7, it is characterized in that the alkaline matter described in the step 3) is a sodium hydroxide or/and Pottasium Hydroxide, preferably its concentration range is 1～7mol/L;
Preferably, used solvent is H in the said alkaline substance solution
2The mixture of O and DMSO, preferred DMSO and H
2The volume ratio of O is 1: 10～1: 1 (v/v);
Preferably, described linking agent is selected from one or several in ethylene glycol diglycidylether, epoxy chloropropane, two polyethyleneglycol diglycidylethers; Preferred its consumption is to be crosslinked 1～10 times of quality of materials.
9. the hydrophilic modifying polyacrylate(s) or its copolymer material that make according to each described method of claim 1～8; It is characterized in that; Material surface comprise the internal surface chemical coupling of microballoon duct one deck be rich in the wetting ability agarose or the dextran molecule of hydroxyl, can be used for further modification or derive.
10. hydrophilic modifying polyacrylate(s) according to claim 9 or its copolymer material; It is characterized in that described hydrophilic modifying polyacrylate(s) or its copolymer material are polymethyl acrylic acid glycidyl ether material or the polymethyl acrylic acid glycidyl ether and the divinyl benzene copolymer material of hydrophilic modifying.
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