CN103252177B - The affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying, Preparation Method And The Use - Google Patents
The affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying, Preparation Method And The Use Download PDFInfo
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- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention discloses affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying and preparation method thereof.This film is made up of fluoropolymer resin, sulfonate polymer resin and carbohydrate macromolecule, under preferred raw material and ratio, there is good specific adsorption effect to LDL, and there is good stability and biocompatibility, reusable, with low cost, be expected to the scale clinical practice that has high input.Its preparation method comprises following process: film fluoropolymer resin, sulfonate polymer resin, carbohydrate macromolecule, pore-foaming agent are dissolved in solvent by a certain percentage, make homogeneous spinning membrane system liquid, after the filtration of spinning membrane system liquid, vacuum defoamation, prepare doughnut film forming by immersion precipitation phase inversion process spinning, then by obtained hollow-fibre membrane successively in deionized water and the abundant rinsing of ultra-pure water.The blended dissolving preparation method that the present invention adopts has the advantages such as easy to operate and safe, raw material are cheap and easy to get.
Description
Technical field
The invention belongs to bio-separation engineering field, be specifically related to the affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying, Preparation Method And The Use.
Background technology
Angiocardiopathy is the primary disease (" the first killer ") threatening human health, and according to the World Health Organization's assessment report of 2008 display, the number dying from angiocardiopathy accounts for 29% of the total death toll in the whole world.Epidemiological study and clinical practice show, the LDL excessive concentration in angiocardiopathy and blood and to cause thus in LDL intravasation wall and to be oxidized to low-density lipoprotein (ox ~ LDL) close relation of oxidized form.
Low-density lipoprotein (low density lipoprotein, LDL) is that the endogenous cholesterol of liver synthesis and Cholesterol ester transfer are to the principal mode of its hetero-organization.LDL is the spheric granules that diameter is about 20 ~ 30 nm, and its number-average molecular weight excursion is 2 ~ 35 × 10
6, in particle, lipid content accounts for 79%, wherein CHF 8%, cholesteryl ester 38%, phosphatide about 22%, triglycerides 10%, and carrying ester gp is 21%.The major apolipoprotein of LDL is ApoB(93%), remaining is ApoA, ApoC, ApoD, ApoE etc.
When LDL excessive concentration in blood, then blood viscosity can be caused to rise, the damaged or stenosis at blood vessel, oxidized LDL easily and other albumen form patch, continue accumulate thus cause atherosclerotic.Reduce LDL content in blood and can obviously improve cardiovascular rheological characteristic, therefore become the important measures reducing cardiovascular disease incidence rate.Blood purification therapy is a kind of method that effectively can reduce LDL concentration in blood, result for the treatment of fast, significantly, for carrying out control effects by fat-reducing medicament and meals and unconspicuous serious heredity hypercholesterolemiapatients patients is particularly applicable.But it should be noted that other useful components in blood, especially HDL (high density lipoprotein, HDL) is at maintenance blood cholesterol level, alleviates in angiocardiopathy and has very useful effect.Therefore, when carrying out LDL specific adsorption, the non-specific adsorption of sorbing material to other useful components in blood farthest should be reduced.
In preparation LDL sorbing material, researcher has done a large amount of work, and carrier and the part of prepared LDL sorbing material are varied.Carrier mainly comprises polysulfones, polyvinyl alcohol, glucan, shitosan etc.Part can be divided into immuno absorbence and affine absorption two class by mechanism difference, mainly comprises heparin, polypeptide, chlorosulfonic acid etc.Processing method is then based on chemical synthesis.Chinese patent CN200610200095.7 discloses a kind of sorbing material with taurine and heteroauxin two kinds of adsorption function bases, by the acting in conjunction of function base, has higher adsorption capacity to LDL, simultaneously less to the non-specific adsorption of HDL.Canadian Patent CA2001358 discloses a kind of that LDL antibody coupling is surperficial to sorbing material, and make the method for its specific adsorption LDL, adsorptive selectivity is high, adsorption effect is obvious.German patent DE 3782657D discloses a kind of preparation method of porous cellulose, and it has the selective of height to the absorption of LDL, and adsorbance increases along with cellulosic increase, and adsorbance is large and blood compatibility is better.But the cost of material of above-mentioned sorbing material is higher, not easily obtains, the preparation technology of sorbing material is comparatively complicated, cannot meet the needs that larger scale clinical uses.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of has the sorbing material simple and with low cost compared with high selectivity, biocompatibility, preparation technology to low-density lipoprotein (LDL).Sorbing material provided by the invention is the affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying, described polymeric hollow fibre diffusion barrier is made up of fluoropolymer resin, sulfonate polymer resin and carbohydrate macromolecule, in described polymeric hollow fibre diffusion barrier, the mass fraction of fluoropolymer resin is 10% ~ 70%, the mass fraction of sulfonate polymer resin is 2% ~ 30%, and the high molecular mass fraction of carbohydrate is 5% ~ 90%; Described polymeric hollow fibre separation membrane surface is rich in has hydrophilic sulfonic group and the high molecular hydroxyl of carbohydrate, and described polymeric hollow fibre diffusion barrier has Selective recognition absorption property to low-density lipoprotein white matter; Described polymeric hollow fibre diffusion barrier aperture is 0.01 ~ 0.5 μm.
