CN105504320A - Biological affinity membrane, preparation method and application thereof - Google Patents
Biological affinity membrane, preparation method and application thereof Download PDFInfo
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- CN105504320A CN105504320A CN201511002359.3A CN201511002359A CN105504320A CN 105504320 A CN105504320 A CN 105504320A CN 201511002359 A CN201511002359 A CN 201511002359A CN 105504320 A CN105504320 A CN 105504320A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention discloses a biological affinity membrane, a preparation method and application thereof. The biological affinity membrane is made by using an amphipathic carbon material as matrix carrier, grafting affinity ligands on the surface of the amphipathic carbon material by adopting a covalent binding method and using the functionalized amphipathic carbon material as an additive to be blended with a hydrophobic membrane material. The functionalized amphipathic carbon material is obtained by evenly fixing the affinity ligands to the surface of the amphipathic carbon material by means of the covalent binding method and is used as the additive to prepare the affinity membrane. The prepared biological affinity membrane is of a micropore/macroporous structure, has large inner surface area, high connectivity and mechanical stability and can remove endotoxin in a protein solution in a high-selectivity mode.
Description
Technical field
The invention belongs to technical field of membrane, be specifically related to a kind of affine microbial film, preparation method and application thereof.
Background technology
Intracellular toxin be a kind of toxicity extremely strong cause inflammation and pyrogenic substances, be the principal causative medium of endotoxemia and septic shock, the intracellular toxin of low dosage just can bring out the disease that systemic inflammatory response syndrome (SIRs), multiple organ dysfunction syndrome syndromes (MODS), Sepsis etc. cause the important death of each age group.
Along with the development of bio-pharmaceuticals and biomedical engineering association area, the removing of people to the microscale harmful substance that may exist in biological product is more and more paid attention to.Because endotoxic relative molecular mass is comparatively large, with macromole biological products at the same order of magnitude, the intracellular toxin effectively to remove in goods, particularly polluted in biological products is the focus of the area researches such as medical science, pharmacy, biotechnology always.
Up to now, endotoxic materials and methods in the removing biological products can applied in actual production process is also few.Some oneself also to there is adsorption efficiency through commercial product low, and the problems such as production cost is high, are difficult to promote the use of on a large scale.Therefore, find one to prepare simply, cheap, endotoxic material in removing biological products, remains focus and the difficult point of technical field of biological material research, still has very important value and practical significance efficiently.
Summary of the invention
The object of the present invention is to provide a kind of affine microbial film, preparation method and application thereof.
Based on above-mentioned purpose, the present invention takes following technical scheme:
A kind of affine biomembranous preparation method, comprises the steps:
(1) preparation of amphipathic carbon material: intestinal bacteria or yeast are jolted and is uniformly dispersed, get its upper strata bacteria suspension centrifugal, discard waste liquid, then acetone is added, jolt, centrifugal, discard acetone, with method repetitive operation 3 ~ 5 times, obtain intestinal bacteria or saccharomycetic cell walls, 2%(v/v is added again in the cell walls obtained) the glutaraldehyde PBS damping fluid of pH=6.0, reacts (hydrothermal carbonization synthesis method) 8 ~ 10h, after reaction terminates at 150 ~ 200 DEG C, be chilled to room temperature, lower sediment is washed, dry, obtain amphipathic carbon material;
(2) amphipathic carbon material surface grafting polyethylene imine or PXB: get amphipathic carbon material and be scattered in the PBS damping fluid of pH=5.5, add 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride successively, after N-hydroxysuccinimide activates, used the PBS damping fluid of pH=5.5 dispersed, add the polymine with the PBS buffer solution of pH=5.5 or Polymyxin B-sulfate USP, oscillatory reaction 4 ~ 8h, after reaction terminates, washing, drying, obtains the amphipathic carbon material of polymine or polymyxin functionalization;
(3) with the amphipathic carbon material of polymine or PXB functionalization for additive prepares affine microbial film: the amphipathic carbon material to above-mentioned polymine or polymyxin functionalization adds N, N-dimethylformamide, ultrasonic disperse is even, add polyvinylidene fluoride resin and polyvinylpyrrolidone, mechanical stirring 18 ~ 24h is to homodisperse film-casting liquid; By even for film-casting liquid plastic film mulch, be immersed in solidification liquid after prevapourising 1 ~ 3min in atmosphere and treat that film solidification is separated out, after soaking in pure water, namely obtain the affine microbial film that thickness is 150 ~ 200um.
