CN109158063A - A kind of magnetic macromolecular microsphere structure and its preparation - Google Patents
A kind of magnetic macromolecular microsphere structure and its preparation Download PDFInfo
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- CN109158063A CN109158063A CN201810859416.7A CN201810859416A CN109158063A CN 109158063 A CN109158063 A CN 109158063A CN 201810859416 A CN201810859416 A CN 201810859416A CN 109158063 A CN109158063 A CN 109158063A
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
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Abstract
A kind of magnetic macromolecular microsphere, spherical MULTILAYER COMPOSITE interlayer structure, is made of high-molecular organic material and magnetic material, which is characterized in that shell and internal layer are high-molecular organic material, and magnetic-particle and sandwich of layers are magnetic material；For magnetic-particle in being symmetrically and evenly published between organic polymer outer shell and magnetic sandwich of layers, sandwich of layers two sides are high-molecular organic material.
Description
Technical field
This application involves high-molecular biologics, and in particular to magnetic macromolecular microsphere.
Background technique
The magnetic microsphere of core-shell structure is that another material cladding is got up to be formed by one kind by chemical bond or other effects
The specific function material of ordered fabrication structure has wide in fields such as catalysis, biomedicine, electrochemistry, optics and separating-purifyings
General application prospect.For the material of one-component, the composite material of core-shell structure is more easily by core or shell
Chemical modification or physical modification and obtain new function.The magnetic composite microsphere of core-shell structure, such as four oxidations three of core-shell structure
The multi-functional microballoon of iron is concerned because having the function of the target function of externally-applied magnetic field, magnetic thermotherapeutic function and NMR imaging.It is magnetic
After complex microsphere occurs from late 1970s, it is developed rapidly in the late three decades, is seen in the various magnetism of document
Microballoon, some have been used as product to sell on the market.With regard to the composition aspect of magnetic composite microsphere, the inorganic material such as silica
It is all attempted with high molecular materials such as poly- polystyrene as basis material, a variety of magnetic materials such as iron oxide, nickel are with nanometer shape
State is used as magnetic function component.From configuration aspects, there is the different structures feature such as core-shell structure, interlayer structure and hybrid structure
Magnetic composite microsphere.From preparation method and process aspect, it is related to the original of the basis material in complex microsphere preparation process
The methods of fabricated in situ of position synthesis or nano-magnetic component and the two kinds of components prepared respectively in advance in some way into
The compound method etc. of row.From aspect of performance, magnetic composite microsphere that prepared different scale, that magnetic size is controllable, and
Other function feature can be introduced, the complex microsphere of functionalization is obtained.It assigns new function to magnetic microsphere, its application can be expanded
The grade and added value of magnetic composite microsphere are improved in field, provide more extensive application for magnetic composite microsphere and development is empty
Between.For functional magnetic complex microsphere, the intension of " functionalization " include two aspect: one is to so-called noumenon function
Change, i.e. the component of ontology of composition microballoon itself has a specific function, such as conduction, fluorescence, temperature sensitive.It is seen in report at present
The magnetic composite microsphere of noumenon function is using magnetic particle as core, using functionalization clad as the core-shell structure of shell mostly.Two
Be it is so-called surface-functionalized, i.e., by preparing compound design or subsequent modified technique to magnetic microsphere outer layer, draw
Enter functionalization component or chemical functional group, so that microballoon be made to have such as parent/hydrophobicity, bioaffinity can conjugate enzyme, anti-
The characteristics such as the bioactive substances such as body, antigen.
There are two distinguishing features for such microballoon tool: 1. superparamagnetism are magnetic under the action of an external magnetic field, remove magnetic field
The magnetic characteristic to disappear afterwards；2. the characteristic of polymer particles can be assigned by the methods of copolymerization on its surface due to the property
A variety of biologically active functional groups (such as-COOH ,-NH2) are given, so that (such as targeted drug, clinic is examined in biomedicine
Break), cytology, the fields such as bioengineering are with a wide range of applications and potentiality.Magnetic macromolecular microsphere refers to containing magnetic
Property metal or metal oxide superfines, and with magnetic response polymer microsphere.The core part of magnetic microsphere
Magnetic material assigns magnetic microsphere with separation function, and outer layer boiomacromolecule functional group assigns magnetic microsphere with the function of carrier
Energy.From the current study, magnetic microsphere is generally core-shell type, magnetic metal oxide (such as iron, cobalt, nickel as shown in Figure 1
Oxide) group nucleation, high molecular material forms shell, or high molecular material is as core as shown in Figure 2, and magnetic material is as shell
Layer；Hybrid as shown in Figure 3, magnetic-particle is dispersed in inside magnetic microsphere；Multilayer sandwiched formula as shown in Figure 4, ectonexine are height
Molecular material, intermediate sandwich of layers are magnetic material.Magnetic composite microsphere is as a kind of new function composite material, in cell point
From, protein purification, nucleic acid extraction, clinical diagnosis, target administration, immobilised enzymes etc. have increasingly extensive and important answer
With.
