CN1059356C - Modified polysulphone super-filter membrane and its preparation and application - Google Patents
Modified polysulphone super-filter membrane and its preparation and application Download PDFInfo
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- CN1059356C CN1059356C CN94112724A CN94112724A CN1059356C CN 1059356 C CN1059356 C CN 1059356C CN 94112724 A CN94112724 A CN 94112724A CN 94112724 A CN94112724 A CN 94112724A CN 1059356 C CN1059356 C CN 1059356C
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- polysulfones
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- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 56
- 239000012528 membrane Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000005576 amination reaction Methods 0.000 claims abstract description 12
- 239000002753 trypsin inhibitor Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 9
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000704 physical effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 101710162629 Trypsin inhibitor Proteins 0.000 claims description 10
- 229940122618 Trypsin inhibitor Drugs 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 5
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 238000005917 acylation reaction Methods 0.000 claims description 2
- -1 anilino- Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000007265 chloromethylation reaction Methods 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 230000032696 parturition Effects 0.000 claims 1
- 238000000108 ultra-filtration Methods 0.000 abstract description 9
- 102000004142 Trypsin Human genes 0.000 abstract 2
- 108090000631 Trypsin Proteins 0.000 abstract 2
- 239000012588 trypsin Substances 0.000 abstract 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000006193 diazotization reaction Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- 238000010137 moulding (plastic) Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical compound NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
一种改性聚砜超滤膜，是聚砜经酰化-胺化或氯甲基化-胺化法进行改性反应制得的，该超滤膜的物性为：平均孔径：20～80μm；孔密度：5×109～8×109孔/cm2，膜的皮层厚度为5～12μm;支撑层厚度:50～120μm。这种超滤膜，可通过戊二醛的交联作用下与胰蛋白酶进行交联，也可通过重氮化反应在0～4℃下与胰蛋白醇固载化制成亲和超滤膜，该膜可用于纯化分离胰蛋白酶抑制剂，使其纯度达到98.5%。A modified polysulfone ultrafiltration membrane, which is obtained by modifying polysulfone through acylation-amination or chloromethylation-amination. The physical properties of the ultrafiltration membrane are: average pore size: 20-80 μm ; Pore density: 5×10 9 ～8×10 9 pores/cm 2 , the thickness of the skin layer of the membrane is 5～12 μm; the thickness of the support layer: 50～120 μm. This ultrafiltration membrane can be cross-linked with trypsin under the cross-linking action of glutaraldehyde, and can also be immobilized with trypsin by diazotization reaction at 0-4°C to make an affinity ultrafiltration membrane , the membrane can be used to purify and separate trypsin inhibitors to a purity of 98.5%.
Description
The present invention relates to a kind of membrane separation technique, specifically provide a kind of polysulphone super-filter membrane and preparation method thereof of modification.Simultaneously provide the method for utilizing this film to make the affinity ultrafiltration film again, this film can carry out purifies and separates to trypsin inhibitor.
Affine separation is owing to have very high specificity, good selectivity, high purifying multiple, so this technical development is very rapid, make multiple affine separation chromatography filler, be widely used in the research of the purifies and separates and the life science of bioengineering target product.Recently, along with affinity ligand is covalently bound on miillpore filter or the milipore filter have been appearred in film separation science develop rapidly, make affinity membrane, be applied on the purifies and separates of some large biological molecules such as enzyme, protein etc., used membrane material major part is cellulose membrane or cellulose blending film.Also have affinity ligand is covalently bound to (as polyacrylamide, poly-trimethylolpropene acid esters etc.) on some high polymer particles, adopt general milipore filter, large biological molecule is carried out purifies and separates, obtain effect preferably.Close with technology of the present invention, and people such as ALNguyen (BiotechnolBioeng, 1989,34:1186) adopt acryloyl chloride and aminobenzene carbonamidine and acrylamide under the condition of secluding air, to carry out liquid-phase bulk polymerization, make a kind of water miscible high polymer.This copolymer and trypsase are directly produced affinity interaction, made the water-soluble polymer of band trypsase affinity ligand.Utilize again that to hold back be that 100,000 daltonian general milipore filters carry out ultra-filtration and separation,, reach the purpose of purifies and separates trypsase or its inhibitor to remove other foreign protein.But adopt this method, toxicity such as used acryloyl chloride, benzenecarboximidamide are bigger when not only synthetic, and the formality complexity.Simultaneously, because copolymer and trypsase are direct-connected, do not have spacerarm, so separative efficiency being low again, only is 90% to the highest tryptic rejection, and binding capacity is 10.5mg/ml.
