CN101029138A - Production of soluble polysaccharide-based magnetic composite nano-grain - Google Patents
Production of soluble polysaccharide-based magnetic composite nano-grain Download PDFInfo
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- CN101029138A CN101029138A CN 200710037301 CN200710037301A CN101029138A CN 101029138 A CN101029138 A CN 101029138A CN 200710037301 CN200710037301 CN 200710037301 CN 200710037301 A CN200710037301 A CN 200710037301A CN 101029138 A CN101029138 A CN 101029138A
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- soluble polysaccharide
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Abstract
Production of soluble polyose-magnetic composite nano-grain is carried out by synthesizing soluble polyose nano-template grain containing carboxy, inducing metal cation into template grain solution, bonding with carboxy in template grain by ionic bond and complex coordinate bond, dripping alkali deposit into solution, and in-situ co-precipitating to obtain the final product. The magnetic grain is 5-50wt%, it's simple, cheap, efficient and controllable and has no environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation method of technical field of nano material, be specifically related to a kind of preparation method of soluble polysaccharide-based magnetic composite nano-grain.
Background technology
The polymer magnetic nano-particle is meant by suitable preparation method and makes organic polymer combine the composite particles that formation has certain magnetic and special construction with the inorganic magnetic particle.Owing to quantum effect and the surface effects that the less size of nanoparticle, big specific surface area produce, give its many special nature.Composite particles has magnetic responsiveness and special surface functional group, can combine with other small molecules, macromole or cell etc., under the effect in magnetic field, make some response then, therefore, the polymer magnetic nano-particle is widely used in clinical diagnosis, contrast imaging, targeted drug, biomarker and separates and the fields such as immobilization of enzyme.
But because the affinity of organism and inorganics is relatively poor, it is difficult job that magnetic-particle is evenly dispersed in the polymer particle, and present preparation method comprises: entrapping method, monomer polymerization method, in-situ method three classes.
Entrapping method, be dispersed in magnetic-particle natural or synthetic macromolecule solution in, make the magnetic high-molecular particle by methods such as spraying, crosslinked, volatilization, depositions then.Entrapping method is simple to operate, but the particle diameter that makes is bigger, reaches more than the micron order, and the friendship that distributes is wide.
Monomer polymerization method, it is several to mainly contain suspension polymerization, dispersion polymerization, letex polymerization etc., but the particle of this method preparation generally uses a large amount of emulsifying agents and dispersion agent, the feasible polymer particle purification difficult that makes, and these class methods generally can only prepare hydrophobic particle, have further limited its use range.
Find through literature search prior art, " in-situ method " that at first proposes by Ugelstad etc., United States Patent (USP) title: Magnetic polymer particles and process for the preparationthereof, WO83/03920, this method is the suitable polymer particle of preparation earlier, generate by the chemical reaction original position under the controlled environment (nano-form or nano-reactor) that inorganic particle provides at polymer then, thus the preparation of realization polymer magnetic nano-particle.But in its used method, be to be template, limited use range with the oil soluble polymer particle that contains benzene.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of preparation method of soluble polysaccharide-based magnetic composite nano-grain is provided, make it utilize the function functional group of soluble polysaccharide-based nano-form particle and the key and the effect of metallic cation, synthetic polysaccharide of original position and magnetic-particle compound nanoparticle.The present invention is based on environmental protection, low cost, is conceived to efficiently, convenient, can be applied in the bio-medical field.
The objective of the invention is to be achieved through the following technical solutions, the present invention contains at first synthetic inside the soluble polysaccharide-based nano-form particle of carboxyl.Then, in the template particles aqueous solution, introduce metallic cation, make it by the abundant bonding of the carboxyl in ionic linkage, complex coordination key and the template particles, after solution is added dropwise to alkaline precipitating agent, generate inorganic magnetic nano particle (magnetic-particle) in the inner original position co-precipitation of template particles, thereby obtain soluble polysaccharide-based template and magnetic-particle compound nanoparticle.
The soluble polysaccharide-based nano-form particle of carboxyl is contained in described synthetic inside, and it is the method for describing among the ZL 200410053029.2 that its method adopts China Patent No..
The mol ratio of described metallic cation and carboxyl is 0.1-10.
