CN1093428C - Chemical modification of microporous nylon film and preparation of affinity film with histidine ligand - Google Patents
Chemical modification of microporous nylon film and preparation of affinity film with histidine ligand Download PDFInfo
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- CN1093428C CN1093428C CN97103649A CN97103649A CN1093428C CN 1093428 C CN1093428 C CN 1093428C CN 97103649 A CN97103649 A CN 97103649A CN 97103649 A CN97103649 A CN 97103649A CN 1093428 C CN1093428 C CN 1093428C
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- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003446 ligand Substances 0.000 title abstract description 6
- 238000007385 chemical modification Methods 0.000 title description 8
- 229920006284 nylon film Polymers 0.000 title 1
- 239000012528 membrane Substances 0.000 claims abstract description 55
- 239000004677 Nylon Substances 0.000 claims abstract description 27
- 229920001778 nylon Polymers 0.000 claims abstract description 27
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000012982 microporous membrane Substances 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007853 buffer solution Substances 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 2
- 239000002158 endotoxin Substances 0.000 abstract description 15
- 125000003277 amino group Chemical group 0.000 abstract 2
- 125000003700 epoxy group Chemical group 0.000 abstract 2
- 125000006850 spacer group Chemical group 0.000 abstract 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 abstract 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 27
- 231100000284 endotoxic Toxicity 0.000 description 11
- 230000002346 endotoxic effect Effects 0.000 description 11
- 102000016943 Muramidase Human genes 0.000 description 5
- 108010014251 Muramidase Proteins 0.000 description 5
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 5
- 239000004325 lysozyme Substances 0.000 description 5
- 229960000274 lysozyme Drugs 0.000 description 5
- 235000010335 lysozyme Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001042 affinity chromatography Methods 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010999 medical injection Methods 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920000936 Agarose Polymers 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 208000037487 Endotoxemia Diseases 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001261 affinity purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000012501 chromatography medium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- External Artificial Organs (AREA)
Abstract
一种带组氨酸配基尼龙亲和膜的制备方法，其特征在于用分子量分布为2～80万道尔吨的尼龙微孔膜为原料，按下步骤：1)用盐酸溶液中对尼龙微孔膜进行水解，使膜上的酰胺键转变为氨基；2)用环氧法使水解后的尼龙膜上的氨基与环氧氯丙烷上的氯反应，生成带环氧基的尼龙膜；3)用已结合环氧基的尼龙膜与己二胺共价连接成间隔臂；4)采用戊二醛法使已接上间隔臂的尼龙膜与组氨酸配基共价结合成亲和膜。该亲和膜可用于对溶液中的内毒素进行有效的清除，为内毒素的去除又提供一种有效的新途径。A preparation method of a nylon affinity membrane with a histidine ligand, which is characterized in that a nylon microporous membrane with a molecular weight distribution of 2 to 800,000 daltons is used as a raw material, and the steps are as follows: 1) react nylon with hydrochloric acid solution The microporous membrane is hydrolyzed to convert the amide bond on the membrane into an amino group; 2) the amino group on the hydrolyzed nylon membrane is reacted with the chlorine on the epichlorohydrin to generate a nylon membrane with an epoxy group by an epoxy method; 3) Covalently link the nylon membrane with the epoxy group and hexamethylenediamine to form a spacer; 4) use the glutaraldehyde method to covalently combine the nylon membrane with the spacer and histidine ligand to form an affinity membrane . The affinity membrane can be used for effectively removing the endotoxin in the solution, and provides an effective new way for removing the endotoxin.
Description
Technical field
The invention provides a kind of chemical modification method of micropore nylon membrane and utilize the crosslinked histidine of this modified micropore nylon membrane to make affinity membrane.This affinity membrane can be used for endotoxin in the solution is removed.