Further, in step (2), amphipathic carbon material and 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, N-hydroxysuccinimide mass ratio are 1:(1 ~ 4): (1 ~ 4).
In step (2), the mass ratio of amphipathic carbon material and polymine or PXB is 1:(1 ~ 3).
Solidification liquid is ethanol and distilled water volume ratio in step (3) is 1:(3 ~ 6) mixed solution.
Affine microbial film obtained by above-mentioned preparation method.
The endotoxic application in removal biological products of described affine microbial film.
Its even particle size distribution of the amphipathic carbon material of functionalization of grafting affinity ligand in the present invention, monodispersity is better, can be dispersed and not easily gather in membrane formation mechanism, and hydrophobic membrane has good consistency.With the affine microbial film that the amphipathic carbon material of above-mentioned functionalization is prepared for additive and hydrophobic membrane materials polyvinylidene blending, possess millipore filtration and there is micropore/macroporous structure, large inner surface area, the feature of high connectivity and mechanical stability.This is affine, and microbial film had both had the recognition function of intracellular toxin molecule, can highly select to remove the intracellular toxin in biological product, have again good mechanical property and antifouling property, and preparation be simple, cheap.
The amphipathic of carbon material and the characteristic of rich surface containing functional group is made full use of in the present invention, affinity ligand is grafted to the method for amphipathic carbon material surface, can be used as multiple fixing, the preparation functionalization amphipathic carbon material of affinity ligand (such as: polymine, chitosan, histamine, Histidine etc.) at amphipathic carbon material surface that are rich in amino and imino-.
The affine microbial film that the present invention is prepared for additive with the amphipathic carbon material after grafting, can be used for and the affine microbial film of the blended preparation of other hydrophobic film materials.
Affine microbial film prepared by the present invention, overcomes the shortcoming easily gathered when inorganic nano-particle improves film character as additive, improves hydrophilicity and the mechanical property of film, film antifouling property is improved, greatly improves the work-ing life of film.
Affine microbial film of the present invention as a kind of affine filter membrane can be used for biological products purifying, extract and the removal of poisonous and harmful substances in preparation and serum, traditional Chinese medicine extraction, blood perfusion, the aspects such as water treatment.
Affine microbial film of the present invention can be widely used in biochemical industry and pharmaceutical sanitary field.
Accompanying drawing explanation
Fig. 1 be grafting affinity groups amphipathic carbon material structural representation, wherein: a is amphipathic carbon material; B is that amido linkage connects; C is intracellular toxin affinity ligand.
Fig. 2 is the affine biomembranous sample drawing of polyvinylidene difluoride (PVDF), wherein: a is polyvinylidene fluoride film; B is the polyvinylidene fluoride film adding amphipathic carbon material; C is the polyvinylidene fluoride film of the amphipathic carbon material adding grafting polyethylene imine; D is the polyvinylidene fluoride film of the amphipathic carbon material adding grafting PXB; As seen from the figure, add amphipathic carbon material in figure or all can prepare the uniform polyvinylidene fluoride film of Granular composite with the amphipathic carbon material of polyvinylidene difluoride (PVDF) or PXB functionalization.
Fig. 3 is the affine biomembranous contact angle figure of polyvinylidene difluoride (PVDF), wherein: a is polyvinylidene fluoride film; B is the polyvinylidene fluoride film adding amphipathic carbon material; C is the polyvinylidene fluoride film of the amphipathic carbon material adding grafting polyethylene imine; D is the polyvinylidene fluoride film of the amphipathic carbon material adding grafting PXB.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in detail.
