CN1309779C - Process for preparing biological degradable polymer magnetic composite nano particle - Google Patents
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- CN1309779C CN1309779C CNB2004100664583A CN200410066458A CN1309779C CN 1309779 C CN1309779 C CN 1309779C CN B2004100664583 A CNB2004100664583 A CN B2004100664583A CN 200410066458 A CN200410066458 A CN 200410066458A CN 1309779 C CN1309779 C CN 1309779C
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Abstract
The present invention discloses a preparation mehthod for biodegradable polymer magnetic compound nanometer particles. The method is characterized in that the water solution of polyvinyl alcohol or the water solution of polyethylene glycol or distilled water itself is adopted as a water phase, the solution of biodegradable polymer acetone of synthesis polyesters is adopted as an oil phase, wherein nanometer ferroferric oxide magnetic powder can firstly dispersed in an oil phase solution by means of ultrasonic dispersion, and the oil phase is then added into the water phase, the acetone is eliminated by natural volatilization, and an emulsion of the biodegradable polymer magnetic compound nanometer particles can be obtained after the magnetic particles which do not be compounded are eliminated. The method has the advantages of easy and operation and realization, and since the water and the water solution of the polyvinyl alcohol (PVA) or the polyethylene glycol (PEG) are adopted as the water phase, the acetone is adopted as the oil phase, the present invention also has the advantages of safety, low toxicity and high selectivity when drugs are packaged.
Description
Technical field
The present invention relates to the preparation method of polymer magnetic composite nano particle, relate in particular to a kind of preparation method of Biodegradable polyester magnetic composite nano particle.
Background technology
The polymer magnetic complex microsphere is a kind of new function material that development in recent years is got up, and it has the wide prospect of quoting at aspects such as fine chemistry industry, environmental monitoring, immobilized enzyme, targeted drug, immunoassay, cellular segregation, makeup.The solid support material of the magnetic microsphere that research at present is more has polyethylene, polystyrene, polymethylmethacrylate, polyoxyethylene glycol, polyvinyl alcohol, albumin, gelatin etc.
The polymer magnetic complex microsphere is applied to the drug targeting system, and particularly the cancer therapy drug targeted system is that the seventies begins latter stage.1979, it was that the magnetic microsphere of carrier is used for the theory of targeted drug system that Mosbach etc. disclose in american documentation literature 4335094 biodegradable polymers, and has set forth the method for using it for pharmacological agent.Cancer therapy drug magnetic microsphere carrier system be with medicine with have the magnetic responsiveness material and combine the complete pharmacology system that constitutes.In magnetic and medicated injection body, apply simultaneously the foreign field of certain field intensity in the tumour outside, utilize magnetic and medicated flowing property and induced by magnetic field performance, with magnetic medicine carrier fixing with the tumour target area in.Its advantage is to avoid engulfing of reticuloendothelial system scavenger cell, and medicine is concentrated in the target area, can reduce dosage, and the toxic side effect that reduction or elimination medicine whole body distribute and cause improves drug effect.If is pharmaceutical carrier with the Biodegradable Polymers, also can give its sustained release performance, slowly discharge in the target area, controlled release.
The preparation method of magnetic medicinal microglobule is different because of its solid support material.For amino polymer is the magnetic medicinal microglobule of carrier, as albumin, gelatin, enzyme, polylysine etc., general chemically crosslinked curing or the heat cross-linking solidification method of adopting, after promptly earlier magnetic substance, solid support material, medicine three being mixed and made into emulsion, the method by heating or chemically crosslinked makes solid support material solidify balling-up.As far back as 1977, it was one of preparation method of carrier magnetic microsphere that Yapel JR etc. just disclose this base polymer---heat cross-linking solidification method (american documentation literature 4169804).
For polyethylene, polystyrene, solid support materials such as polymethylmethacrylate generally adopt polymerization, as dispersion polymerization, suspension polymerization, letex polymerization etc.With this base polymer is that the magnetic microsphere of carrier can obtain comparatively ideal core-shell type structure, but because it lacks biological degradability, makes its application limited.