Background technology
In the manufacturing process of biological medicine preparation, more or less can bring some thermal source materials into, bacterial endotoxin is wherein important a kind of, it is that the Gram-negative bacteria growing discharges or produced by the cracking of okioplast film when dead.Its existence has great harm to human body, and the denier endotoxin enters human body can cause fever, blood vessel dilatation, and symptoms such as diarrhea, even cause faintness and dead.Endotoxemia is the very high very dangerous disease of a kind of death rate clinically.The endotoxin molecule is complex structure not only, and is of a great variety, and molecular weight is big, and distribution is wide, therefore removes various medical water, and medicine, the endotoxin in biochemical preparation and the blood are very difficult tasks.The physical absorption of Cai Yonging in the past, acid, alkali or oxidising agent decompose, and it is all undesirable that technology such as ion-exchange or ultrafiltration are carried out removal effect to it.Adopt in recent years high specific and optionally affinity chromatography obtained very big success, succeeded in developing several posts system and chromatographic media and can be used for removing endotoxin in water and some pharmaceutical preparations, but after chemical modification, made the affinity membrane of being with the histidine aglucon and still be not reported with the technology that this film is used for endotoxic removal with nylon 66 films.
Summary of the invention
The chemical modification method that the purpose of this invention is to provide a kind of micropore nylon membrane, and this crosslinked histidine of micropore nylon membrane through chemical modification is made affinity membrane.This affinity membrane can be used for the endotoxin in the solution is effectively removed, for endotoxic removal provides a kind of effective new way again.
The preparation method of the chemical modification of micropore Buddhist nun Buddhist nun film of the present invention and band histidine aglucon affinity membrane thereof presses step:
1. with hydrochloric acid nylon 66 miillpore filters are hydrolyzed, even the amido link on the film changes amino into, its course of reaction is as (1):
2. the activation of hydrolysis nylon membrane promptly makes amino and the reaction of the chlorine on the epoxychloropropane on nylon 66 films after the hydrolysis with epoxy method, generates nylon 66 films of band epoxy radicals, and its course of reaction is as (II):
3. being connected of activation nylon 66 films and spacerarm, promptly in conjunction with nylon 66 films and the covalently bound arm at interval of hexamethylene diamine of epoxy radicals, its course of reaction is as (III):
4. immobilized the make affinity membrane of affinity ligand on film, nylon 66 films and the histidine aglucon covalent bond that promptly adopt glutaraldehyde method to make to connect spacerarm are made affinity membrane, its course of reaction as (IV) and (V):
Specifically, in the above-mentioned reaction (1), be that nylon 66 films with molecular weight distribution from 20,000 to 800,000 dalton's (ton) are raw material, in 1～6MHCl solution in 25～40 ℃ of following oscillating reactions 10～72 hours, make the abundant hydrolysis of amido link on nylon 66 films become amino, fully wash with distilled water after the hydrolysis to neutrality.In the said hydrolyzed process as can shorten the reaction time with dense HCl solution; Reaction (II) is carried out in alkaline solution, under 50～60 ℃, hydrolysis nylon 66 films are under agitation put into the dimethyl sulfoxide (DMSO) be the epoxychloropropane of solvent to react 3～5 hours, make amino and the reaction of the chlorine on the epoxychloropropane on the nylon membrane, generate nylon 66 films of band epoxy radicals, reaction finishes the back earlier with rare HCl solution, repeatedly film is rinsed well with distilled water again.Can replace epoxychloropropane with glutaraldehyde in the above-mentioned reaction.Reaction (III) is carried out in ethanol water, with NaOH or HCl the pH value of solution value is transferred to 11, to join while stirring in the ethanol water that contains hexamethylene diamine through the film that reaction (II) is handled, under 50～60 ℃, reacted 2～4 hours, reaction finishes the back earlier with rare HCl solution, and is with deionized water that film is fully clean again, and sops up water remaining on the film with filter paper.The also available hexamethylene diamine of hexamethylene diamine in the above-mentioned reaction, octamethylenediamine, the certain herbaceous plants with big flowers diamines replaces.Reaction (IV) is at NaH
2PO
4Make glutaraldehyde and nylon 66 film reactions that connect spacerarm in the buffer solution (pH7.2～7.5), reaction temperature is 20～30 ℃, reaction carries out making in 2～4 hours the amino on the spacerarm to change aldehyde radical into, and reaction finishes the back and uses the buffer solution flushing membrane, uses the distilled water washes clean again.Above-mentioned reaction also can replace glutaraldehyde to carry out with epoxychloropropane.Reaction (V) is also at NaH
2PO
4Finish in the buffer solution, the pH value is 7.2～7.5, under 25～30 ℃, make histidine and nylon 66 film reactions that activated with glutaraldehyde 4～6 hours, histidine is immobilized to film, after reaction finishes, film is clean with distilled water flushing, and promptly making of the present inventionly has interactional nylon 66 affinity membranes of specificity to endotoxin.
