CN103462806A - Magnetic polyelectrolyte microcapsule and preparation method thereof - Google Patents
Magnetic polyelectrolyte microcapsule and preparation method thereof Download PDFInfo
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- CN103462806A CN103462806A CN2013104441263A CN201310444126A CN103462806A CN 103462806 A CN103462806 A CN 103462806A CN 2013104441263 A CN2013104441263 A CN 2013104441263A CN 201310444126 A CN201310444126 A CN 201310444126A CN 103462806 A CN103462806 A CN 103462806A
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Abstract
The invention relates to a magnetic polyelectrolyte microcapsule and a preparation method of the microcapsule. A porous or hollow layer by layer self-assembly polyelectrolyte microcapsule is taken as a carrier, magnetic nanoparticles AFe2O4 (A is a divalent metal ion) are modified to enable the surfaces of the magnetic nanoparticles to have charges, and the magnetic polyelectrolyte microcapsule can be prepared by the electrostatic interaction between different charges of the polyelectrolyte arranged at the outermost layer of the microcapsule and the modified magnetic nanoparticles; the mass of the AFe2O4 nanoparticles is 15-50% of that of the polyelectrolyte microcapsule. The particle sizes of the microcapsule and the AFe2O4 nanoparticles can be adjusted, wherein the particle size of the microcapsule is 0.1-10mu m, and the particle sizes of AFe2O4 nanoparticles are 1-100mu m; the magnetism load quantity is high, so that the magnetic polyelectrolyte microcapsule is good in mangnetic responsiveness. According to the method, the modified magnetic nanoparticles AFe2O4 are absorbed electrostatically by the polyelectrolyte microcapsule, so that the magnetic microcapsule with targeting property can be prepared; the particle sizes of the AFe2O4 nanoparticles and the magnetism load quantity can be controlled; furthermore, the method is simple and convenient to operate, thus having good application prospect in the fields such as magnetic materials, cytobiology, molecular biology, medical science and the like.
Description
Technical field
The present invention relates to a kind of magnetic polyelectrolyte multiplayer microcapsule and preparation method thereof.
Background technology
Self assembly layer by layer (LBL) is the common method for preparing at present polyelectrolyte multiplayer microcapsule, and the LBL polyelectrolyte multiplayer microcapsule has significant advantage as pharmaceutical carrier, and it can be regulated and controled size, composition, structure, form and the wall thickness of microcapsule.At first, its particle diameter is controlled, monodispersity good, specific surface area is large, chemical stability is high, meets that the microcapsule drug loading is high, the requirement of slow release, protection pharmaceutically active; Secondly, its cyst material is generally water miscible macromolecule, can realize the structure of microcapsule and supporting of medicine under the gentle conditions such as room temperature, water environment, the toxic and side effects of avoiding organic solvent to exist; Again, the structural design of LBL polyelectrolyte multiplayer microcapsule has very large motility, as microsphere template or the porous microsphere template by selecting, can more easily obtain the polyelectrolyte multiplayer microcapsule of hollow or loose structure, also can build erose microcapsule by irregularly shaped template.Polyelectrolyte kind used comprises natural polymer and synthetic macromolecule, according to the purposes difference, can adopt one or more cyst materials to prepare microcapsule.
In recent years, along with nanosecond science and technology and biomedicine day by day deep, the magnetic nano-particle physical characteristic superior with it (as large as paramagnetism, specific surface area, gyromagnetism etc.), gradually at biomedicine field, as the aspects such as cell marking and separation, magnetic resonance Cheng Ying, pharmaceutical carrier and mangneto hyperthermia demonstrate application prospect widely.In actual applications, can be by its surface modification be improved to its dispersion stabilization.
The combination of magnetic nano-particle and microcapsule obtains the magnetic polyelectrolyte multiplayer microcapsule, it has a lot of good characteristics, as there is magnetic responsiveness, can realize targeting drug release under the effect of externally-applied magnetic field, particle diameter is little, and specific surface area is large, and surface characteristic is various, be easy to absorption, can by surface modification give its multiple reactive functional group in surface (as-OH ,-COOH ,-CHO ,-NH
2and then can, in conjunction with various functional mass, make microcapsule there is several functions ,-SH etc.), simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of magnetic polyelectrolyte multiplayer microcapsule and preparation method thereof.The method is by previously prepared good magnetic nanoparticle AFe
2o
4(A is bivalent metal ion, as Fe, and Ni, Mn, Zn, Co etc.) carry out being dispersed in microcapsule solution after surface modification, carry out Electrostatic Absorption.The Electrostatic Absorption method has advantages of many: particle diameter and the particle size distribution of (1) magnetic nano-particle are controlled, have good monodispersity; (2) prepared magnetic polyelectrolyte multiplayer microcapsule magnetic content is high and controlled; (3) carry the magnetic process simple, easy operating.