Embodiment 1
With polymine or PXB for the affine biomembranous preparation of aglucon:
(1) preparation of amphipathic carbon material (ACPs): get 10g saccharomyces cerevisiae (Henan Losec brew-house provides) and jolt and be uniformly dispersed, get its upper strata canescence bacteria suspension centrifugal, discard waste liquid, then 10 ~ 15ml acetone is added, place 180r/min on shaking table and jolt 10 ~ 20min, centrifugal, discard acetone supernatant, with method repetitive operation 3 ~ 5 times, obtain the cell walls of cereuisiae fermentum, by substrate (cell walls namely obtained) 100ml2%(v/v) dispersion of the glutaraldehyde PBS damping fluid of pH=6.0, pour into after in high-temperature high-pressure reaction kettle and put into baking oven, hydrothermal carbonization synthesis 8 ~ 10h at 150 ~ 200 DEG C, after reaction terminates, be cooled to room temperature, outwell upper solution, the distilled water ultrasonic disperse washing of 100 ~ 150ml is added in lower sediment, after static 1 ~ 2min, retain upper strata and disperse good solution, solution continuation distilled water denseer for lower floor is continued ultrasonic disperse washing, repeat 7 ~ 10 times, discard the residue not easily disperseed, after upper solution is merged, centrifugal, abandoning supernatant, lower sediment is placed in baking oven 60 DEG C of drying 6 ~ 10h namely to obtain amphipathic carbon material and be labeled as ACPs.
(2) amphipathic carbon material surface grafting polyethylene imine or PXB: get dry amphipathic carbon material 100mg and be scattered in the PBS damping fluid of 10mlpH=5.5, add 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride of 192mg and the N-hydroxysuccinimide of 123mg successively, carry out activation 1 ~ 2h.Activation terminates rear centrifugal, abandoning supernatant, with the PBS buffer solution 3 ~ 5 times of pH=5.5, add the PBS damping fluid of 5mlpH=5.5 more wherein, 50mg polymine (the aladdin of the PBS buffer solution with 5mlpH=5.5 is added wherein after concussion dispersion, E107079, M.W.10000, 99%) or 25mg Polymyxin B-sulfate USP (purchased from Military Medical Science Institute), oscillatory reaction 4 ~ 8h, after reaction terminates, centrifugal, abandoning supernatant, by washing of precipitate 3 ~ 5 times, 50 DEG C of drying 8 ~ 10h in baking oven, obtain the amphipathic carbon material of polymine or PXB functionalization.The amphipathic carbon material of polyethyleneimine: amino-functionalization and the amphipathic carbon material of PXB functionalization are labeled as ACPs-PEI and ACPs-PMB respectively.
(3) with the amphipathic carbon material of polymine or PXB functionalization for additive prepares affine microbial film: get 85.5mg polymine or the amphipathic carbon material of PXB functionalization, join the N of 10ml, in N-dimethylformamide, ultrasonic disperse is even, then 1.71g polyvinylidene fluoride resin (Shanghai Sanaifu New Material Co., Ltd is added, FR904) and 0.285g polyvinylpyrrolidone, mechanical stirring 18 ~ 24h is to homodisperse film-casting liquid; By even for film-casting liquid plastic film mulch, be immersed in after prevapourising 1 ~ 3min in atmosphere in solidification liquid (ethanol and distilled water volume ratio are the mixed solution of 1:3 ~ 6) and treat that film solidification is separated out, by film pure water rinsing 3 ~ 5 times, then be placed in pure water to soak, every 8 ~ 12h changes water once, after changing water 7 ~ 8 times, naturally dries under normal temperature, obtain the affine microbial film that film thickness is 150 ~ 200 μm, be labeled as ACPs-PEI/PVDF film and ACPs-PMB/PVDF film respectively.The affine microbial film prepared according to above-mentioned same the method polyvinylidene fluoride film preparing blank and the amphipathic carbon material adding non-functionalization is in contrast labeled as pvdf membrane and ACPs/PVDF film respectively.
For above-described embodiment, Fig. 1 is the amphipathic carbon material structural representation of functionalization.
For above-described embodiment, the present invention by laser particle size and Zeta potential analyser the grafting result to polymine and PXB verify, test result is as shown in table 1:
Table 1
The successful grafting at amphipathic carbon material surface of polymine and PXB can be determined by polymine in table 1 and the amphipathic carbon material current potential of PXB functionalization and the change of particle diameter.
For above-described embodiment, Fig. 2 is the affine diffraction patterns for biomembrane samples figure of preparation.