Glycosyl/sulfonation modifying of the present invention is affine, and polymeric hollow fibre diffusion barrier has the principle of specific adsorption to be to LDL: for the character of LDL with positive charge, and the sulfonate polymer resin with negative electrical charge in polymeric hollow fibre diffusion barrier produces suction-operated by charge interaction to LDL; The hydroxyl that carbohydrate macromolecule in polymeric hollow fibre diffusion barrier contains has poor phase isomery character, recognition reaction site can be provided, specific binding effect is produced with the protein structure in LDL, and then absorption LDL, and, described carbohydrate molecule can not with positive charge, to prevent sulfonate polymer resin weakening the charge adsorption effect of LDL.In order to reach above-mentioned effect, the present invention select not positively charged, the carbohydrate macromolecule of specific binding effect can be produced with the protein structure in LDL.Therefore, the specific adsorption effect of glycosyl/sulfonation modifying of the present invention affine polymeric hollow fibre diffusion barrier to LDL is the synergistic result of specific binding of charge adsorption effect by the sulfonic acid group of sulfonate polymer resin and carbohydrate high molecular weight hydroxy, good synergy is reached in order to make these two kinds of effects, in described polymeric hollow fibre diffusion barrier, the mass fraction of fluoropolymer resin is 10% ~ 70%, the mass fraction of sulfonate polymer resin is 2% ~ 50%, and the high molecular mass fraction of carbohydrate is 5% ~ 90%; Preferably, in described polymeric hollow fibre diffusion barrier, the mass fraction of fluoropolymer resin is 15% ~ 60%, and the mass fraction of sulfonate polymer resin is 5% ~ 35%, and the high molecular mass fraction of carbohydrate is 10% ~ 75%.Fluoropolymer resin, as the matrix of polymeric hollow fibre diffusion barrier, can be fixed sulfonate polymer resin and carbohydrate macromolecule preferably, and have good biocompatibility, is comparatively ideal backing material.Described polymeric hollow fibre diffusion barrier is doughnut structure, have selected suitable aperture (aperture is 0.01 ~ 0.5 μm), is conducive to the adsorption effect improving polymeric hollow fibre diffusion barrier.
Further, described fluoropolymer resin is polysulfones or polyether sulfone; Wherein, polysulfones number-average molecular weight is 40000 ~ 120000; Polyether sulfone number-average molecular weight is 40000 ~ 150000.Preferably, polysulfones number-average molecular weight is 60000 ~ 90000; Polyether sulfone number-average molecular weight is 60000 ~ 110000.
Further, described sulfonate polymer resin is SPSF or sulfonated polyether sulfone; Wherein, SPSF number-average molecular weight is 60000 ~ 120000, sulfonation degree is 5% ~ 80%; Sulfonated polyether sulfone number-average molecular weight is 60000 ~ 150000, and sulfonation degree is 5% ~ 80%.Preferably, described SPSF number-average molecular weight is 80000 ~ 95000, sulfonation degree 10% ~ 30%; Sulfonated polyether sulfone number-average molecular weight is 85000 ~ 120000, and sulfonation degree is 10% ~ 30%.