(Deng Jianguo, Peng Yuhang, Ding little Bin, Wang Jianhua, Long Xinping, Li Bei, Chen Xingzi in the prior art；Magnetic polyaniline
Chinese Journal of Chemical Physics 2002,15 (2): the synthesis and characterization of nanosphere 149~52) disclose a kind of magnetic polyaniline nanometer
Microballoon, core are ferriferrous oxide nano-particle, are cladded with polyaniline shell, while having magnetic and electric conductivity；Chinese patent application
CN03130269.6 discloses a kind of complex function ultramicro magnetic particle, and internal layer is ferriferous oxide, and middle layer is macromolecule carrier
Material, outermost layer are bioactive functions preparations, can have both magnetic orientation, biological targeting positioning and medicine controlled releasing complex function；
Chinese patent application discloses CN 1375507A and discloses a kind of magnetic composite microsphere, and surface is with epoxy group, hydroxyl, aldehyde radical, carboxylic
The functional groups such as base are modified, and can be used as the load in microarray electromagnetic unit biochip to biomolecule oriented control
Body；Paper (Deng YH, Yang WL, Wang CC, FU SK；A novel approach forpreparation of
Thermoresponsive polymer ma gnetic microspheres withcore-shell structure,
Advanced Materials 2003,15 (20): 1729~32) reporting a kind of magnetic composite microsphere with temperature sensitive function,
Core is ferriferrous oxide nano-particle, is cladded with the poly(N-isopropylacrylamide) shell of crosslinking.Above-mentioned microballoon is designed in structure
On weakness be can not to introduce enough magnetic components, thus not prominent enough the saturation magnetization of its magnetic characteristic is not
Enough, stability is insufficient.The structure of magnetic microsphere itself determines its performance in biological detection application.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of novel high molecule magnetic microsphere structures.
A kind of magnetic macromolecular microsphere is as shown in figure 5, spherical MULTILAYER COMPOSITE interlayer structure, by organic polymer and magnetic material
Material composition, including, outer shell, small granular magnetic layer, magnetic main stratum nucleare；It is characterized in that, by the high-molecular organic material group
At outer shell, for small magnetic-particle in being symmetrically and evenly published between outer shell and magnetic main stratum nucleare, magnetic-particle shell is located at ball
At the heart.
Preferably, small magnetic particle diameter is 10-15um, and the main stratum nucleare volume of internal magnetization is the 1- of small magnetic-particle
1.5 multiple.
Preferably, the magnetic material accounts for the 40%-50% of the weight of magnetic macromolecular microsphere.
Preferably, the magnetic material is the transition metal oxide of iron, nickel, cobalt, manganese, osmium.
The preferably described high-molecular organic material is polystyrene；
Preferably, the high-molecular organic material is polyethylene glycol；
On the other hand, magnetic macromolecular microsphere of the invention is made by the steps, preparation flow such as Fig. 6 institute
Show:
1) high-molecular organic material ball is prepared；
2) magnetic material is prepared by chemical coprecipitation and coats high-molecular organic material ball；
3) by 2 product of above-mentioned steps, using sol-gel process, high-temperature roasting carbonization covers organic high score on its surface
Sub- material layer；
4) the small magnetic-particle is prepared；
5) initiator is added in the small magnetic-particle, crosslinking agent is dissolved into the in the mixed solvent in polystyrene, is added
3 product of above-mentioned steps, stirs evenly, and ultrasonic wave dispersion is stood after sealing is cooling；
6) 160 degree, high-speed stirred party reaction 5 hours are heated to；
7) in fluid environment polymerization reaction at microballoon.
Preferably, crosslinking agent is dissolved into the mixed solvent in polyethylene glycol in the step 5.
Beneficial effects of the present invention:
1, synthesizing the high magnetic microsphere of size uniformity, magnetic material content is that batch is stablized, ambient noise is low, clever for exploitation
The basis of the high diagnostic kit of sensitivity.
2, the intensity of magnetization is saturated, and stability is high；Good sphericity is kept, and core-shell microspheres are uniform in size,
In controlled range.Preparing magnetic particle is spherical structure, has good dispersion, particle size in aqueous solution or alcoholic solution
For 150-250nm, and there is good magnetic responsiveness.