The present invention prepares polyelectrolyte multiplayer microcapsule by porous or the self assembly of hollow template surface layer layer, as to take chitosan, PAH, polylysine etc. be polycation, take polyglutamic acid, sodium alginate, kayexalate, polyacrylic acid etc. as polyanion structure hollow or porous micro-capsule, as carrier, the modification AFe by absorption with polyelectrolyte surface band opposite charges
2o
4magnetic nano-particle, thus the magnetic polyelectrolyte multiplayer microcapsule obtained.
According to above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of magnetic polyelectrolyte multiplayer microcapsule, take adopt porous or hollow layer by layer the self assembly polyelectrolyte multiplayer microcapsule be carrier, by magnetic nano-particle AFe
2o
4modification, wherein A is bivalent metal ion, makes modification AFe
2o
4surface is with the electric charge contrary with microcapsule outermost layer polyelectrolyte, by adopting electrostatic adsorption by modification AFe
2o
4deposit on porous or hollow microcapsule preparation magnetic response microcapsule; 15%～50% of the quality that described magnetic nano-particle is polyelectrolyte multiplayer microcapsule.
The particle diameter of described magnetic polyelectrolyte multiplayer microcapsule is 0.1～10 μ m, and the particle diameter of described magnetic nano-particle is 1～100nm.
Described magnetic nano-particle AFe
2o
4in bivalent metal ion A be: Fe, Ni, Mn, Zn or Co.
Described porous or hollow self assembly polyelectrolyte multiplayer microcapsule layer by layer are: take chitosan, PAH, polylysine etc. is polycation, take porous or the hollow microcapsule that polyglutamic acid, sodium alginate, kayexalate, polyacrylic acid etc. build as polyanion.
A kind of method for preparing the magnetic polyelectrolyte multiplayer microcapsule, concrete steps are:
1) by porous or the poly-yin, yang ion of hollow template surface layer layer self assembly, template is removed and obtained polyelectrolyte multiplayer microcapsule;
2) prepare magnetic nano-particle AFe by chemical coprecipitation
2o
4;
3) porous of surface band positive electricity or hollow microcapsule are written into magnetic nano-particle: the AFe for preparing 0.1 ~ 0.5mg/mL trisodium citrate, anion-modified dose of modification of ammonium citrate
2o
4aqueous solution, take 1 ~ 5mg surface band positive electricity porous or hollow microcapsule and be placed in centrifuge tube, adds the AFe of the above-mentioned modification of 1 ~ 5 mL
2o
4solution, after ultrasonic dispersion, adsorb 2 ~ 6h, and the centrifuge washing removal is not adsorbed magnetic particle and must be carried the magnetic microcapsule; The electronegative porous in surface or hollow microcapsule carry magnetic: prepare 0.1 ~ 0.5mg/mL HNO
3, the modification of the silica-based DOTMA cation modifier of N-trimethoxy AFe
2o
4aqueous solution, take 1 ~ 5mg surface band negative electricity porous or hollow microcapsule and be placed in centrifuge tube, adds the AFe of the above-mentioned modification of 1 ~ 5 mL
2o
4solution, after ultrasonic dispersion, adsorb 2 ~ 6h, and the centrifuge washing removal is not adsorbed magnetic particle and must be carried the magnetic microcapsule.
Compared with prior art, the present invention has following outstanding substantive distinguishing features and significant advantage:
Microcapsule of the present invention and AFe
2o
4the particle diameter of magnetic nano-particle is controlled, and year quantity of magnetism of prepared magnetic microcapsules is high, thereby magnetic responsiveness is good.This process is simple, easy operating.The present invention utilizes polyelectrolyte multiplayer microcapsule Electrostatic Absorption AFe
2o
4magnetic nano-particle, the magnetic microcapsules that preparation has targeting, magnetic content is high and controlled.The novel magnetic microcapsule has good application prospect in fields such as magnetic material, cytobiology, molecular biology and medical science.
The specific embodiment
Below in conjunction with embodiment, describe the present invention.
Embodiment 1: the Fe of preparation 0.32mg/mL trisodium citrate modification
3o
4aqueous solution (Fe
3o
4particle diameter be 10～15nm), take after about 1mg surface band positive electricity porous polyglutamic acid/chitosan microcapsules is placed in centrifuge tube and add 5mL trisodium citrate MODIFIED Fe
3o
4solution, after ultrasonic dispersion, 25 C condition absorption 2h, centrifuge washing is removed and is not adsorbed magnetic particle, then must carry the magnetic microcapsule through lyophilization, and its magnetic content is about 22%, and magnetic saturation intensity is about 7.6emu/g.