Further, described carbohydrate macromolecule be selected from glucan, peptide glycan, marine alga polysaccharide any one or multiple arbitrarily, the high molecular molecular weight of described carbohydrate is 6 ~ 400,000; Preferably, the high molecular molecular weight of described carbohydrate is 10 ~ 300,000.
Further, described polymeric hollow fibre diffusion barrier can be made up of polysulfones, SPSF and carbohydrate macromolecule, also can be made up of polyether sulfone, SPSF and carbohydrate macromolecule, also can be made up of polysulfones, sulfonated polyether sulfone and carbohydrate macromolecule, can also be made up of polyether sulfone, sulfonated polyether sulfone and carbohydrate macromolecule.
Glycosyl/sulfonation modifying provided by the invention affine polymeric hollow fibre diffusion barrier has good adsorption selection effect to low-density lipoprotein, can as hemodialysis membrane or membrane for purifying blood, for haemodialysis or blood purification.Glycosyl/sulfonation modifying of the present invention the is affine polymeric hollow fibre diffusion barrier adsorption rate to low-density lipoprotein (LDL) and HDL (HDL) can reach the adsorption effect of 61.2 ~ 61.5%, 0.2 ~ 0.3% respectively.
The present invention also provides the preparation method of the affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying, comprises the steps::
(1) preparation of preparation liquid: fluoropolymer resin, sulfonate polymer resin and organic solvent are mixed, carry out stirring and dissolving at 10 ~ 90 DEG C, after solute dissolves completely, filter cleaner, obtains polymer resin solution; Carbohydrate macromolecule is dissolved in dimethyl sulfoxide (DMSO), at 20 ~ 90 DEG C, carries out stirring and dissolving, after solute dissolves completely, filter cleaner, obtained concentration is the carbohydrate Polymer Solution of 10 ~ 30%; Above-mentioned obtained polymer resin solution, carbohydrate Polymer Solution and pore-foaming agent are mixed, at 10 ~ 90 DEG C, is uniformly mixed 6 ~ 48h, then obtains preparation liquid with after inert gas deaeration 6 ~ 48h;
(2) extrude immersion precipitation liquid by preparation liquid from spinning head, form as-spun fibre, after abundant rinsing, taking-up is dried, i.e. the obtained affine polymeric hollow fibre diffusion barrier of glycosyl/sulfonation modifying.
Further, the proportioning of fluoropolymer resin, sulfonate polymer resin and the organic solvent mixing described in step (1) is: the mass fraction of fluoropolymer resin is 15 ~ 25%, the mass fraction of sulfonate polymer resin is 5 ~ 15%, and the mass fraction of organic solvent is 60 ~ 80%.
Further, the organic solvent described in step (1) is selected from dimethyl formamide (DMF), DMA (DMAC) and 1-METHYLPYRROLIDONE (NMP).
Further, the proportioning of the polymer resin solution described in step (1), carbohydrate Polymer Solution and pore-foaming agent mixing is: the mass fraction of polymer resin solution is 30 ~ 70%, the mass fraction of carbohydrate Polymer Solution is 20 ~ 60%, and the mass fraction of pore-foaming agent is 1 ~ 20%.
Further, the pore-foaming agent described in step (1) be selected from PEG400, PEG600, PEG800, PEG1000, PEG2000, PVP-K17, PVP-K30, PVP-K90 any one or multiple arbitrarily.
Further, described fluoropolymer resin is polysulfones or polyether sulfone; Wherein, polysulfones number-average molecular weight is 40000 ~ 120000; Polyether sulfone number-average molecular weight is 40000 ~ 150000.Preferably, polysulfones number-average molecular weight is 60000 ~ 90000; Polyether sulfone number-average molecular weight is 60000 ~ 110000;
Further, described sulfonate polymer resin is SPSF or sulfonated polyether sulfone; Wherein, SPSF number-average molecular weight is 60000 ~ 120000, sulfonation degree is 5% ~ 80%; Sulfonated polyether sulfone number-average molecular weight is 60000 ~ 150000, and sulfonation degree is 5% ~ 80%.Preferably, described SPSF number-average molecular weight is 80000 ~ 95000, sulfonation degree 10% ~ 30%; Sulfonated polyether sulfone number-average molecular weight is 85000 ~ 120000, and sulfonation degree is 10% ~ 30%.