The specific embodiment
Below by embodiment technology of the present invention is given to illustrate further.
The preparation of embodiment 1 nylon 66 affinity membranes
With average pore size is 0.45 μ m, thickness is 0.12mm, molecular weight distribution is a raw material from 2～800,000 dalton's's (ton) nylon 66 films, in 2MHCl solution in 35 ℃ of following oscillating reactions 50 hours, finish the hydrolysis (1) of nylon 66 films, with distilled water fully wash until neutrality, be cut into the film that diameter is 50mm thereafter.
In 50ml water, add 12gNaOH and stir even all backs adding 100ml dimethyl sulfoxide (DMSO), 20ml epoxychloropropane, 0.5gKBH
4, after stirring, saying good-bye adds 50 nylon 66 films after the hydrolysis while stirring, 60 ℃ of down reactions 3 hours, finishes reaction (II), thereafter earlier with the rare HCl of 0.01m ol/L, again with the distilled water flushing membrane repeatedly of saying good-bye.
Preparation 80ml contains 50% ethanol water, add the 1g hexamethylene diamine, with 0.1mol/LNaOH or 0.1mol/L HCl solution the pH value of solution value is transferred to 11 after the stirring and dissolving, say good-bye and add nylon 66 films that obtain after above-mentioned (II) reaction while stirring, in 50 ℃ of following oscillating reactions 2 hours, reaction (III) finishes the back and use earlier 0.01NHCl, and is with deionization that film is thoroughly clean and sop up water remaining on the film with filter paper again.
At 80ml 0.05mol/L NaH
2PO
4Add the 75g25% glutaraldehyde solution in the buffer solution (pH7.2～7.5), after stirring, saying good-bye adds nylon 66 films that above-mentioned reaction (III) is handled, and in 25 ℃ of following oscillating reactions 3 hours, finishes reaction (IV), uses earlier 0.1mol/L NaH
2PO
4Buffer solution is said good-bye and is washed 3 times, washs film with distilled water again.
At 80ml 0.1mol/NaH
2PO
4Add the 0.5g histidine, 0.4gKBH in (pH7.2～7.4) buffering
4Stir, in nylon 66 films that add while stirring under 30 ℃ after above-mentioned reaction (IV) is handled, reaction can be finished reaction (V) in 5 hours under vibration, and film is taken out, and saying good-bye to rinse well with distilled water just to make nylon 66 affinity membranes of the present invention.The content of the immobilized affinity ligand of this film is 50～100 μ mol/g, and the desorption constant is 3.0 * 10
-8Mol/L, this medium is suitable for doing affinity purification.
Endotoxic removal in the embodiment 2 medical water
Be assembled into membrane separator with embodiment 1 50 prepared nylon 66 affinity membranes, allow 1 liter of endotoxin concns be 1.3eu/ml, at flow is by this separator under 0.5～2ml/ divides, collecting and measuring by endotoxin concns in the water behind the membrane separator with the quantitative chromogenic assay method of tripeptides UV absorption is 0.03eu/ml, and endotoxic clearance is more than 95%.