The present invention adopts contact angle instrument as follows to the affine biomembranous wetting ability test result that enforcement 1 is obtained:
As Fig. 3: θ a:86.1 °, θ b:65.1 °, θ c:53.4 °, θ d:62.4 ° of (a: polyvinylidene fluoride film; B: the polyvinylidene fluoride film being added with amphipathic carbon material; C: the polyvinylidene fluoride film adding the amphipathic carbon material of grafting polyethylene imine; D: the polyvinylidene fluoride film adding the amphipathic carbon material of grafting PXB).In Fig. 3, the amphipathic carbon material adding polymine or PXB functionalization in hydrophobic membrane materials polyvinylidene difluoride (PVDF) can make wetting ability improve, and then increases the antifouling property of film.
The affine biomembranous mechanical properties that the present invention adopts universal electrical trier obtained to embodiment 1 is tested, and test speed is 10mm/min, and result is as following table 2:
Table 2
As shown in Table 2, the amphipathic carbon material adding polymine or PXB functionalization in polyvinylidene difluoride (PVDF) can the mechanical property of reinforcing membrane.
The present invention's bovine serum albumin is as pollutent, and the affine biomembranous anti-protein contamination performance obtained to embodiment 1 is tested, and test result is as following table 3:
Table 3
As shown in Table 3, in polyvinylidene difluoride (PVDF), add the anti-protein adheres that polymine or the amphipathic carbon material of PXB functionalization can improve film, the antifouling property of film is improved greatly.
Test example 1:
Take polymine as affine microbial film Endotoxin adsorption performance evaluation prepared by aglucon:
The affine microbial film of preparation is assemblied in affinity membrane separator, use 100ml without heat source water successively, the sodium hydroxide solution of 50ml0.1mol/ml, 50ml1.5mol/ml sodium chloride solution, 50ml normal saline solution, 100ml passes through affinity membrane separator without heat source water with the speed of 2ml/min, carries out pre-treatment to affine microbial film separator.
Pretreated affine microbial film separator is used for endotoxic removal in tap water, and endotoxin left amount is lower than 0.01EU/ml, and film regenerates 5 removal efficiency still higher than 99%.
Being used for pretreated membrane separation apparatus removing 0.9wt.%NaCl solution and concentration is intracellular toxin in the bovine serum albumen solution of 1mg/mL, and experimental result is as following table 4:
Table 4
ACPs-PEI/PVDF film first for the treatment of the endotoxin removal rate in physiological saline close to 98%; For process endotoxic in bovine serum albumen solution, endotoxin removal rate is about 94%.After ACPs-PEI/PVDF film of the present invention regenerates five times, clearance is still higher than 93%
Protein recovery, result is as following table 5:
Table 5
Test example 2:
Take PXB as affine microbial film Endotoxin adsorption performance evaluation prepared by aglucon:
The affine microbial film of preparation is assemblied in affinity membrane separator, use 100ml without heat source water successively, the sodium hydroxide solution of 50ml0.1mol/ml, 50ml1.5mol/ml sodium chloride solution, 50ml normal saline solution, 100ml passes through affinity membrane separator without heat source water with the speed of 2ml/min, carries out pre-treatment to affinity membrane separator.
Pretreated affine microbial film separator is used for endotoxic removal in tap water, and endotoxin left amount is lower than 0.01EU/ml, and film regenerates 5 removal efficiency still higher than 99%.
Being respectively used to pretreated membrane separation apparatus to remove 0.9wt.%NaCl solution and concentration is intracellular toxin in 1mg/ml bovine serum albumen solution, and experimental result is as following table 6:
Table 6
ACPs-PMB/PVDF film reaches 95% for the treatment of the endotoxin removal rate in physiological saline first; For process endotoxic in protein solution, endotoxin removal rate is more than 92%.After ACPs-PMB/PVDF film of the present invention regenerates five times, clearance is still higher than 92.4%.
Protein recovery, result is as following table 7:
Table 7
The foregoing is only preferred embodiment of the present invention; not in order to limit the present invention; when not deviating from the present invention's spirit and essence thereof, any amendment done, equivalent to replace and improvement etc., within the protection domain that all should be included in the claim appended by the present invention.