Further, described carbohydrate macromolecule be selected from glucan, peptide glycan, marine alga polysaccharide any one or multiple arbitrarily, the high molecular molecular weight of described carbohydrate is 6 ~ 400,000; Preferably, the high molecular molecular weight of described carbohydrate is 10 ~ 300,000.
The present invention adopts blending method to prepare the affine polymeric hollow fibre diffusion barrier of glycosyl/sulfonation modifying, utilize sulfonated polymer elecrtonegativity selective to what have the electropositive selective and carbohydrate of LDL to protein, the two is blended, and add pore-foaming agent, utilize immersion precipitation phase inversion process spinning, be prepared into hollow-fibre membrane.
Method preparation process of the present invention is simple and raw material are cheap and easy to get, properties of product are stable can repeatedly be used, and greatly reduces medical treatment cost, and good biocompatibility, the side effect that produces patient are little, selective and adsorption rate is all higher to LDL, be expected to for clinical expansion.
Glycosyl/sulfonation modifying affine polymeric hollow fibre diffusion barrier prepared by method of the present invention has good adsorption selection effect to low-density lipoprotein, can as hemodialysis membrane or membrane for purifying blood, for haemodialysis or blood purification.Glycosyl/the sulfonation modifying prepared according to method of the present invention is affine polymeric hollow fibre diffusion barrier, can reach the adsorption effect of 61.2 ~ 61.5%, 0.2 ~ 0.3% respectively to the adsorption rate of low-density lipoprotein (LDL) and HDL (HDL).
Beneficial effect of the present invention is:
Glycosyl/sulfonation modifying provided by the invention affine polymeric hollow fibre diffusion barrier can to low-density lipoprotein adsorption selection, there is good biocompatibility and excellent stability.The present invention determines carbohydrate hydroxyl and the synergistic optimal proportion scope of sulfonic acid group in preparation process, filter out the selective height to LDL, efficiency is high, the comparatively ideal tunica fibrosa of adsorption rate, selected polysulfones, SPSF and macromolecule sugar are the good material of biocompatibility, can play the adsorption selection to low-density lipoprotein after it is blended under the condition keeping better biocompatibility preferably.Film can repeatedly use, and good stability is reproducible, and side effect is little, has good clinical expansion prospect.
Prepare solution by the method for physical blending, working condition gentleness, technique are simple, spray silk jet stability good in spinning process, and tunica fibrosa morphosis can pass easily through and regulate the condition of spinning process to control, and is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is embodiments of the invention related data and test result figure.
Detailed description of the invention
Below by embodiment, technical scheme of the present invention is described in further detail.
embodiment 1
Ratio (mass ratio) in 25: 15: 60 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 90 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 90: 10, at 90 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 10%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG400 add in there-necked flask by ratio (mass ratio) in 70: 20: 10 successively, be uniformly mixed 12h, then namely obtain preparation liquid with after nitrogen deaeration 12h at 90 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 24h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, use 0.5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 58.7 ~ 59.1%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 2
Ratio (mass ratio) in 25: 15: 60 is by dried polysulfones (number-average molecular weight=40000), SPSF (number-average molecular weight=60000, sulfonation degree=5%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 10 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 90: 10, at 80 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 10%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG400 add in there-necked flask by ratio (mass ratio) in 70: 20: 10 successively, be uniformly mixed 48h, then namely obtain preparation liquid with after nitrogen deaeration 48h at 10 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 24h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, use 0.5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 58.1 ~ 58.4%, 0.3 ~ 0.5% is respectively to the adsorption rate of LDL and HDL.