The purpose of this invention is to provide a kind of modified polysulphone super-filter membrane and preparation method.The operation of this technology of preparing is simple and easy, and production cost is low, and the product yield height is easy on the milipore filter of gained that enzyme or protein are carried out the immobilized affinity ultrafiltration film of making and can be used for the technical pure trypsin inhibitor is carried out purifies and separates.
Polysulphone super-filter membrane provided by the invention is that the employing polysulfones is that raw material obtains a kind of milipore filter through the modification processing, it is characterized in that being connected in this filter membrane band active function groups-NH
2Spacerarm possible constructions formula I or II represent:
The physical property of above-mentioned modified polysulphone super-filter membrane is: average pore size is at 20～80 μ m, and hole density is 5 * 10
9～8 * 10
9Hole/cm
2, the skin thickness of film is 5～12 μ m, supporting layer thickness is 50～120 μ m.
The preparation method of modified polysulphone super-filter membrane of the present invention mainly contains two steps: 1. the chemical modification of pair polysulfones raw material is handled and the film forming of 2. milipore filters, it is characterized in that the chemical modification of polysulfones can select one of following two kinds of synthetic methods to carry out:
1) acidylate-amination method:
Acidylate-amination method is to be raw material with the polysulfones; under the catalytic action of alchlor; under 60～80 ℃; make itself and paranitrobenzoyl chloride carry out acylation reaction (1); the gained product is 40～60 ℃ times and hydrazine (diamine) carries out aminating reaction (2), makes and is connected to band polar functional group-NH on the polysulfones molecule
2The spacer groups of base, its reaction equation is:
In the above-mentioned reaction (1), the addition of catalyst be polysulfones heavy 1～8%, the addition of reactant paranitrobenzoyl chloride (molal quantity) should be 1～4 times of polysulfones, reaction time is 1～6 hour, in the reaction (2), the addition of reactant hydrazine should be 1～5 times of polysulfones, and the reaction time is 2～6 hours.After reaction (2) finished, the conversion ratio of polysulfones was 30～50%.
2) chloromethylation-amination method
Chloromethylation-amination method is that polysulfones is carried out chloromethylation (3) with chloromethyl ether earlier down at 20～30 ℃, again product and p-phenylenediamine (PPD) is carried out aminating reaction (4) under 55～65 ℃, makes the chemical modification polysulfones of band anilino-, and its reaction equation is
In the above-mentioned reaction (3), the addition of reactant chloromethyl ether (molal quantity) should be 1～4 times of polysulfones, reaction time is 1～6 hour, the addition of the middle reactant p-phenylenediamine (PPD) of reaction (4) should be 1～4 times of polysulfones, reaction time is 2～6 hours, and reaction (4) finishes the conversion ratio of back polysulfones 40～75%.
The film forming of milipore filter of the present invention, available phase inversion, technology is carried out routinely, it is characterized in that also can carrying out film preparation by following step:
With the chemical modification polysulfones under 45～60 ℃; by continuously evenly stirring and dissolving at N; in the dinethylformamide; fully after the uniform dissolution; under the protection of nitrogen vapour lysate is filtered, scraper striking film forming is used in the degassing then on glass plate; after in air, exposing 20～50 seconds, immerse film forming in the redistilled water that contains 2～10%NaCl.Make average pore size between 20～80 μ m through this process, hole density is 5 * 10
9～8 * 10
9Hole/cm
2, the skin thickness of film is 5～12 μ m, the back strut layer thickness is the milipore filter of 50～120 μ m.
Have active group-NH as above-mentioned by the prepared modified polysulphone super-filter membrane that goes out of method provided by the present invention
2, since can be under the effect of glutaraldehyde crosslinked with large biological molecule such as trypsase, also can by diazo-reaction under 0～4 ℃,, make affine separating medium (affinity ultrafiltration film) with its generation covalent bond.This affinity ultrafiltration film can be used for large biological molecule, carries out purifies and separates as tryptose ester inhibitor, below by example technology of the present invention is given to illustrate further.