Claims (6)
1. an affine biomembranous preparation method, is characterized in that, comprise the steps:
(1) preparation of amphipathic carbon material: intestinal bacteria or yeast are jolted and be uniformly dispersed, gets its upper strata bacteria suspension centrifugal, discards waste liquid, then add acetone, jolt, centrifugal, discard acetone, with method repetitive operation 3 ~ 5 times, obtain intestinal bacteria or saccharomycetic cell walls, in the cell walls obtained, add glutaraldehyde PBS damping fluid, at 150 ~ 200 DEG C, react 8 ~ 10h, after reaction terminates, be chilled to room temperature, lower sediment is washed, dry, obtain amphipathic carbon material;
(2) amphipathic carbon material surface grafting polyethylene imine or PXB: get amphipathic carbon material and be scattered in the PBS damping fluid of pH=5.5, add 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride successively, N-hydroxysuccinimide activates, after end, with the PBS buffer solution 3 ~ 5 times of pH=5.5, then used the PBS damping fluid of pH=5.5 dispersed, add the polymine with the PBS buffer solution of pH=5.5 or Polymyxin B-sulfate USP, oscillatory reaction 4 ~ 8h, after reaction terminates, washing, dry, obtain the amphipathic carbon material of polymine or PXB functionalization,
(3) with the amphipathic carbon material of polymine or PXB functionalization for additive prepares affine microbial film: the amphipathic carbon material getting above-mentioned polymine or PXB functionalization joins N, in N-dimethylformamide, ultrasonic disperse is even, add polyvinylidene fluoride resin and polyvinylpyrrolidone, mechanical stirring 18 ~ 24h obtains homodisperse film-casting liquid; By even for film-casting liquid plastic film mulch, be immersed in solidification liquid after prevapourising 1 ~ 3min in atmosphere and treat that film solidification is separated out, after soaking in pure water, namely obtain the affine microbial film of thickness 150 ~ 200 μm.
2. affine biomembranous preparation method according to claim 1, it is characterized in that, in step (2), amphipathic carbon material and 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, N-hydroxysuccinimide mass ratio are 1:(1 ~ 4): (1 ~ 4).
3. affine biomembranous preparation method according to claim 1, is characterized in that, in step (2), the mass ratio of amphipathic carbon material and polymine or Polymyxin B-sulfate USP is 1:(1 ~ 3).
4. affine biomembranous preparation method according to claim 1, is characterized in that, solidification liquid is ethanol and distilled water volume ratio in step (3) is 1:(3 ~ 6) mixed solution.
5. adopt the arbitrary described affine microbial film obtained by preparation method of Claims 1-4.
6. the endotoxic application in removal biological products of affine microbial film described in claim 5.
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Cited By (2)
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| CN109122678A (en) * | 2018-07-13 | 2019-01-04 | 郑州欧姆康生物材料有限公司 | A kind of nano-silver loaded is in the nano-ag composite and its preparation method and purposes of amphipathic biological carbon material |
| CN110625132A (en) * | 2019-09-05 | 2019-12-31 | 浙江科曼奇生物科技股份有限公司 | Sulfhydrylation amphiphilic carbon residue/nano-silver compound, preparation method thereof and antibacterial leather |
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| CN101596422A (en) * | 2009-07-07 | 2009-12-09 | 浙江大学 | With amino acid is the preparation method of the polyvinylidene fluoride affinity membrane of aglucon |
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| US20050186218A1 (en) * | 2001-04-13 | 2005-08-25 | Wyeth Holdings Corporation | Removal of bacterial endotoxin in a protein solution by immobilized metal affinity chromatography |
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| CN101596422A (en) * | 2009-07-07 | 2009-12-09 | 浙江大学 | With amino acid is the preparation method of the polyvinylidene fluoride affinity membrane of aglucon |
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| CN110625132A (en) * | 2019-09-05 | 2019-12-31 | 浙江科曼奇生物科技股份有限公司 | Sulfhydrylation amphiphilic carbon residue/nano-silver compound, preparation method thereof and antibacterial leather |
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| CN105504320B (en) | 2018-01-26 |
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