embodiment 3
Ratio (mass ratio) in 20: 10: 70 is by dried polysulfones (number-average molecular weight=120000), SPSF (number-average molecular weight=80000, sulfonation degree=80%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 50 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; The mixture (number-average molecular weight=100000) of dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=100000) and glucan slowly adds in there-necked flask by the ratio (mass ratio) in 85: 15, stirring and dissolving is carried out at 50 DEG C, after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 15%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG600 add in there-necked flask by ratio (mass ratio) in 70: 20: 10 successively, be uniformly mixed 18h, then namely obtain preparation liquid with after nitrogen deaeration 12h at 50 DEG C.Extruded from spinning head under 500kPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 24h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 57.2 ~ 57.7%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 4
Ratio (mass ratio) in 25: 15: 60 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=120000, sulfonation degree=10%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=60000) slowly add in there-necked flask by the ratio (mass ratio) in 75: 25, at 80 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 25%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG600 add in there-necked flask by ratio (mass ratio) in 30: 60: 10 successively, be uniformly mixed 12h, then namely obtain preparation liquid with after nitrogen deaeration 12h at 80 DEG C.Extruded from spinning head under 500kPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 24h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 53.1 ~ 53.4%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 5
Ratio (mass ratio) in 15: 15: 70 is by dried polysulfones (number-average molecular weight=80000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 50 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=60000) slowly add in there-necked flask by the ratio (mass ratio) in 90: 10, at 80 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 10%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG600 add in there-necked flask by ratio (mass ratio) in 30: 60: 10 successively, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 50 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 59.4 ~ 59.8%, 0.2 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 6
Ratio (mass ratio) in 15: 5: 80 is by dried polysulfones (number-average molecular weight=100000), SPSF (number-average molecular weight=95000, sulfonation degree=30%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=200000) slowly add in there-necked flask by the ratio (mass ratio) in 90: 10, at 60 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 10%.Above two kinds of solution and pore-foaming agent PVP-K30 add in there-necked flask by ratio (mass ratio) in 40: 40: 20 successively, at 50 DEG C, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 12h.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 52.7 ~ 52.9%, 0.3 ~ 0.5% is respectively to the adsorption rate of LDL and HDL.
embodiment 7
Ratio (mass ratio) in 25: 5: 70 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=30%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=400000) slowly add in there-necked flask by the ratio (mass ratio) in 88: 12, at 80 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 12%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PVP-K30 add in there-necked flask by ratio (mass ratio) in 30: 60: 10 successively, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 80 DEG C.Extruded from spinning head under 500kPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 51.4 ~ 52.0%, 0.2 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 8
Ratio (mass ratio) in 25: 15: 60 is by dried polyether sulfone (number-average molecular weight=40000), sulfonated polyether sulfone (number-average molecular weight=95000, sulfonation degree=5%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 60 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polyether sulfone and sulfonation ether polysulfones; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 90: 10, at 60 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 10%.The mixed solution of polyether sulfone and sulfonation ether polysulfones, sugar juice and pore-foaming agent PEG400 add in there-necked flask by ratio (mass ratio) in 60: 30: 10 successively, be uniformly mixed 20h, then namely obtain preparation liquid with after nitrogen deaeration 20h at 60 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 24h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 56.1 ~ 56.8%, 0.5 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 9
Ratio (mass ratio) in 25: 15: 60 is by dried polyether sulfone (number-average molecular weight=60000), sulfonated polyether sulfone (number-average molecular weight=85000, sulfonation degree=30%), NMP slowly adds in there-necked flask successively, stirring and dissolving is carried out at 60 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polyether sulfone and sulfonated polyether sulfone; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 90: 10, at 30 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 10%.The mixed solution of polyether sulfone and sulfonation ether polysulfones, sugar juice and pore-foaming agent PVP-K90 add in there-necked flask by ratio (mass ratio) in 50: 45: 5 successively, be uniformly mixed 12h, then namely obtain preparation liquid with after nitrogen deaeration 12h at 60 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 55.6 ~ 55.9%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 10
Ratio (mass ratio) in 20: 5: 75 is by dried polyether sulfone (number-average molecular weight=150000), sulfonated polyether sulfone (number-average molecular weight=80000, sulfonation degree=30%), DMF slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polyether sulfone and sulfonated polyether sulfone; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=60000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 80 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polyether sulfone and sulfonation ether polysulfones, sugar juice and pore-foaming agent PEG400 add in there-necked flask by ratio (mass ratio) in 60: 30: 10 successively, be uniformly mixed 15h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 80 DEG C.Extruded from spinning head under 1MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 36h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 54.2 ~ 54.8%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 11
Ratio (mass ratio) in 25: 15: 60 is by dried polyether sulfone (number-average molecular weight=90000), SPSF (number-average molecular weight=60000, sulfonation degree=80%), DMF slowly adds in there-necked flask successively, stirring and dissolving is carried out at 60 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=200000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 60 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PVP-K17 add in there-necked flask by ratio (mass ratio) in 60: 30: 10 successively, be uniformly mixed 12h, then namely obtain preparation liquid with after nitrogen deaeration 12h at 70 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 36h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 57.9 ~ 58.2%, 0.3 ~ 0.5% is respectively to the adsorption rate of LDL and HDL.
