CN106512749B - It is a kind of for the two-sided modified seperation film of blood purification and its preparation, application method - Google Patents

It is a kind of for the two-sided modified seperation film of blood purification and its preparation, application method Download PDF

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CN106512749B
CN106512749B CN201611108215.0A CN201611108215A CN106512749B CN 106512749 B CN106512749 B CN 106512749B CN 201611108215 A CN201611108215 A CN 201611108215A CN 106512749 B CN106512749 B CN 106512749B
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blood
seperation film
reverse side
film
seperation
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CN106512749A (en
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吕晓龙
武春瑞
倪非非
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Tianjin Polytechnic University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/36—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/36—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits
    • A61M1/3621—Extra-corporeal blood circuits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04—Tubular membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/38—Graft polymerization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/50—Polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones

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  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)
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Abstract

The present invention relates to a kind of two-sided modified seperation films for blood purification, seperation film contact blood stoste side is that positive, seperation film the side that penetrates is reverse side, the blood compatibility modification for improving material is done in the front of seperation film, is grafted the modified layer to the selective absorption of substance toxic in blood in the reverse side of seperation film.The separation membrane aperture for being usually used in blood purification is 0.2~0.45 μm, and present invention separation membrane aperture used is 0.5~5 μm, can through albumen entrapped cell；The front of microporous barrier optimizes modification by blood compatibility courage and uprightness, and specific aim improves the blood compatibility on membrane material surface；The reverse side of microporous barrier, grafting form selective absorption layer, and the property of can choose is adsorbed and removed the toxic molecule in blood, and specific aim improves the Selective adsorption of membrane material.