3, multi-layer core-shell structure complex microsphere has good dispersion stabilization and surface modificability appropriate in water,
It can be separated in protein, cell, the fields such as product recycling are applied in complex reaction.
Detailed description of the invention
Fig. 1 is magnetic material group nucleation, and high molecular material forms the micro-sphere structure of shell；
Fig. 2 is high molecular material group nucleation, and magnetic material forms the micro-sphere structure of shell；
Fig. 3 is the microballoon of mixed structure；
Fig. 4 is sandwich micro-sphere structure；
Fig. 5 is the sandwich polymer microsphere structure of MULTILAYER COMPOSITE；
Fig. 6 is preparation flow.
Dash area is magnetic material, and blank parts are high molecular material.
Specific embodiment
Embodiment 1
The monodisperse polystyrene particle that partial size 1um is prepared by dispersion polymerization, by amount of substance than the trivalent for 2:1
Molysite and divalent iron salt mixed solution are applied directly in the aqueous solution of highly basic sodium hydroxide, prepare four oxygen by chemical coprecipitation
Change three-iron and coats polystyrene；Using sol-gel process, high-temperature roasting carbonization covers polystyrene polymeric on its surface
Material layer；Using hydrogen peroxide as oxidant, ferroferric oxide nano granules are prepared by hydrogen peroxide oxidation hydro-thermal method；It is added and causes
Agent, crosslinking agent are dissolved into the in the mixed solvent in polystyrene, stir evenly, and ultrasonic wave dispersion is stood after sealing is cooling；Heating
To 160 degree, high-speed stirred polymerization reaction 5 hours；In fluid environment polymerization reaction at microballoon.Magnetic macromolecular microsphere saturated magnetization
Intensity is 32.42emu/g.
Embodiment 2
The monodisperse polyethylene glycol particle that partial size 1um is prepared by bulk polymerization, by amount of substance than the trivalent for 2:1
Molysite and divalent iron salt mixed solution are applied directly in the aqueous solution of highly basic sodium hydroxide, prepare four oxygen by chemical coprecipitation
Change three-iron and coats polystyrene；Using sol-gel process, high-temperature roasting carbonization covers polyethylene glycol polymer on its surface
Material layer；Using hydrogen peroxide as oxidant, ferroferric oxide nano granules are prepared by hydrogen peroxide oxidation hydro-thermal method；It is added and causes
Agent, crosslinking agent are dissolved into the in the mixed solvent in polystyrene, stir evenly, and ultrasonic wave dispersion is stood after sealing is cooling；Heating
To 160 degree, high-speed stirred polymerization reaction 5 hours；In fluid environment polymerization reaction at microballoon.Magnetic macromolecular microsphere saturated magnetization
Intensity is 32.12emu/g.
Embodiment 3
The monodisperse polyethylene glycol particle that partial size 2um is prepared by dispersion polymerization, by amount of substance than the trivalent for 2:1
Molysite and divalent iron salt mixed solution are applied directly in the aqueous solution of highly basic potassium hydroxide, prepare four oxygen by chemical coprecipitation
Change three-iron and coats polystyrene；Using sol-gel process, high-temperature roasting carbonization covers polyethylene glycol polymer on its surface
Material layer；Using hydrogen peroxide as oxidant, ferroferric oxide nano granules are prepared by hydrogen peroxide oxidation hydro-thermal method；It is added and causes
Agent, crosslinking agent are dissolved into the in the mixed solvent in polystyrene, stir evenly, and ultrasonic wave dispersion is stood after sealing is cooling；Heating
To 160 degree, high-speed stirred polymerization reaction 5 hours；In fluid environment polymerization reaction at microballoon.Magnetic macromolecular microsphere saturated magnetization
Intensity is 30.25emu/g.
Embodiment 4
Sample structure analysis and performance test
Turn the microcosmic knot of target X-ray diffractometer CuK α (λ=0.15400nm) analysis sample using D/max2550VB+18kw
Structure, targeting voltage are 40kV, target current 300mA, scanning range 5-90 degree；Morphology observation transmits electricity using JEM01-1230 type
Mirror and JSM-5600LV type scanning electron microscope sem are adopted using JDM-13D type vibration sample magnetometer come the magnetic property of test sample
Partial size and particle diameter distribution are measured with Malvern laser particle analyzer MASTERSIZER2000.