embodiment 12
Ratio (mass ratio) in 25: 15: 60 is by dried polysulfones (number-average molecular weight=90000), sulfonated polyether sulfone (number-average molecular weight=120000, sulfonation degree=40%), DMAC slowly adds in there-necked flask successively, stirring and dissolving is carried out at 70 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; The mixture (number-average molecular weight=400000) of dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=400000) and peptide glycan slowly adds in there-necked flask by the ratio (mass ratio) in 72: 28, stirring and dissolving is carried out at 70 DEG C, after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 28%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PVP-K17 add in there-necked flask by ratio (mass ratio) in 70: 20: 10 successively, be uniformly mixed 6h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 80 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 58.4 ~ 59.1%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 13
Ratio (mass ratio) in 25: 15: 60 is by dried polysulfones (number-average molecular weight=90000), sulfonated polyether sulfone (number-average molecular weight=95000, sulfonation degree=30%), DMAC slowly adds in there-necked flask successively, stirring and dissolving is carried out at 50 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 90: 10, at 50 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 10%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG400 add in there-necked flask by ratio (mass ratio) in 70: 20: 10 successively, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 50 DEG C.Extruded from spinning head under 500kPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 24h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 54.3 ~ 54.7%, 0.2 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 14
Ratio (mass ratio) in 25: 15: 60 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), DMF slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 80: 20, at 20 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 20%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG400 add in there-necked flask by ratio (mass ratio) in 60: 30: 10 successively, be uniformly mixed 6h, then namely obtain preparation liquid with after nitrogen deaeration 6h at 80 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 61.2 ~ 61.5%, 0.2 ~ 0.3% is respectively to the adsorption rate of LDL and HDL.
embodiment 15
Ratio (mass ratio) in 25: 15: 60 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), DMF slowly adds in there-necked flask successively, stirring and dissolving is carried out at 60 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 80: 20, at 80 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 20%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG2000 add in there-necked flask by ratio (mass ratio) in 45: 40: 15 successively, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 60 DEG C.Extruded from spinning head under 500kPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 24h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 60.8 ~ 61.1%, 0.3 ~ 0.5% is respectively to the adsorption rate of LDL and HDL.
embodiment 16
Ratio (mass ratio) in 15: 5: 80 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), DMF slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=80000) slowly add in there-necked flask by the ratio (mass ratio) in 83: 17, at 40 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 17%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG800 add in there-necked flask by ratio (mass ratio) in 70: 20: 10 successively, be uniformly mixed 18h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 70 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 59.3 ~ 60.1%, 0.4 ~ 0.6% is respectively to the adsorption rate of LDL and HDL.
embodiment 17
Ratio (mass ratio) in 15: 5: 80 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), DMF slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=250000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 70 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG800 add in there-necked flask by ratio (mass ratio) in 45: 45: 10 successively, be uniformly mixed 30h, then namely obtain preparation liquid with after nitrogen deaeration 12h at 40 DEG C.Extruded from spinning head under 1MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 24h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 59.6 ~ 60.2%, 0.3 ~ 0.5% is respectively to the adsorption rate of LDL and HDL.
embodiment 18
Ratio (mass ratio) in 15: 5: 80 is by dried polysulfones (number-average molecular weight=90000), sulfonated polyether sulfone (number-average molecular weight=150000, sulfonation degree=50%), DMF slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and sulfonated polyether sulfone; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 80 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and sulfonated polyether sulfone, sugar juice and pore-foaming agent PEG1000 add in there-necked flask by ratio (mass ratio) in 45: 45: 10 successively, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 40 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 54.1 ~ 54.8%, 0.3 ~ 0.5% is respectively to the adsorption rate of LDL and HDL.
embodiment 19
Ratio (mass ratio) in 15: 5: 80 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=30%), DMF slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=150000) slowly add in there-necked flask by the ratio (mass ratio) in 75: 25, at 50 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 25%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG1000 add in there-necked flask by ratio (mass ratio) in 50: 42: 8 successively, be uniformly mixed 6h, then namely obtain preparation liquid with after nitrogen deaeration 10h at 90 DEG C.Extruded from spinning head under 1MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 59.2 ~ 59.5%, 0.4 ~ 0.5% is respectively to the adsorption rate of LDL and HDL.