Description

It is a kind of for the two-sided modified seperation film of blood purification and its preparation, application method
Technical field
The invention belongs to seperation film fields, are related to blood separation, especially a kind of blood purification seperation film and its user Method.
Background technique
Blood plasma separation is to isolate blood plasma from blood first, then via blood perfusion device, what will be caused a disease in blood plasma divides greatly Sub- substance, then will be to the useful cell component of human body, displacement liquid and the defeated ex vivo of purified blood plasma by absorption resin removal It is interior, reach the purpose for the treatment of disease.The pathogenic macromolecular substances mainly removed of blood plasma separation have: free heavy chain or light chain protein and The various paraprotein such as cryoglobulin；Deposition can cause the immune complex of tissue damage within the organization；Human autoimmune's property The autoantibodies such as IgG, the IgM formed in disease；Excessive low-density albumen and excessive poisonous substance, drug etc. recycle toxin.Blood Slurry separation removes these virulence factors, so that it may which the generation or development for preventing certain diseases mitigate the damage of histoorgan, even It can restore organ dysfunction.Blood plasma separation can fast and effeciently remove liver function for giving treatment to serious hepatitis, hepatic failure patients Impaired poisonous substance and drug is that current a variety of causes of curing leads to the most strong side of poisoning to prevent further damaging liver function Method.The shortage of albumin and coagulation factor as caused by dyshepatia can be improved by supplement displacement liquid simultaneously, it is more beneficial In liver cell regeneration and liver function recovery.Meanwhile blood plasma separation can give treatment to anxious critical disease in the blood system and pancreatitis, severe are high The diseases such as pionemia.In addition, blood plasma separation also has adjustment effect to function of immune system, the ratio of antigen/antibody is such as converted More soluble immune complex is formed it into, its removing is promoted.
Blood plasma separation supportive treatment can regenerate for hepatic tissue provides stable vivo environment, regenerates beneficial to hepatic tissue, bright The endotoxin, serum bilirubin and medium molecular substance etc. for reducing severe hepatitis patient aobviously, from largely reducing The death rate of patient, and to morning, mid-term severe hepatitis treatment better effect.
Blood perfusion (Hemoperfusion, HP) is outside the blood lead body by patient, by with spectrum antidotal effect Adsorbent equipment, remove blood in exogenous and endogenic toxin, with reach purify blood method.To adsorbent material It is required that: safe to the human body nontoxic, no allergic reaction does not cause heat source, has stable chemical property, is not crushed, not easily to fall off, With good blood compatibility, it is provided simultaneously with good adsorption capacity.Adsorbent material includes: multifunctional C material, polysaccharide, Preparation, immunosorbent.Adsorbing adsorption mechanism includes: chemisorption, physical absorption and affine absorption.
The structure of presently used adsorbent material is generally porous microsphere, fibrous or porous prilled, adsorbent material Selective adsorption need to be improved, meanwhile, the blood compatibility that hydrophobic adsorbent material will lead to material is deteriorated, and destroys thin Born of the same parents lead to haemolysis, blood coagulation, therefore also need to take into account the blood compatibility of adsorbent material.It is adsorbed again after film filtering, two steps Method operation, increases contacting blood pollution risk, also, residual blood volume is big.Expensive, problem complicated for operation that there is also equipment.
Affine separation is a kind of method separated using biomolecule with the affinity interaction of predetermined substance realization substance, to mesh Mark product has selection specific adsorption well, affine to separate the life that will not influence biomolecule because separation condition is mild The rate of recovery of object activity, product is high.So affinity chromatography is widely used in, production concentration is low, biology in system of complicated component The separating-purifying of molecule.Combination of the affinity membrane as affinity chromatography technology and membrane technology is inheriting affinity chromatography technology Gao Xuan Advantage not available for the affinity chromatographies such as amplification fast with separating rate, easy while the features such as selecting property, high lytic activity.It is related to Range is very wide, including enzyme, protein and other large biological molecules isolate and purify；Isomer, the fractionation of chiral object；It is molten The detection of noxious material and adsorbing separation etc. in liquid, blood.But there are still blood compatibilities and selection separation property to take into account problem.
Bilirubin is typical toxin in a kind of blood, molecular formula C33H36O6N4, relative molecular mass 584.67 is A kind of nonpolar organic compound.The structural formula of bilirubin is as made of two methine bridges and a methylene bridges Chain tetrapyrrole, due to bilirubin hydrophilic radical in the molecule portion formed 6 pairs of hydrogen bonds, can be by bilirubin molecular folding At ridge tiles shape, therefore its internal hydrophilic radical can not form hydrogen bond with hydrone again, water-soluble poor.But easily penetrate cell membrane Even blood-brain barrier generates physiological-toxicity effect to human body.Since there are two propionic acid base side chains in bilirubin molecule, make bilirubin It is weakly acidic, to be soluble in alkaline solution.Bilirubin in blood is mainly with free state and in conjunction with human serum albumins Form exists, and will generate hyperbilirubinemia when its excessive concentration in blood.
Have containing hydrophobic gap to the bilirubin in blood in beta-cyclodextrin molecular structure containing 7 glucopyranose units Good suction-operated.The present invention is grafted Cyclodextrin Bridged in the reverse side of polyvinylidene fluoride microporous film, to remove the gallbladder in blood Red pigment.
Summary of the invention
It is an object of the invention to provide a kind of two-sided modification for blood purification in place of overcome the deficiencies in the prior art Seperation film and its preparation, application method, specific aim improve the blood compatibility and Selective adsorption on membrane material surface.
The technical proposal for solving the technical problem of the invention is:
A kind of two-sided modified seperation film for blood purification, it is front, seperation film that seperation film, which contacts blood stoste side, Through side be reverse side, the front of seperation film do improve material blood compatibility modification, connect in the reverse side of seperation film Modified layer of the branch to the selective absorption of substance toxic in blood.
Noxious material includes: to be poisoned for (1) medicine or poisonous substance: organophosphorus pesticide, rat poison, herbicide etc.；(2) severe Acute pancreatitis: cell factor, endotoxin, aromatic amino acid；(3) multiple organ failure syndrome: cell factor and inflammatory are situated between Matter；(4) shock lung diffuse alveolar injury: endotoxin etc.；(5) liver failure: bilirubin, bile acid, blood ammonia, short-chain fat Acid.In the compound grafting layer material of the reverse side specific aim of seperation film, detrimental substance in blood is specifically isolated, and is retained The ingredient useful to human body in blood.
Moreover, the separation membrane material is Kynoar, polyether sulfone, polysulfones, nylon, cellulose acetate.