Claims (6)
1. a kind of magnetic macromolecular microsphere, spherical MULTILAYER COMPOSITE interlayer structure, are made of high-molecular organic material and magnetic material,
It is characterized in that, shell and internal layer are high-molecular organic material, magnetic-particle and sandwich of layers are magnetic material；Magnetic-particle is in pair
Claim uniformly to be published between organic polymer outer shell and magnetic sandwich of layers, sandwich of layers two sides are high-molecular organic material.
2. magnetic macromolecular microsphere as described in claim 1, which is characterized in that the magnetic material is iron, nickel, cobalt, manganese, osmium
Metal oxide.
3. magnetic macromolecular microsphere as described in claim 1, which is characterized in that the high-molecular organic material is polyphenyl second
Alkene.
4. magnetic macromolecular microsphere as described in claim 1, which is characterized in that the high-molecular organic material is poly- second two
Alcohol.
5. the preparation method of preparation such as claim 1-4 any one magnetic macromolecular microsphere, including,
1) high-molecular organic material prepares orbicule；
2) high-molecular organic material preparation for being prepared magnetic material encapsulation steps 1 by chemical coprecipitation is spherical
Body；
3) by 2 product of above-mentioned steps, using sol-gel process, high-temperature roasting carbonization covers organic polymer material on its surface
The bed of material；
4) the small magnetic-particle is prepared；
5) initiator is added in the small magnetic-particle, crosslinking agent is dissolved into the in the mixed solvent in polystyrene, is added above-mentioned
Step 3 product, stirs evenly, and ultrasonic wave dispersion is stood after sealing is cooling；
6) 160 degree, high-speed stirred party reaction 5 hours are heated to；
7) in fluid environment polymerization reaction at microballoon.
6. the preparation method of preparation such as claim 1-4 any one magnetic macromolecular microsphere, including,
1) high-molecular organic material prepares orbicule；
2) high-molecular organic material preparation for being prepared magnetic material encapsulation steps 1 by chemical coprecipitation is spherical
Body；
3) by 2 product of above-mentioned steps, using sol-gel process, high-temperature roasting carbonization covers organic polymer material on its surface
The bed of material；
4) the small magnetic-particle is prepared；
5) initiator is added in the small magnetic-particle, crosslinking agent is dissolved into the in the mixed solvent in polyethylene glycol, is added above-mentioned
Step 3 product, stirs evenly, and ultrasonic wave dispersion is stood after sealing is cooling；
6) 160 degree, high-speed stirred party reaction 5 hours are heated to；
7) in fluid environment polymerization reaction at microballoon.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115127974A (en) * | 2021-03-24 | 2022-09-30 | 深圳市帝迈生物技术有限公司 | Magnetic bead and manufacturing method thereof |
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| CN101004414A (en) * | 2007-01-16 | 2007-07-25 | 华东理工大学 | Magnetic microspheres of macromolecule, and synthesizing preparation method in situ |
| CN101817960A (en) * | 2010-03-17 | 2010-09-01 | 中国石油大学(华东) | Method for preparing magnetic composite nanoparticles with core-shell structure |
| CN102030952A (en) * | 2010-11-12 | 2011-04-27 | 厦门大学 | Magnetic core-shell polymer composite microsphere and preparation method thereof |
| CN103657545A (en) * | 2012-09-18 | 2014-03-26 | 复旦大学 | Magnetic polymer/carbon-based microsphere material with core-shell structure and preparation method thereof |
| US20160266103A1 (en) * | 2005-01-20 | 2016-09-15 | Luminex Corporation | Magnetic microspheres for use in fluorescence-based applications |
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2018
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20160266103A1 (en) * | 2005-01-20 | 2016-09-15 | Luminex Corporation | Magnetic microspheres for use in fluorescence-based applications |
| CN101004414A (en) * | 2007-01-16 | 2007-07-25 | 华东理工大学 | Magnetic microspheres of macromolecule, and synthesizing preparation method in situ |
| CN101817960A (en) * | 2010-03-17 | 2010-09-01 | 中国石油大学(华东) | Method for preparing magnetic composite nanoparticles with core-shell structure |
| CN102030952A (en) * | 2010-11-12 | 2011-04-27 | 厦门大学 | Magnetic core-shell polymer composite microsphere and preparation method thereof |
| CN103657545A (en) * | 2012-09-18 | 2014-03-26 | 复旦大学 | Magnetic polymer/carbon-based microsphere material with core-shell structure and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115127974A (en) * | 2021-03-24 | 2022-09-30 | 深圳市帝迈生物技术有限公司 | Magnetic bead and manufacturing method thereof |
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