Embodiment 2: preparation 0.25mg/mL HNO
3the Fe of modification
3o
4aqueous solution (Fe
3o
4particle diameter be 10～20nm), take about 1mg surface band negative electricity porous alginate/chitosan microcapsule, add 5mL HNO
3mODIFIED Fe
3o
4solution, carry the magnetic process with embodiment 1.The magnetic microcapsules magnetic content obtained is about 17%, and magnetic saturation intensity is about 5.9 emu/g.
Embodiment 3: after taking about 1mg surface band positive electricity porous polylysine/the polyacrylic acid microcapsule being placed in centrifuge tube, add the CoFe that 8mL concentration is the modification of 0.28mg/mL ammonium citrate
2o
4solution (CoFe
2o
4particle diameter be 6～8nm), after ultrasonic dispersion, 37 C conditions absorption 2h, centrifuge washing, lyophilization must be carried the magnetic microcapsule, its magnetic content is about 28.8%, magnetic saturation intensity is about 9.6emu/g.
Embodiment 4: after taking about 1mg surface band negative electricity hollow PAH/the kayexalate microcapsule being placed in centrifuge tube, adding 7mL concentration is 0.25mg/mL HNO
3the Fe of modification
3o
4solution (Fe
3o
4particle diameter be 12～15nm), after ultrasonic dispersion, 25 C conditions absorption 4h, centrifuge washing, lyophilization must be carried the magnetic microcapsule, its magnetic content is about 23.5%, magnetic saturation intensity is about 7.2emu/g.
Embodiment 5: the Fe of preparation 0.4mg/mL trisodium citrate modification
3o
4aqueous solution (Fe
3o
4particle diameter be about 8～12nm), take about 1mg surface band positive electricity hollow PAH/polyacrylic acid microcapsule and add 5mL trisodium citrate MODIFIED Fe after being placed in centrifuge tube
3o
4solution, after ultrasonic dispersion, 25 C condition absorption 4h, centrifuge washing, lyophilization must be carried the magnetic microcapsule, and its magnetic content is about 27.2%, and magnetic saturation intensity is about 8.9emu/g.
Embodiment 6: after taking about 1mg surface band negative electricity polylysine/the polyglutamic acid porous micro-capsule being placed in centrifuge tube, adding 5mL concentration is 0.35mg/mL HNO
3the Fe of modification
3o
4solution (Fe
3o
4particle diameter be 6～10nm), after ultrasonic dispersion, 37 C conditions absorption 4h, centrifuge washing, lyophilization must be carried the magnetic microcapsule, its magnetic content is about 35.4%, magnetic saturation intensity is about 11.3emu/g.
Claims (5)
1. a magnetic polyelectrolyte multiplayer microcapsule, is characterized in that, take adopt porous or hollow layer by layer the self assembly polyelectrolyte multiplayer microcapsule be carrier, by magnetic nano-particle AFe
2o
4modification, wherein A is bivalent metal ion, makes modification AFe
2o
4surface is with the electric charge contrary with microcapsule outermost layer polyelectrolyte, by adopting electrostatic adsorption by modification AFe
2o
4deposit on porous or hollow microcapsule preparation magnetic response microcapsule; 15%～50% of the quality that described magnetic nano-particle is polyelectrolyte multiplayer microcapsule.
2. magnetic polyelectrolyte multiplayer microcapsule according to claim 1, is characterized in that, the particle diameter of described magnetic polyelectrolyte multiplayer microcapsule is 0.1～10 μ m, and the particle diameter of described magnetic nano-particle is 1～100nm.
3. magnetic polyelectrolyte multiplayer microcapsule according to claim 1, is characterized in that, described magnetic nano-particle AFe
2o
4in bivalent metal ion A be: Fe, Ni, Mn, Zn or Co.
4. magnetic polyelectrolyte multiplayer microcapsule according to claim 1 and 2, it is characterized in that, described porous or hollow self assembly polyelectrolyte multiplayer microcapsule layer by layer are: take chitosan, PAH, polylysine etc. is polycation, take porous or the hollow microcapsule that polyglutamic acid, sodium alginate, kayexalate, polyacrylic acid etc. build as polyanion.