Clinically common plasma separation membrane material mainly has: cellulose acetate (CA), polyvinyl alcohol (PVA), poly- methyl Methyl acrylate (PMMA), polyethylene (PE), polypropylene (PP) etc., Kynoar (PVDF) are a kind of excellent film materials Material, it has good chemical stability, mechanical performance and thermal stability, with the medical materials such as polyvinyl chloride, polyethylene, ABS Compare, be a kind of most hygienic engineering material, using its as raw material preparation membrane material extensive use in water treatment field.It is poly- Vinylidene film surface is smooth, and protein adsorption quantity is low, and blood can be effectively suppressed in the protein adsorption layer of film surface, make the filtering of film Velocity-stabilization.
Moreover, the separation membrane aperture is 0.5~5 μm.
Moreover, the shape of the seperation film is hollow-fibre membrane, plate membrane, tubular membrane.
Moreover, the noxious material is bilirubin, the modified layer is beta-cyclodextrin.
β-CD can and alkyl halide, carboxyl reaction, while can also with the hydroxyl of cyclodextrin react substance have hexa-methylene- 1,6- diisocyanate, carbonyl dimidazoles, glutaraldehyde, 4- vinyl benzyl chloride etc..
A kind of preparation method of the two-sided modified seperation film for blood purification: it is first done in seperation film front and improves material Hemocompatible surfaces processing, then in seperation film reverse side using grafting method grafting absorption macromolecular material.
Such as Kynoar blood separation membrane, positive anticoagulation etc. improves the surface of the blood compatibility of material Processing, can first use basic treatment method, it may be assumed that containing phase transfer catalyst, using NaOH, KOH/KMnO4, KOH/ methanol, LiOH/ isopropanol, NaOH/ phase reforming catalyst etc. can slough the HF of Kynoar film surface, be formed unsaturated Key.Great amount of hydroxy group is introduced by necleophilic reaction again.It can be with using plasma processing method: it is plasma-induced by Ar, PEG is grafted on pvdf membrane.Photochemical modification can also be used: use Electron beam pre-irradiation grafting method for modification pvdf membrane, it will Methyl methacrylate-grafted improves the blood compatibility of the materials such as the anticoagulant property of separation membrane surface to pvdf membrane surface. It can also be the methods of modified again using separation membrane surface ozone activation.
A kind of application method of the two-sided modified seperation film for blood purification: the blood for needing to purify is separate first The front of film, large scale ingredient are retained by seperation film, and referred to as dope is grafted functional layer through the liquid of seperation film first Selective absorption purification forms permeate, and permeate merges with dope completes blood purification process.Specifically: it will need to purify Blood introduce blood purification, blood first with the front face of seperation film, driven by pressure, the small molecular in blood Ingredient, such as haemocyanin, toxin can penetrate seperation film, and then toxic component can be inhaled by the adsorbent material of seperation film reverse side Attached, the blood stream after adsorption cleaning goes out blood purification, then merges with the blood cell etc. retained by seperation film, as net Change blood to return.Compared with after Conventional blood filtering in the two step purification methods for carrying out blood perfusion, the blood purification Advantage is that purification can be realized in a step, and reduces blood loss.
The advantages and positive effects of the present invention are:
1, the separation membrane aperture for being usually used in blood purification is 0.2~0.45 μm, present invention separation membrane aperture used is 0.5~ 5 μm, large-sized cell can be retained through the small-medium size substance in blood, such as albumen；Blood is passed through in the front of microporous barrier Compatibility optimizes modification, and specific aim improves the blood compatibility on membrane material surface；The reverse side of microporous barrier, grafting form selection Property adsorption layer, the property of can choose is adsorbed and removed the toxic molecule in blood, and specific aim improves the Selective adsorption of membrane material.
2, by the way that after micro-pore-film filtration blood, filtered solution is selectively adsorbed purification again, can be with high efficiency selected adsorbent material And reduce and the adsorption capacity of selective absorbent is required, moreover, filtering, absorption single stepping carry out, implementation process is simple, Existing blood filtration, the operation of perfusion resin two-step method can be replaced, equipment is simplified, easy to operate, reduces contacting blood and pollutes wind Danger, and reduce residual blood volume.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of this two-sided modified seperation film.
Specific embodiment
The invention will be further described below and by specific embodiment, following embodiment be it is descriptive, be not Limited, this does not limit the scope of protection of the present invention.
A kind of two-sided modified seperation film for blood purification, it is front, seperation film that seperation film, which contacts blood stoste side, Be reverse side through side, the blood compatibility modification for improving material is done in the front of seperation film, and the reverse side of seperation film is grafted with To the modified layer of the selective absorption of substance toxic in blood.
As shown in Figure 1,1 is the positive surface modifying material of film, blood compatibility is improved；2 be seperation film bulk material；3 For UF membrane hole；4 be the grafting adsorbent material of film reverse side.
Embodiment 1
The reverse side of the polyvinylidene fluoride hollow fiber microporous membrane blood purification of sealing two ends is immersed to the peroxidating of 5wt% 10min in benzoyl diethyl ether solution is dried at room temperature for after taking-up, removes ether.100mL volume 3wt% acrylic acid is water-soluble Liquid is added in flask, adds the n-butanol of 10mL, is passed through dissolved oxygen 30min in nitrogen removing solution, is passed through Kynoar The reverse side of hollow-fibre membrane blood purification, sealing, is heated to 70 DEG C of reaction 4h.It is poly- in the grafting of polyvinylidene fluoride microporous film reverse side It after acrylic acid, then reacts with beta-cyclodextrin, forms beta-cyclodextrin adsorption function layer in polyvinylidene fluoride microporous film reverse side.By blood The front of clarifier Pvdf Microporous Hollow Fiber Membrane and the NaOH aqueous solution of 20wt% haptoreaction 10 hours under 40 degree, then Polyethylene glycol is grafted on polyvinylidene fluoride film front.
Embodiment 2
5wt% ethylenediamine solution is prepared, NaOH aqueous solution is added, solution ph is adjusted to 12, sealing two ends are added Polyvinylidene fluoride hollow fiber microporous membrane, react 5h at 80 DEG C, cleaned to obtain the poly- inclined fluorine of reverse side amination with deionized water Ethylene microporous barrier.Then it is immersed in 5wt% polyacrylic acid aqueous solution, reaction overnight, is cleaned with deionized water at room temperature. It after polyvinylidene fluoride microporous film reverse side grafted polyacrylic acid, is reacted with beta-cyclodextrin, in polyvinylidene fluoride microporous film reverse side shape At beta-cyclodextrin adsorption function layer.By the NaOH aqueous solution of the front of Pvdf Microporous Hollow Fiber Membrane and 20wt% under 40 degree Haptoreaction 10 hours, then polyethylene glycol is grafted on polyvinylidene fluoride film front.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art For, under the premise of not departing from inventive concept, various modifications and improvements can be made, these belong to protection of the invention Range.