Polyvinyl alcohol (PVA), polyoxyethylene glycol materials such as (PEG) reports to some extent also that as the magnetic microsphere carrier its preparation method is emulsification-solvent evaporation method, compound emulsion method etc.Report with the biodegradable synthesizing polyester class material magnetic microsphere that is carrier is less.1991, Duguay DG etc. prepared the large grain size magnetic polylactic acid microsphere with emulsion-solvent evaporation method, and introducing content in poly(lactic acid) is the magnetic substance of 5-10%, because its particle diameter is not suitable for targeting drug delivery system in the millimeter level.Calendar year 2001, it is the magnetic polylactic acid medicine carrying microballoons of 0.16 ± 0.06 μ m that the method for human emulsions such as Spain Gomez-Lopera has made particle diameter.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polymer magnetic composite nano particle.
For achieving the above object, the present invention is achieved in that a kind of preparation method of biological degradable polymer magnetic composite nano particle, this method water adopts polyvinyl alcohol water solution or the polyoxyethylene glycol aqueous solution or distilled water itself, oil phase adopts synthesizing polyester class biodegradable polymer acetone soln, earlier the nano ferriferrous oxide magnetic through ultra-sonic dispersion in oil-phase solution, again oil phase is added aqueous phase, naturally acetone is removed in volatilization, remove not composite magnetic particle, must stablize the magnetic responsiveness emulsion at last.
When the aqueous phase described in the present invention adopted polyvinyl alcohol, polyvinyl alcohol water solution concentration was 1～20%, and the polyvinyl alcohol alcoholysis degree is higher than 88%; When water adopted polyoxyethylene glycol, the polyoxyethylene glycol concentration of aqueous solution was 1～20%, and polyoxyethylene glycol PEG molecular weight is 2000～10000.
Adopting oil phase concentration in the described oil phase is 0.001～0.015g/ml.
Better, the profit volume ratio is 0.1～2.5 among the present invention.
Polyester biodegradable polymkeric substance described in the present invention can be poly(lactic acid), polycaprolactone, polyglycolic acid or its combination.
Nano ferriferrous oxide magnetic magnetic amount described in the present invention is 4%～50% of an amount of polymers.
The present invention utilizes biodegradable synthesizing polyester class material to be carrier, adopts non-solvent to cause the method that is separated, and the polymer magnetic composite particles particle diameter of preparation is controlled below 200nm, and operation is simple.It is water that the present invention adopts the aqueous solution of water and PVA, PEG, and acetone is oil phase, has the advantage of safety and low toxicity, alternative strong, simple to operate during packaging medicine, does not have complicated last handling process.The present invention can be by telomerized polymer kind, polymer formation component parameter such as molecular weight, copolymerization ratio, polymer concentration, magnetic charging capacity, water component, oil-water ratio control its particle diameter, to satisfy more needs.
Embodiment
Be described in further detail below in conjunction with example, the example of being lifted below being to be understood that does not comprise all the elements of the present invention just in order to explain the present invention:
Embodiment 1
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 4/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, and concentration is 0.01g/ml, the magnetic charging capacity is 4.8%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 82.3nm, Fe content is 1.7%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 52.03%.
Embodiment 2
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.3080dl/g, and concentration is 0.01g/ml, the magnetic charging capacity is 4.9%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 135nm, Fe content is 1.5%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 27.80%.
Embodiment 3
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 12/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.3408dl/g, and concentration is 0.01g/ml, the magnetic charging capacity is 4.9%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 134nm, Fe content is 1.3%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 14.68%.
Embodiment 4
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 2000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.5322dl/g, and concentration is 0.01g/ml, the magnetic charging capacity is 4.8%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 193nm, Fe content is 1.100%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 0.01%.
Embodiment 5
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 8000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.5901dl/g, and concentration is 0.01g/ml, the magnetic charging capacity is 4.8%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 81.6nm, Fe content is 1.460%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 60.12%.
Embodiment 6
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 10000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.7021dl/g, and concentration is 0.01g/ml, the magnetic charging capacity is 4.9%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 81.9nm, Fe content is 1.157%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 61.44%.
Embodiment 7
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, and concentration is 0.005g/ml, the magnetic charging capacity is 10.1%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 81.4nm, Fe content is 3.958%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 56.97%.
Embodiment 8
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, and concentration is 0.003g/ml, the magnetic charging capacity is 15.6%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 81.3nm, Fe content is 5.223%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 59.64%.
Embodiment 9
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, and concentration is 0.001g/ml, the magnetic charging capacity is 25.8%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 82.6nm, Fe content is 10.235%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 62.80%.