5. a method for preparing magnetic polyelectrolyte multiplayer microcapsule according to claim 1, is characterized in that, concrete steps are:
1) by porous or the poly-yin, yang ion of hollow template surface layer layer self assembly, template is removed and obtained polyelectrolyte multiplayer microcapsule;
2) prepare magnetic nano-particle AFe by chemical coprecipitation
2o
4;
3) porous of surface band positive electricity or hollow microcapsule are written into magnetic nano-particle: the AFe for preparing 0.1 ~ 0.5mg/mL trisodium citrate, anion-modified dose of modification of ammonium citrate
2o
4aqueous solution, take 1 ~ 5mg surface band positive electricity porous or hollow microcapsule and be placed in centrifuge tube, adds the AFe of the above-mentioned modification of 1 ~ 5 mL
2o
4solution, after ultrasonic dispersion, adsorb 2 ~ 6h, and the centrifuge washing removal is not adsorbed magnetic particle and must be carried the magnetic microcapsule; The electronegative porous in surface or hollow microcapsule carry magnetic: prepare 0.1 ~ 0.5mg/mL HNO
3, the modification of the silica-based DOTMA cation modifier of N-trimethoxy AFe
2o
4aqueous solution, take 1 ~ 5mg surface band negative electricity porous or hollow microcapsule and be placed in centrifuge tube, adds the AFe of the above-mentioned modification of 1 ~ 5 mL
2o
4solution, after ultrasonic dispersion, adsorb 2 ~ 6h, and the centrifuge washing removal is not adsorbed magnetic particle and must be carried the magnetic microcapsule.
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Cited By (5)
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|---|---|---|---|---|
| CN104622845A (en) * | 2015-01-02 | 2015-05-20 | 吉林大学 | Preparation method of chitosan microcapsules containing magnetic nano particles inside |
| CN108451931A (en) * | 2018-04-04 | 2018-08-28 | 华侨大学 | A kind of PAH/F compound polyelectrolytes nano-carrier and preparation method thereof |
| CN108685841A (en) * | 2018-07-12 | 2018-10-23 | 广东药科大学 | Miniature drug delivery apparatus and preparation method thereof |
| CN110102229A (en) * | 2019-05-07 | 2019-08-09 | 深圳九星印刷包装集团有限公司 | Magnetic fluid liquid crystal microcapsule and preparation method and ink |
| CN112961526A (en) * | 2021-03-03 | 2021-06-15 | 中国船舶重工集团公司第七二五研究所 | Preparation method of magnetic particle enriched anticorrosion and antifouling integrated self-repairing microcapsule |
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| US20030219384A1 (en) * | 1998-03-19 | 2003-11-27 | Edwin Donath | Production of nanocapsules and microcapsules by layer-wise polyelectrolyte self-assembly |
| CN101077417A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院理化技术研究所 | Magnetic target medicine sustained and controlled release carrier material and preparation method and application thereof |
| CN101288664A (en) * | 2008-06-11 | 2008-10-22 | 东南大学 | Preparation method of magnetic nano microcapsule with nucleus/shell structure |
| CN102513046A (en) * | 2011-12-21 | 2012-06-27 | 上海大学 | Magnetic polyelectrolyte microcapsule and its preparation method |
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2013
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Patent Citations (4)
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| US20030219384A1 (en) * | 1998-03-19 | 2003-11-27 | Edwin Donath | Production of nanocapsules and microcapsules by layer-wise polyelectrolyte self-assembly |
| CN101077417A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院理化技术研究所 | Magnetic target medicine sustained and controlled release carrier material and preparation method and application thereof |
| CN101288664A (en) * | 2008-06-11 | 2008-10-22 | 东南大学 | Preparation method of magnetic nano microcapsule with nucleus/shell structure |
| CN102513046A (en) * | 2011-12-21 | 2012-06-27 | 上海大学 | Magnetic polyelectrolyte microcapsule and its preparation method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104622845A (en) * | 2015-01-02 | 2015-05-20 | 吉林大学 | Preparation method of chitosan microcapsules containing magnetic nano particles inside |
| CN108451931A (en) * | 2018-04-04 | 2018-08-28 | 华侨大学 | A kind of PAH/F compound polyelectrolytes nano-carrier and preparation method thereof |
| CN108685841A (en) * | 2018-07-12 | 2018-10-23 | 广东药科大学 | Miniature drug delivery apparatus and preparation method thereof |
| CN108685841B (en) * | 2018-07-12 | 2020-03-24 | 广东药科大学 | Miniature drug delivery device and method of making same |
| CN110102229A (en) * | 2019-05-07 | 2019-08-09 | 深圳九星印刷包装集团有限公司 | Magnetic fluid liquid crystal microcapsule and preparation method and ink |
| CN112961526A (en) * | 2021-03-03 | 2021-06-15 | 中国船舶重工集团公司第七二五研究所 | Preparation method of magnetic particle enriched anticorrosion and antifouling integrated self-repairing microcapsule |
| CN112961526B (en) * | 2021-03-03 | 2021-11-23 | 中国船舶重工集团公司第七二五研究所 | Preparation method of magnetic particle enriched anticorrosion and antifouling integrated self-repairing microcapsule |
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Application publication date: 20131225 |