embodiment 20
Ratio (mass ratio) in 15: 5: 80 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), DMAC slowly adds in there-necked flask successively, stirring and dissolving is carried out at 60 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 65 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PVP-K90 add in there-necked flask by ratio (mass ratio) in 45: 45: 10 successively, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 20 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 58.3 ~ 58.7%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 21
Ratio (mass ratio) in 15: 5: 80 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=30%), DMAC slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=150000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 80 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PVP-K90 add in there-necked flask by ratio (mass ratio) in 39: 60: 1 successively, be uniformly mixed 20h, then namely obtain preparation liquid with after nitrogen deaeration 20h at 50 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 59.2 ~ 59.5%, 0.2 ~ 0.3% is respectively to the adsorption rate of LDL and HDL.
embodiment 22
Ratio (mass ratio) in 15: 15: 70 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), DMAC slowly adds in there-necked flask successively, stirring and dissolving is carried out at 20 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; The mixture of dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=100000) and glucan (number-average molecular weight=100000) slowly adds in there-necked flask by the ratio (mass ratio) in 70: 30, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG800: PVP-K30=1: 1 add in there-necked flask by ratio (mass ratio) in 39: 60: 1 successively, at 80 DEG C, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 58.5 ~ 58.9%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 23
Ratio (mass ratio) in 15: 15: 70 is by dried polysulfones (number-average molecular weight=110000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), DMAC slowly adds in there-necked flask successively, stirring and dissolving is carried out at 30 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 55 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PVP-K17 add in there-necked flask by ratio (mass ratio) in 50: 40: 10 successively, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 50 ~ 80 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 8h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 60.1 ~ 60.8%, 0.3 ~ 0.5% is respectively to the adsorption rate of LDL and HDL.
embodiment 24
Ratio (mass ratio) in 15: 15: 70 is by dried polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000, sulfonation degree=60%), DMAC slowly adds in there-necked flask successively, stirring and dissolving is carried out at 45 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polysulfones and SPSF; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 45 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PVP-K90 add in there-necked flask by ratio (mass ratio) in 60: 39: 10 successively, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 24h at 40 DEG C.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 60.4 ~ 61.1%, 0.3 ~ 0.4% is respectively to the adsorption rate of LDL and HDL.
embodiment 25
Ratio (mass ratio) in 15: 15: 70 is by dried polyether sulfone (number-average molecular weight=110000), SPSF (number-average molecular weight=95000, sulfonation degree=50%), DMAC slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, filter cleaner, obtains the mixed solution of polyether sulfone and SPSF; Dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=400000) slowly add in there-necked flask by the ratio (mass ratio) in 70: 30, at 50 DEG C, carry out stirring and dissolving, and after solute dissolves completely, filter cleaner, obtains the sugar juice that concentration is 30%.The mixed solution of polysulfones and SPSF, sugar juice and pore-foaming agent PEG800: PVP-K30=1: 1 add in there-necked flask by ratio (mass ratio) in 70: 25: 5 successively, at 50 DEG C, be uniformly mixed 24h, then namely obtain preparation liquid with after nitrogen deaeration 12h.Extruded from spinning head under 2MPa by preparation liquid, in immersion precipitation liquid, form as-spun fibre, immerse in deionized water and ultra-pure water after rinsing 48h successively respectively, taking-up is dried, i.e. the obtained affine polymer hollow fiber membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with 0. 5ml normal saline dilution, wash away the affine polymer hollow fiber membrane of glycosyl/sulfonation modifying with the speed of 20ml per minute, carry out three times, 59.5 ~ 60.5%, 0.2 ~ 0.3% is respectively to the adsorption rate of LDL and HDL.