Embodiment 10
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, and concentration is 0.015g/ml, the magnetic charging capacity is 4%, water is a distilled water, and the profit volume ratio is 1 o'clock, and the median size that obtains magnetic composite microsphere is 84.9nm, Fe content is 1.156%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 33.05%.
Embodiment 11
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, and concentration is 0.01g/ml, the magnetic charging capacity is 5.4%, water is a distilled water, and the profit volume ratio is 0.1 o'clock, and the median size that obtains magnetic composite microsphere is 70.3nm, Fe content is 0.965%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 26.65%.
Embodiment 12
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, and intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, and concentration is 0.01g/ml, the magnetic charging capacity is 5.7%, water is a distilled water, and the profit volume ratio is 2.5 o'clock, and the median size that obtains magnetic composite microsphere is 95.4nm, Fe content is 1.008%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 25.36%.
Embodiment 13
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, concentration is 0.01g/ml, the magnetic charging capacity is 4.9%, it is 88% polyvinyl alcohol water solution that water adopts 1% alcoholysis degree, the profit volume ratio is 1 o'clock, the median size that obtains magnetic composite microsphere is 84.9nm, Fe content is 1.168%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 25.66%.
Embodiment 14
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, concentration is 0.01g/ml, the magnetic charging capacity is 4.8%, it is 88% polyvinyl alcohol water solution that water adopts 10% alcoholysis degree, the profit volume ratio is 1 o'clock, the median size that obtains magnetic composite microsphere is 83.5nm, Fe content is 2.248%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 23.47%.
Embodiment 15
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, concentration is 0.01g/ml, the magnetic charging capacity is 4.9%, it is 88% polyvinyl alcohol water solution that water adopts 20% alcoholysis degree, the profit volume ratio is 1 o'clock, the median size that obtains magnetic composite microsphere is 83.9nm, Fe content is 2.598%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 20.69%.
Embodiment 16
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, concentration is 0.01g/ml, the magnetic charging capacity is 4.8%, water adopts 1% polyoxyethylene glycol-2000 aqueous solution, the profit volume ratio is 1 o'clock, the median size that obtains magnetic composite microsphere is 74.6nm, Fe content is 1.795%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 27.56%.
Embodiment 17
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, concentration is 0.01g/ml, the magnetic charging capacity is 4.9%, water adopts the 15% polyoxyethylene glycol aqueous solution-6000, the profit volume ratio is 1 o'clock, the median size that obtains magnetic composite microsphere is 82.9nm, Fe content is 2.184%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 24.28%.
Embodiment 18
The polymkeric substance that oil phase adopts is the polylactic acid-polyglycol multipolymer, it is 4000 that polymkeric substance adopts molecular weight polyethylene glycol, the copolymerization ratio is 5/1, intrinsic viscosity is the polylactic acid-polyglycol multipolymer of 0.2175dl/g, concentration is 0.01g/ml, the magnetic charging capacity is 4.9%, water adopts 20% polyoxyethylene glycol-10000 aqueous solution, the profit volume ratio is 1 o'clock, the median size that obtains magnetic composite microsphere is 86.7nm, Fe content is 2.658%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 23.89%.
Embodiment 19
It is the polycaprolactone of 0.5263dl/g that the polymkeric substance that oil phase adopts adopts intrinsic viscosity, concentration is 0.01g/ml, the magnetic charging capacity is 5.6%, water adopts 1% polyoxyethylene glycol-10000 aqueous solution, the profit volume ratio is 1 o'clock, the median size that obtains magnetic composite microsphere is 156nm, and Fe content is 2.587%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 25.46%.
Embodiment 20
It is the polyglycolic acid of 0.2567dl/g that the polymkeric substance that oil phase adopts adopts intrinsic viscosity, concentration is 0.01g/ml, the magnetic charging capacity is 6.3%, water is a distilled water, the profit volume ratio is 1 o'clock, the median size that obtains magnetic composite microsphere is 178nm, and Fe content is 2.697%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 28.47%.
Embodiment 21
It is polyglycolic acid-copolymer of poly lactic acid of 0.2785dl/g that the polymkeric substance that oil phase adopts adopts intrinsic viscosity, concentration is 0.01g/ml, the magnetic charging capacity is 50%, water is a distilled water, the profit volume ratio is 2.5 o'clock, the median size that obtains magnetic composite microsphere is 186nm, and Fe content is 13.46%, and the rate of descent with respect to natural subsidence under the 0.01T the action of a magnetic field increases 38.65%.