Described alkaline precipitating agent, its pH value is between 10-14.Used alkaline precipitating agent can be a kind of in ammoniacal liquor, sodium hydroxide, the potassium hydroxide, but is not limited to above listed several.
Described generation magnetic-particle is to carry out under 10 ℃-80 ℃, and simultaneously with stirring, stirring velocity remains on 100-5000rpm.The magnetic-particle that generates can be a kind of in the magnetic oxide of iron, manganese, zinc, copper, nickel, cobalt, chromium and their the magnetic oxide mixture, but is not limited to above listed several.
Described soluble polysaccharide-based template and magnetic-particle compound nanoparticle, wherein the weight percent of magnetic-particle is 5%-50%, particle diameter is 5-50nm.
The present invention is applicable to all water-soluble polysaccharides, a kind of as in Natvosol, dextran, the chitosan, but be not limited to above listed several.
Soluble polysaccharide-based template that the present invention obtains and magnetic-particle compound nanoparticle, particle diameter are in the 50-800nm scope, and be controlled by the adjusting of polysaccharide molecular weight and polysaccharide, each set of dispense ratio of carboxylic monomer.Saturation magnetization is in the scope of 3-55emu/g, and its control can realize by the adjusting of metallic cation and carboxylic monomeric mol ratio.
The prepared magnetic composite nanoparticles aqueous solution of the present invention is purified through separation means such as dialysis, magnetic separation, washings, then can obtain the solid nanoparticle powder by cryodesiccated method, helps storing, transports and sells.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
With 0.86 gram MnCl
24H
2O, 0.15 gram ZnCl
2With 2.94 gram FeCl
36H
2O is dissolved in 50 ml deionized water; with previously prepared 50ml (0.1g/mL) particle diameter be that the mol ratio of 118nm, inner carboxyl and sugared ring element is 1: 10 a Natvosol base nano-form particle aqueous solution; under nitrogen protection, 80 ℃ of water-baths and even agitation condition, make both thorough mixing 15-20 minutes.Afterwards, this mixed aqueous solution is slowly splashed in the aqueous sodium hydroxide solution of 50 milliliters of 0.05mol/L, and keep stirring velocity more than 1000 rev/mins, react and stop after 1 hour, and be that 14000 dialysis tubing was dialysed 72 hours in a large amount of deionized waters with molecular weight cut-off, remove the unreacted metal ion.The composite nanoparticle aqueous solution that obtains frozen drying after magnetic separates is removed water and is obtained the nanoparticle pressed powder.This powder can water-solublely repeatedly obtain the stabilized nano particle aqueous solution.
Nanoparticle is regular globosity by transmission electron microscope observing in the above-mentioned system, and the dynamic laser scattering of light characterizes the about 126nm of its median size, and saturation magnetization is 3emu/g, and its aqueous solution can be stablized preservation for a long time.Wherein, the about 50nm of inorganic magnetic grain diameter, mass percent about 15%.
Embodiment 2:
With 0.91 gram FeCl
24H
2O and 2.48 gram FeCl
36H
2O is dissolved in 50 ml deionized water; with previously prepared 50ml (0.05g/mL) particle diameter be that the mol ratio of 54nm, inner carboxyl and sugared ring element is 1: 1 a dextran base nano-form particle aqueous solution; under nitrogen protection, 10 ℃ of room temperatures and even agitation condition, make both thorough mixing 17 minutes.Afterwards, this mixed aqueous solution is slowly splashed in the ammonia soln of 50 milliliter 5% (wt), and keep stirring velocity more than 1000 rev/mins, react and stop after 2 hours, and be that 14000 dialysis tubing was dialysed 72 hours in a large amount of deionized waters with molecular weight cut-off, remove the unreacted metal ion.The composite nanoparticle aqueous solution that obtains frozen drying after magnetic separates is removed water and is obtained the nanoparticle pressed powder.This powder can water-solublely repeatedly obtain the stabilized nano particle aqueous solution.
Nanoparticle is regular globosity by transmission electron microscope observing in the above-mentioned system, and the dynamic laser scattering of light characterizes the about 58nm of its median size, and saturation magnetization is 55emu/g, and its aqueous solution can be stablized preservation for a long time.Wherein, the about 5nm of inorganic magnetic grain diameter, mass percent about 50%.