Claims (4)

1. a kind of two-sided modified seperation film for blood purification, it is characterised in that: seperation film contact blood stoste side is positive Face, seperation film through side be reverse side, the front of seperation film do improve material blood compatibility modification, seperation film it is anti- Face is grafted with the modified layer to the selective absorption of substance toxic in blood, and the separation membrane aperture is 0.5~5 μm, should The preparation method of two-sided modified seperation film includes the following steps:
(1) the reverse side of seperation film is immersed into certain time in benzoyl peroxide diethyl ether solution, be dried at room temperature for, remove after taking-up Remove ether；
(2) acrylic acid aqueous solution is added to the container, adds n-butanol, be passed through dissolved oxygen in nitrogen removing solution；
(3) the reverse side of seperation film is put into step (2) in solution, is heated to 70~80 DEG C of 4~5h of reaction, is grafted in seperation film reverse side It after polyacrylic acid, then reacts with beta-cyclodextrin, forms beta-cyclodextrin adsorption function layer；
By seperation film front with NaOH aqueous solution haptoreaction, then by polyethylene glycol be grafted on film front.
2. blood purification seperation film according to claim 1, is characterized in that: the separation membrane material is polyvinylidene fluoride Alkene, polyether sulfone, polysulfones, nylon, cellulose acetate.
3. blood purification seperation film according to claim 1, is characterized in that: the shape of the seperation film is doughnut Film, plate membrane, tubular membrane.
4. blood purification seperation film according to claim 1, is characterized in that: the noxious material is bilirubin, described Modified layer be beta-cyclodextrin.
CN201611108215.0A 2016-12-06 2016-12-06 It is a kind of for the two-sided modified seperation film of blood purification and its preparation, application method Expired - Fee Related CN106512749B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1557538A (en) * 2004-01-30 2004-12-29 浙江科锐生物科技有限公司 Method for preparing macromolecule resin type bilirubin sorbent
CN101862610A (en) * 2010-05-05 2010-10-20 大连理工大学 Absorption film for eliminating bilirubin and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1557538A (en) * 2004-01-30 2004-12-29 浙江科锐生物科技有限公司 Method for preparing macromolecule resin type bilirubin sorbent
CN101862610A (en) * 2010-05-05 2010-10-20 大连理工大学 Absorption film for eliminating bilirubin and preparation method thereof

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