3 couples of embodiment contain endotoxic removal in the amino acid whose medical injection
Utilize the membrane separator of example 2, the medical injection 500ml that forms by essential amino acids such as Gly, Thr, Val, Mat, Leu, Phe, Lys, make it contain endotoxin 220eu, under 0.5～1.5ml/ shunt volume, pass through example 2 described affinity membrane separators, collect endotoxin and various amino acid whose content in the liquid after measuring film respectively, the result shows endotoxic clearance more than 75%, to the amino acid whose rate of recovery more than 90%.
Endotoxic removal in the solution such as 4 pairs of albumin of embodiment, lysozyme
Allow the concentration be that bovine serum albumin(BSA) (BSA) and the lysozyme of 5mg/ml, 1mg/ml absorbs (in them contained in plain concentration be 100eu/ml) by by diameter 50mm respectively, the membrane separator of 30 nylon 66 histidine affinity membranes assemblings, in solution salt concentration is 0.1～0.2mol/L, the pH value is 3～8, flow is to pass through membrane separator under the experiment condition that divides of 0.5～2ml/, measure to collect the concentration of endotoxin and BSA in the liquid, lysozyme respectively, endotoxic clearance is respectively 82% and 85%, and the rate of recovery of BSA and lysozyme can reach 95% and 90% respectively.
Nylon 66 affinity membranes that utilize the inventive method preparation are at solution salt concentration 0.1～0.2mol/L, in the solution of pH value 3～8, interior plain in the multiple pharmaceutical preparation are had preferable removal effect.
The regeneration of embodiment 5 nylon 66 affinity membranes
Used nylon 66 affinity membranes of example 2～4 can be with the NaOH that contains 0.2mol/L and 0.5%, the NaTDC of W/W does not have heat source water solution and washs, make affinity media obtain regeneration, nylon affinity membrane after the regeneration carries out the endotoxic separation process of example 2～4 removals equally can reach same effect, and regenerative process can be carried out repeatedly.
Comparative example
The agarose Sepharose4B that biotechnology and applied biology magazine (volume was 134 pages in 1988 the 10th) have been reported the production of human Sweden Pharmacia companies such as Japanese H.Matsumae is a raw material, the post affinity chromatograph filling of the band histidine affinity ligand of after chemical modification, making, aglucon content is 0.2～0.5mg/g, the affinity chromatographic column of loading with this affinity media is about 90% to endotoxic clearance in the water, to bovine serum albumin(BSA), endotoxic clearance is about 80% in the biologic products such as lysozyme, and their rate of recovery is respectively 90% and 86%.Compare with the film affinity chromatography, the major defect of post affinity chromatography is to be difficult to realize scale, serialization, automation mechanized operation, and might make the large biological molecule inactivation.
Claims (4)
1. preparation method with histidine aglucon nylon affinity membrane is characterized in that with molecular weight distribution being that 2～800,000 dalton's's (ton) nylon-microporous membrane is a raw material, presses step:
1), make the amido link on the film change amino into in the hydrochloric acid solution nylon-microporous membrane being hydrolyzed;
2) make amino and the reaction of the chlorine on the epoxychloropropane on the nylon membrane after the hydrolysis with epoxy method, generate the nylon membrane of band epoxy radicals;
3) with in conjunction with the nylon membrane and the covalently bound arm at interval of hexamethylene diamine of epoxy radicals;
4) adopt glutaraldehyde method to make the nylon membrane that connects spacerarm become affinity membrane with histidine aglucon covalent bond.