Example 1, the preparation 1 of modified polysulphone super-filter membrane
Adopting acidylate-amination method that polysulfones is carried out modification handles; its process is as follows: PS-DL (1) (η=0.57) polysulfones that produces with Dalian first plastic molding and processing plant is a raw material; alchlor is catalyst (addition be polysulfones weight 5%); under 70 ℃; make itself and paranitrobenzoyl chloride react (addition is 3 times of polysulfones mole gram number); react after 2 hours, isolate product.Be under 50 ℃,, reacted 4 hours, isolate reactant, washed product with product hydrazine reaction (the hydrazine addition is 4 times of polysulfones mole gram number).The conversion ratio of its polysulfones reaches 45%, utilizes conventional phase inversion to make modified polysulphone super-filter membrane with above-mentioned product, and its film thickness is 100 μ m, and average pore size is the modified polysulphone super-filter membrane 1 of the band finger-like pore structure of 40 μ m.
The preparation 2 of example 2 modified polysulphone super-filter membranes
Adopting chloromethylation-amination method that polysulfones is carried out modification handles, its process is as follows: PS-DL (1) (η=0.57) polysulfones that produces with Dalian first plastic molding and processing plant is a raw material, react (the chloromethyl ether addition is 4 times of polysulfones molal quantity) with chloromethyl ether earlier down at 25 ℃, reacted 1 hour, again with reactant and p-phenylenediamine (PPD) (addition is 3 times of polysulfones molal quantity) reaction, reacted 4 hours down at 60 ℃, separated product washs, and the conversion ratio of its polysulfones is 70%.
Utilize above-mentioned modification polysulfones to be raw material, under 50～60 ℃, be dissolved in N, in the N-dimethylformamide (weight ratio of polysulfones and dimethylformamide is 8～15%), at N
2Under the gas lysate is filtered, the degassing then, on glass plate with scraper striking film forming, in air, expose 40～50 seconds after, immerse film forming in the second distillation aqueous solution of 10%NaCl, its thickness is the modified polysulphone super-filter membrane of the band finger-like pore structure of 105 μ m.
Example 3, the preparation of the affine filter membrane of modification polysulfones
Use-case 1 and 2 prepared modified polysulphone super-filter membranes, utilize the diazotising method to carry out the immobilized reaction of tryptose ferment. its reaction temperature is 4 ℃, use the phosphate buffer (0.05mol/l of tryptic concentration as 0.5mg/ml, PH8.1), be reactant liquor, carry out immobilized reaction 4 hours, after reaction finishes, use deionized water successively, 0.1 the NaCl solution of～1.0mol/L, deionized water repeated multiple times cleaning filter membranes, up to cleaning fluid till trypsase can not detect in the 280mm place of ultraviolet specrophotometer.Immobilized enzyme membrane is measured: immobilized 13.5mg trypsase on every gram modification PS membrane on the affinity membrane of example 1, supported tryptic relative vigor is 13000u/g.Immobilized 15mg trypsase on every gram modification PS membrane on the affinity membrane of example 2, supported tryptic relative vigor is 18200u/g,
The application of the affine filter membrane of example 4 modification polysulfones
The affine filter membrane that utilizes example 3 to make, be assembled in the membrane separator, and use this separator, the technical pure soybean trypsin inhibitor is carried out purifying, purification condition is: the slow middle liquid of phosphoric acid that with concentration is 0.2mg/ml technical pure soybean trypsin inhibitor, flow with 0.5mol/min cycles through affinity membrane separator, fully washs the film storehouse with 0.05mol/L phosphate buffer and deionized water respectively after 1 hour, in flowing out liquid, can not detect the existence of trypsin inhibitor till.Urea liquid with 6mol/L passes through affinity membrane separator under same flow velocity again, collects eluent, analyzes with high performance liquid chromatography, and the purity of its trypsin inhibitor can reach 98.5%, has improved 68 times than former industrial trypsin inhibitor purity.
By above-mentioned example, the preparation method that modification polysulfones provided by the present invention plays filter membrane is simple, reaction condition is easy to control, and prepared milipore filter is easy to tryptic immobilized, and obtains the practical milipore filter that can be used for the purifies and separates trypsin inhibitor.
Claims (4)
1. a modified polysulphone super-filter membrane is characterized in that being connected in this filter membrane band active function groups-NH
2Spacer groups, represent with structural formula I or II:
2. according to the described milipore filter of claim 1, it is characterized in that this filter membrane has following physical property: average pore size: 20～80 μ m; Hole density: 5 * 10
9～8 * 10
9Hole/cm
2, the skin thickness of film is 5～12 μ m; Supporting layer thickness: 50～120 μ m.