Embodiment 3:
With 7.42 gram FeCl
36H
2O is dissolved in 50 ml deionized water; with previously prepared 50ml (0.1g/mL) particle diameter be that the mol ratio of 352nm, inner carboxyl and sugared ring element is 10: 1 a dextran base nano-form particle aqueous solution; under nitrogen protection, 60 ℃ of water-baths and even agitation condition, make both thorough mixing 15 minutes.Afterwards, this mixed aqueous solution is slowly splashed in the potassium hydroxide aqueous solution of 50 milliliter of 0.01 mol, and keep stirring velocity more than 1000 rev/mins, react and stop after 2 hours, and be that 14000 dialysis tubing was dialysed 72 hours in a large amount of deionized waters with molecular weight cut-off, remove the unreacted metal ion.The composite nanoparticle aqueous solution that obtains frozen drying after magnetic separates is removed water and is obtained the nanoparticle pressed powder.This powder can water-solublely repeatedly obtain the stabilized nano particle aqueous solution.
Nanoparticle is regular globosity by transmission electron microscope observing in the above-mentioned system, and the dynamic laser scattering of light characterizes the about 382nm of its median size, and saturation magnetization is 27.4emu/g, and its aqueous solution can be stablized preservation for a long time.Wherein, the about 10nm of inorganic magnetic grain diameter, mass percent about 25%.
Embodiment 4:
With 0.10 gram Ni (NO
3)
26H
2O and 0.19 gram FeCl
36H
2O is dissolved in 50 ml deionized water; with previously prepared 50ml (0.05g/mL) particle diameter be that the mol ratio of 726nm, inner carboxyl and sugared ring element is the chitosan-based nano-form particle aqueous solution of 1:5; under nitrogen protection, 60 ℃ of water-baths and even agitation condition, make both thorough mixing 20 minutes.Afterwards, this mixed aqueous solution is slowly splashed in the aqueous sodium hydroxide solution of 50 milliliters of 1mol/L, and keep stirring velocity more than 1000 rev/mins, react and stop after 2 hours, and be that 14000 dialysis tubing was dialysed 72 hours in a large amount of deionized waters with molecular weight cut-off, remove the unreacted metal ion.The composite nanoparticle aqueous solution that obtains frozen drying after magnetic separates is removed water and is obtained the nanoparticle pressed powder.This powder can water-solublely repeatedly obtain the stabilized nano particle aqueous solution.
Nanoparticle is regular globosity by transmission electron microscope observing in the above-mentioned system, and the dynamic laser scattering of light characterizes the about 782nm of its median size, the about 35emu/g of saturation magnetization, and its aqueous solution can be stablized preservation for a long time.Wherein, the about 16.7nm of inorganic magnetic grain diameter, mass percent about 5%.
Claims (10)
1, a kind of preparation method of soluble polysaccharide-based magnetic composite nano-grain, it is characterized in that, the soluble polysaccharide-based nano-form particle of carboxyl is contained at first synthetic inside, then, in the template particles aqueous solution, introduce metallic cation, make it by the abundant bonding of the carboxyl in ionic linkage, complex coordination key and the template particles, alkaline precipitating agent is added drop-wise in the solution, generate magnetic-particle in the inner original position co-precipitation of template particles, thereby obtain soluble polysaccharide-based template and magnetic-particle compound nanoparticle; Described soluble polysaccharide-based template and magnetic-particle compound nanoparticle, wherein the weight percent of magnetic-particle is 5%-50%.
2, the preparation method of soluble polysaccharide-based magnetic composite nano-grain according to claim 1 is characterized in that, the mol ratio of described metallic cation and carboxyl is 0.1-10.
3, the preparation method of soluble polysaccharide-based magnetic composite nano-grain according to claim 1 is characterized in that, described alkaline precipitating agent, and its pH value is between 10-14.
According to the preparation method of claim 1 or 3 described soluble polysaccharide-based magnetic composite nano-grains, it is characterized in that 4, described alkaline precipitating agent is a kind of in ammoniacal liquor, sodium hydroxide, the potassium hydroxide.
5, the preparation method of soluble polysaccharide-based magnetic composite nano-grain according to claim 1 is characterized in that, described generation magnetic-particle is to carry out under 10 ℃-80 ℃, simultaneously with stirring.