2. according to the described preparation method of claim 1, it is characterized in that step:
1) be in 1～6MHCl solution in 25～40 ℃ of following oscillating reactions 10～72 hours, make the amido link hydrolysis on the nylon membrane become amino, fully wash to neutrality with distilled water after the hydrolysis;
2) be in alkaline solution, to carry out, under 50～60 ℃, the hydrolysis nylon membrane is under agitation put into the dimethyl sulfoxide (DMSO) be the epoxychloropropane of solvent to react 3～5 hours, make amino and the reaction of the chlorine on the epoxychloropropane on the nylon membrane, generate the nylon membrane of band epoxy radicals, reaction finishes the back earlier with rare HCl solution, repeatedly film is rinsed well with distilled water again;
3) in ethanol water, carry out, with NaOH or HCl the pH value of solution value is transferred to 11, will be through reacting 2) film handled joins in the ethanol water that contains ethylenediamine while stirring, under 50～60 ℃, reacted 2～4 hours, reaction finishes the back earlier with rare HCl solution, and is with deionized water that film is fully clean again, and sops up water remaining on the film with filter paper;
4) be at NaH
2PO
4Make glutaraldehyde and second connect the nylon membrane reaction of spacerarm in the buffer solution (pH7.2～7.5), reaction temperature is 20～30 ℃, reaction carries out using in 2～4 hours the amino on arm to change aldehyde radical into, and reaction finishes the back and uses the buffer solution flushing membrane, uses the distilled water washes clean again; Then at NaH
2PO
4In the buffer solution, the pH value is 7.2～7.5, makes histidine and the nylon membrane reaction that activated with glutaraldehyde 4～6 hours under 25～30 ℃, and histidine is immobilized to film, and is after reaction finishes that film is clean with distilled water flushing, makes nylon affinity membrane.
3. according to the described preparation method of claim 1, it is characterized in that step 2) replace epoxychloropropane to react with glutaraldehyde.
4. according to the described preparation method of claim 1, it is characterized in that the step 3) ethylenediamine, octamethylenediamine or certain herbaceous plants with big flowers diamines replace hexamethylene diamine to react.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103649A CN1093428C (en) | 1997-03-26 | 1997-03-26 | Chemical modification of microporous nylon film and preparation of affinity film with histidine ligand |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103649A CN1093428C (en) | 1997-03-26 | 1997-03-26 | Chemical modification of microporous nylon film and preparation of affinity film with histidine ligand |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1194179A CN1194179A (en) | 1998-09-30 |
| CN1093428C true CN1093428C (en) | 2002-10-30 |
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ID=5166797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97103649A Expired - Fee Related CN1093428C (en) | 1997-03-26 | 1997-03-26 | Chemical modification of microporous nylon film and preparation of affinity film with histidine ligand |
Country Status (1)
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|---|---|
| CN (1) | CN1093428C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324048C (en) * | 2003-02-21 | 2007-07-04 | 中国科学院大连化学物理研究所 | Method of eliminating endotoxin from interferon preparation |
| CN102743985B (en) * | 2012-06-19 | 2014-08-13 | 浙江大学 | Preparation method for polysulfone-serine affinity membrane used for removing endotoxin |
| JP6334522B2 (en) * | 2012-07-19 | 2018-05-30 | ダウ グローバル テクノロジーズ エルエルシー | Composite polyamide membranes with increased carboxylic acid functionality |
| WO2014179024A1 (en) * | 2013-05-03 | 2014-11-06 | Dow Global Technologies Llc | Composite polyamide membrane derived from an aliphatic acyclic tertiary amine compound |
| CN104190272A (en) * | 2014-09-04 | 2014-12-10 | 北京碧水源膜科技有限公司 | Anti-pollution composite reverse osmosis membrane and preparation method thereof |
| CN107011481B (en) * | 2016-01-27 | 2018-11-02 | 中国科学院大连化学物理研究所 | A kind of preparation method of endotoxin absorbent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3746668A (en) * | 1970-12-26 | 1973-07-17 | Fuji Photo Film Co Ltd | Process for preparing a porous nylon film |
| US4673504A (en) * | 1980-10-27 | 1987-06-16 | Cuno Inc. | Charge modified microporous membrane |
-
1997
- 1997-03-26 CN CN97103649A patent/CN1093428C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3746668A (en) * | 1970-12-26 | 1973-07-17 | Fuji Photo Film Co Ltd | Process for preparing a porous nylon film |
| US4673504A (en) * | 1980-10-27 | 1987-06-16 | Cuno Inc. | Charge modified microporous membrane |
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| Publication number | Publication date |
|---|---|
| CN1194179A (en) | 1998-09-30 |
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