Claims (6)
1. the preparation method of a biological degradable polymer magnetic composite nano particle, this method water adopts polyvinyl alcohol water solution or the polyoxyethylene glycol aqueous solution or distilled water itself, oil phase adopts synthesizing polyester class biological degradation polyalcohol acetone soln, earlier the nano ferriferrous oxide magnetic through ultra-sonic dispersion in oil-phase solution, again oil phase is added aqueous phase, naturally acetone is removed in volatilization, remove not composite magnetic particle, obtain the biological degradable polymer magnetic composite nano particle emulsion, the used oil phase concentration is 0.001～0.015g/ml.
2. according to the preparation method of claims 1 described a kind of biological degradable polymer magnetic composite nano particle, it is characterized in that: when described water adopts polyvinyl alcohol water solution, polyvinyl alcohol water solution concentration is 1～20%, and the polyvinyl alcohol alcoholysis degree is higher than 88%.
3. according to the preparation method of claims 1 described a kind of biological degradable polymer magnetic composite nano particle, it is characterized in that: when described water adopts the polyoxyethylene glycol aqueous solution, the polyoxyethylene glycol concentration of aqueous solution is 1～20%, and molecular weight polyethylene glycol is 2000～10000.
4. according to the preparation method of described any biological degradable polymer magnetic composite nano particle of claim 1～3, it is characterized in that: the profit volume ratio is 0.1～2.5.
5. the preparation method of a kind of biological degradable polymer magnetic composite nano particle according to claim 4, it is characterized in that: described polyester biodegradable polymkeric substance is meant poly(lactic acid), polycaprolactone, polyglycolic acid or its combination.
6. according to the preparation method of claims 5 described a kind of biological degradable polymer magnetic composite nano particles, it is characterized in that: described nano ferriferrous oxide magnetic magnetic amount is 4%～50% of an amount of polymers.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434456C (en) * | 2006-06-23 | 2008-11-19 | 武汉大学 | Method of preparing polymer nanometerl micron ball assisted by ultrasonic wave |
| JP2008056827A (en) * | 2006-08-31 | 2008-03-13 | Canon Inc | Magnetic particle and method for producing the same |
| CN100489032C (en) * | 2007-06-15 | 2009-05-20 | 中国科学院广州地球化学研究所 | Method for preparing composite magnetic polyurethane foam carrier and use thereof |
| CN101884805A (en) * | 2010-06-13 | 2010-11-17 | 西安交通大学 | Degradable composite material for anastomosis of canals and tissues in human body |
| CN102688494A (en) * | 2011-03-23 | 2012-09-26 | 卢世璧 | Preparation method of protein drug-carrying magnetic composite nano-material and application thereof |
| CN105440618A (en) * | 2015-12-23 | 2016-03-30 | 江苏道勤新材料科技有限公司 | Degradable magnetic plastic material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4335094A (en) * | 1979-01-26 | 1982-06-15 | Mosbach Klaus H | Magnetic polymer particles |
| DE4325386A1 (en) * | 1993-07-23 | 1995-01-26 | Ikosta Gmbh Inst Fuer Korrosio | Magnetic fluid based on an aqueous carrier fluid |
| EP0689430A1 (en) * | 1993-03-17 | 1996-01-03 | Silica Gel Gmbh | Superparamagnetic particles, process for producing the same and their use |
| CN1132758A (en) * | 1995-04-06 | 1996-10-09 | 中国科学院成都有机化学研究所 | High-molecular microglobe and its prepn and use |
-
2004
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4335094A (en) * | 1979-01-26 | 1982-06-15 | Mosbach Klaus H | Magnetic polymer particles |
| EP0689430A1 (en) * | 1993-03-17 | 1996-01-03 | Silica Gel Gmbh | Superparamagnetic particles, process for producing the same and their use |
| DE4325386A1 (en) * | 1993-07-23 | 1995-01-26 | Ikosta Gmbh Inst Fuer Korrosio | Magnetic fluid based on an aqueous carrier fluid |
| CN1132758A (en) * | 1995-04-06 | 1996-10-09 | 中国科学院成都有机化学研究所 | High-molecular microglobe and its prepn and use |
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