6, the preparation method of soluble polysaccharide-based magnetic composite nano-grain according to claim 5 is characterized in that, described stirring, and its speed remains on 100-5000rpm.
7, the preparation method of soluble polysaccharide-based magnetic composite nano-grain according to claim 1 or 5, it is characterized in that, described magnetic-particle is a kind of in the magnetic oxide of iron, manganese, zinc, copper, nickel, cobalt, chromium and their the magnetic oxide mixture.
8, the preparation method of soluble polysaccharide-based magnetic composite nano-grain according to claim 1 or 5 is characterized in that described magnetic-particle, its particle diameter are 5-50nm.
9, the preparation method of soluble polysaccharide-based magnetic composite nano-grain according to claim 1, it is characterized in that, described soluble polysaccharide-based template and magnetic-particle compound nanoparticle, particle diameter is in the 50-800nm scope, and saturation magnetization is in the scope of 3-55emu/g.
10, according to the preparation method of claim 1 or 9 described soluble polysaccharide-based magnetic composite nano-grains, it is characterized in that described water-soluble polysaccharide, a kind of in Natvosol, dextran, the chitosan.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009127045A1 (en) * | 2008-04-16 | 2009-10-22 | Stemcell Technologies Inc. | Magnetic particles |
| WO2010078675A1 (en) * | 2008-12-30 | 2010-07-15 | 陕西北美基因股份有限公司 | The drug delivery vehicle using gold-magnetic composite particles coated by polysaccharides and its preparation |
| CN101890173A (en) * | 2010-07-16 | 2010-11-24 | 江苏大学 | Preparation method of magnetic resonance imaging contrast agent of magnetic water-soluble chitosan |
| CN102863655A (en) * | 2012-09-24 | 2013-01-09 | 厦门大学 | Chain-ball-shaped magnetic chitosan/acetate cellulose and preparation method thereof |
| CN105084498A (en) * | 2015-07-14 | 2015-11-25 | 湖南科技大学 | Preparation method and application for chitosan modified collagen-iron-manganese oxide |
| CN105174406A (en) * | 2015-08-04 | 2015-12-23 | 湖南科技大学 | Preparation method of chitosan modified collagen-iron manganese oxide under ultraviolet irradiation condition and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO155316C (en) * | 1982-04-23 | 1987-03-11 | Sintef | PROCEDURE FOR MAKING MAGNETIC POLYMER PARTICLES. |
| GB2393728A (en) * | 2002-10-04 | 2004-04-07 | Nanomagnetics Ltd | Magnetic nanoparticles |
| CN1254488C (en) * | 2004-07-22 | 2006-05-03 | 上海交通大学 | High efficient preparing method for nano particles based on water soluble polysaccharide |
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2007
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009127045A1 (en) * | 2008-04-16 | 2009-10-22 | Stemcell Technologies Inc. | Magnetic particles |
| CN102067250A (en) * | 2008-04-16 | 2011-05-18 | 干细胞技术公司 | Magnetic particles |
| US9701935B2 (en) | 2008-04-16 | 2017-07-11 | Stemcell Technologies Inc. | Magnetic particles |
| WO2010078675A1 (en) * | 2008-12-30 | 2010-07-15 | 陕西北美基因股份有限公司 | The drug delivery vehicle using gold-magnetic composite particles coated by polysaccharides and its preparation |
| CN101890173A (en) * | 2010-07-16 | 2010-11-24 | 江苏大学 | Preparation method of magnetic resonance imaging contrast agent of magnetic water-soluble chitosan |
| CN102863655A (en) * | 2012-09-24 | 2013-01-09 | 厦门大学 | Chain-ball-shaped magnetic chitosan/acetate cellulose and preparation method thereof |
| CN102863655B (en) * | 2012-09-24 | 2015-03-25 | 厦门大学 | Chain-ball-shaped magnetic chitosan/acetate cellulose and preparation method thereof |
| CN105084498A (en) * | 2015-07-14 | 2015-11-25 | 湖南科技大学 | Preparation method and application for chitosan modified collagen-iron-manganese oxide |
| CN105174406A (en) * | 2015-08-04 | 2015-12-23 | 湖南科技大学 | Preparation method of chitosan modified collagen-iron manganese oxide under ultraviolet irradiation condition and application |
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