3. preparation method according to the described modified polysulphone super-filter membrane of claim 1 comprises modification and two key steps of film forming of polysulfones, and it is special gives birth to the modification that is polysulfones and adopt acidylate-amination method or chloromethylation-amination method to carry out; It is so-called that acidylate-the amination method is that polysulfones is under the catalytic action of alchlor; in 60～80 ℃; make itself and paranitrobenzoyl chloride carry out acylation reaction, the gained product is 40～60 ℃ times and hydrazine carries out aminating reaction, makes and is connected to band polar functional group-NH on the polysulfones molecule
2The spacer groups of base;
So-called chloromethylation-amination method is that polysulfones carries out chloromethylation with chloromethyl ether earlier down at 20～30 ℃, again reactant and p-phenylenediamine (PPD) is carried out aminating reaction under 55～65 ℃, makes the modification polysulfones of band anilino-.
4. purifies and separates that is used for trypsin inhibitor according to the described modified polysulphone super-filter membrane of claim 1, its special giving birth to is to carry out crosslinked with trypsase this milipore filter under the effect of glutaraldehyde earlier, or by diazo-reaction 0～4 ℃ down and trypsase immobilized, make affine filter membrane; Be assembled in this affine filter membrane and be used on the membrane separator technical pure trypsin inhibitor is carried out purifies and separates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112724A CN1059356C (en) | 1994-12-28 | 1994-12-28 | Modified polysulphone super-filter membrane and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112724A CN1059356C (en) | 1994-12-28 | 1994-12-28 | Modified polysulphone super-filter membrane and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1125635A CN1125635A (en) | 1996-07-03 |
| CN1059356C true CN1059356C (en) | 2000-12-13 |
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| CN94112724A Expired - Fee Related CN1059356C (en) | 1994-12-28 | 1994-12-28 | Modified polysulphone super-filter membrane and its preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978038B (en) * | 2005-12-09 | 2010-05-05 | 中国科学技术大学 | Method for preparing homogeneous-phase anion exchange film |
| CN100395008C (en) * | 2006-03-31 | 2008-06-18 | 华南理工大学 | A kind of hydrophilic-hydrophobic bipolar composite membrane and its preparation method |
| KR100813249B1 (en) | 2006-10-31 | 2008-03-13 | 삼성에스디아이 주식회사 | Polysulfone, electrolyte membrane using same and fuel cell using same |
| CN101100484B (en) * | 2007-06-12 | 2011-02-09 | 东华大学 | A method for rapid purification of cysteine protease inhibitors |
| CN102935336A (en) * | 2012-11-26 | 2013-02-20 | 天津工业大学 | Manufacturing method of blended flat affinity filter membrane |
| CN108939957B (en) * | 2018-08-01 | 2020-11-27 | 中南大学湘雅医院 | A kind of preparation method of Avacopan modified dialysis membrane |
| CN110943237B (en) * | 2018-09-21 | 2021-09-28 | 中国科学院大连化学物理研究所 | Application of ion-conducting membrane in flow battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63178806A (en) * | 1987-10-29 | 1988-07-22 | Toray Ind Inc | Production of semipermeable compound film having high performance |
| JPH05220389A (en) * | 1992-02-12 | 1993-08-31 | Showa Denko Kk | Affinity separation membrane |
| EP0569229A1 (en) * | 1992-05-05 | 1993-11-10 | W.R. Grace & Co. | High efficiency removal of low density lipoprotein-cholesterol from whole blood |
-
1994
- 1994-12-28 CN CN94112724A patent/CN1059356C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63178806A (en) * | 1987-10-29 | 1988-07-22 | Toray Ind Inc | Production of semipermeable compound film having high performance |
| JPH05220389A (en) * | 1992-02-12 | 1993-08-31 | Showa Denko Kk | Affinity separation membrane |
| EP0569229A1 (en) * | 1992-05-05 | 1993-11-10 | W.R. Grace & Co. | High efficiency removal of low density lipoprotein-cholesterol from whole blood |
Non-Patent Citations (1)
| Title |
|---|
| BIOTECHNOL BIOENG 34 1989.1.1 A.L.NGUYEN * |
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| Publication number | Publication date |
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| CN1125635A (en) | 1996-07-03 |
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