Above-described embodiment is only not used in for illustration of the present invention and limits the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Claims (11)
1. the affine polymeric hollow fibre diffusion barrier of glycosyl/sulfonation modifying, it is characterized in that: described polymeric hollow fibre diffusion barrier is made up of fluoropolymer resin, sulfonate polymer resin and carbohydrate macromolecule, in described polymeric hollow fibre diffusion barrier, the mass fraction of fluoropolymer resin is 10% ~ 70%, the mass fraction of sulfonate polymer resin is 2% ~ 30%, and the high molecular mass fraction of carbohydrate is 5% ~ 90%; Described polymeric hollow fibre separation membrane surface is rich in has hydrophilic sulfonic group and the high molecular hydroxyl of carbohydrate, and described polymeric hollow fibre diffusion barrier has Selective recognition absorption property to low-density lipoprotein white matter; Described polymeric hollow fibre diffusion barrier aperture is 0.01 ~ 0.5 μm.
2. the affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying as claimed in claim 1, is characterized in that: described fluoropolymer resin is polysulfones or polyether sulfone; Wherein, polysulfones number-average molecular weight is 40000 ~ 120000; Polyether sulfone number-average molecular weight is 40000 ~ 150000.
3. the affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying as claimed in claim 1, is characterized in that: described sulfonate polymer resin is SPSF or sulfonated polyether sulfone; Wherein, SPSF number-average molecular weight is 60000 ~ 120000, sulfonation degree is 5% ~ 80%; Sulfonated polyether sulfone number-average molecular weight is 60000 ~ 150000, and sulfonation degree is 5% ~ 80%.
4. the affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying as claimed in claim 1, it is characterized in that: described carbohydrate macromolecule be selected from glucan, peptide glycan, marine alga polysaccharide any one or multiple arbitrarily, the high molecular molecular weight of described carbohydrate is 6 ~ 400,000.
5. the preparation method of the affine polymeric hollow fibre diffusion barrier of glycosyl/sulfonation modifying according to claim 1, comprises the steps::
(1) preparation of preparation liquid: fluoropolymer resin, sulfonate polymer resin and organic solvent are mixed, carry out stirring and dissolving at 10 ~ 90 DEG C, after solute dissolves completely, filter cleaner, obtains polymer resin solution; Carbohydrate macromolecule is dissolved in dimethyl sulfoxide (DMSO), at 20 ~ 90 DEG C, carries out stirring and dissolving, after solute dissolves completely, filter cleaner, obtained concentration is the carbohydrate Polymer Solution of 10 ~ 30%; Above-mentioned obtained polymer resin solution, carbohydrate Polymer Solution and pore-foaming agent are mixed, at 10 ~ 90 DEG C, is uniformly mixed 6 ~ 48h, then obtains preparation liquid with after inert gas deaeration 6 ~ 48h;
(2) extrude immersion precipitation liquid by preparation liquid from spinning head, form as-spun fibre, after abundant rinsing, taking-up is dried, i.e. the obtained affine polymeric hollow fibre diffusion barrier of glycosyl/sulfonation modifying.
6. preparation method as claimed in claim 5, it is characterized in that: the proportioning of fluoropolymer resin, sulfonate polymer resin and the organic solvent mixing described in step (1) is: the mass fraction of fluoropolymer resin is 15 ~ 25%, the mass fraction of sulfonate polymer resin is 5 ~ 15%, and the mass fraction of organic solvent is 60 ~ 80%.
7. preparation method as claimed in claim 5, is characterized in that: the organic solvent described in step (1) is selected from dimethyl formamide, DMA and 1-METHYLPYRROLIDONE.
8. preparation method as claimed in claim 5, it is characterized in that: the proportioning of the polymer resin solution described in step (1), carbohydrate Polymer Solution and pore-foaming agent mixing is: the mass fraction of polymer resin solution is 30 ~ 70%, the mass fraction of carbohydrate Polymer Solution is 20 ~ 60%, and the mass fraction of pore-foaming agent is 1 ~ 20%.
9. preparation method as claimed in claim 5, is characterized in that: the pore-foaming agent described in step (1) be selected from PEG400, PEG600, PEG800, PEG1000, PEG2000, PVP-K17, PVP-K30, PVP-K90 any one or multiple arbitrarily.
10. the purposes of polymeric hollow fibre diffusion barrier in haemodialysis that the glycosyl/sulfonation modifying described in any one of claim 1-4 is affine.
The purposes of polymeric hollow fibre diffusion barrier in blood purification that glycosyl/sulfonation modifying described in 11. any one of claim 1-4 is affine.
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