CN1193383C - Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method - Google Patents
Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method Download PDFInfo
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- CN1193383C CN1193383C CNB031113516A CN03111351A CN1193383C CN 1193383 C CN1193383 C CN 1193383C CN B031113516 A CNB031113516 A CN B031113516A CN 03111351 A CN03111351 A CN 03111351A CN 1193383 C CN1193383 C CN 1193383C
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000004044 response Effects 0.000 title claims abstract 4
- 239000010419 fine particle Substances 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002105 nanoparticle Substances 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 37
- 239000011258 core-shell material Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 238000004381 surface treatment Methods 0.000 claims abstract description 4
- 229910052681 coesite Inorganic materials 0.000 claims abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 2
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 2
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000004043 responsiveness Effects 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 2
- 239000011859 microparticle Substances 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 18
- 239000006249 magnetic particle Substances 0.000 abstract description 12
- 239000003814 drug Substances 0.000 abstract description 6
- 229940079593 drug Drugs 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000012620 biological material Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000007306 functionalization reaction Methods 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- 239000000696 magnetic material Substances 0.000 abstract description 2
- 239000000825 pharmaceutical preparation Substances 0.000 abstract description 2
- 229940127557 pharmaceutical product Drugs 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 229910001566 austenite Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 229910003321 CoFe Inorganic materials 0.000 description 4
- 241000872198 Serjania polyphylla Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 239000004593 Epoxy Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 amino, sulfydryl Chemical group 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000005426 magnetic field effect Effects 0.000 description 1
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Landscapes
- Hard Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
- Silicon Compounds (AREA)
Abstract
本发明的具有强磁场响应能力的磁性核壳微粒及其制备方法属磁性材料领域。该微粒的内核是具有超顺磁性的磁性铁氧体纳米粒子，外壳是二氧化硅，每个微粒中包覆有20～1000个磁性铁氧体粒子。制备方法包括用共沉淀法制备铁氧体粒子；再将洗好的铁氧体粒子不经过任何表面处理直接分散到含SiO2的水溶性无机盐的水溶液中搅拌进行第一次二氧化硅包覆；通过正硅酸乙酯水解反应进行第二次二氧化硅包覆。本发明工艺过程和设备简单，磁性核壳微粒具有磁性物质含量高，外磁场响应能力强；包覆层结构致密；无裸露磁粒子；在水中分散性好，容易进一步功能化。适用于生物材料和医药制品的分离和纯化，可做为生物分子和药物分子磁控定向输送载体。The magnetic core-shell particles with strong magnetic field response capability and the preparation method thereof belong to the field of magnetic materials. The inner core of the particles is magnetic ferrite nanoparticles with superparamagnetism, the outer shell is silicon dioxide, and each particle is coated with 20-1000 magnetic ferrite particles. The preparation method includes preparing ferrite particles by co-precipitation; and then directly dispersing the washed ferrite particles into an aqueous solution of water-soluble inorganic salt containing SiO2 without any surface treatment and stirring for the first silicon dioxide coating. coating; a second silica coating was performed by hydrolysis of tetraethyl orthosilicate. The process and equipment of the invention are simple, the magnetic core-shell particles have high content of magnetic substances, strong external magnetic field response ability; the cladding layer has a compact structure; no exposed magnetic particles; good dispersion in water and easy further functionalization. It is suitable for the separation and purification of biological materials and pharmaceutical products, and can be used as a magnetically controlled directional delivery carrier for biomolecules and drug molecules.
Description
Technical field
The invention belongs to field of magnetic material, particularly a kind of core-shell type magnetic particulate and preparation method thereof.
Background technology
Magnetic particle biomaterial such as cell, protein, DNA and RNA etc. separate and biological and medical fields such as purifying, biomolecular labeling and detection, immunoassay and targeted drug in application more and more widely.This mainly is based on the external magnetic field responding ability of magnetic particle, such as enrichment under the magnetic particle outside magnetic field and directed movement.Compare with separation method such as the precipitation method, centrifugal process, ion-exchange and various chromatography methods commonly used, the magnetic separation technique that grows up based on the enrichment under the effect of magnetic particle outside magnetic field has convenient and swift, characteristics such as equipment needed thereby is simple, extraction efficiency height.And with magnetic particle as pharmaceutical carrier, can realize the orientation conveying of medicine by the effect of external magnetic field, medicine is directly delivered to diseased region, can improve curative effect greatly, reduce side effects of pharmaceutical drugs, on some major diseases such as treatment for cancer, have a wide range of applications.In the existing commodity, mostly magnetic particle is the polymer microsphere that makes by emulsion polymerization or suspension polymerization.This polymer microsphere is made up of the magnetic core and the surface aggregate thing coating layer of inside; the general more complicated of its synthesis technique; use some poisonous organic solvent or polymerization single polymerization monomers through regular meeting in synthetic, microballoon is in case formation is difficult to it be carried out other finishing again.In addition, because what constitute polymer microsphere surface is some organic polymers, its biocompatibility is relatively poor, can't use in vivo, and the structure of these polymer covering layers is more loose usually, cause the leakage of internal magnetization particle easily, the magnetic particle of leakage has limited its range of application to the toxic effect of a lot of bioactivators.
The prior art that is close most with the present invention is that (Langmuir 1994 for one piece of document " Magnetic Silica Dispersons:Preparation and Stability ofSurface-Modified Silica Particles with a Magnetic Core " of delivering of Albert P.Philipse, 10,92～99) disclosed a kind of Fe in
3O
4-silica magnetic core-shell particle and preparation method thereof.Disclosed Fe with magnetic responsiveness ability
3O
4-silica core-shell particulate is that its kernel is the magnetic Fe with superparamagnetism
3O
4Nano particle, skin are silicon dioxide, have 6 or be less than 6 magnetic Fe in the coated with silica layer
3O
4Nano particle.The method of making this magnetic particle has the following steps: the preparation magnetic Fe
3O
4---surface treatment---coating of inorganic silicon source---organosilicon source coats nano particle.Said preparation magnetic Fe
3O
4Nano particle is to adopt known coprecipitation.Said surface treatment is to use Tetramethylammonium hydroxide to make peptizing agent, to magnetic Fe
3O
4Nano particle carries out peptization to be handled.It is with Na that said inorganic silicon source coats
2SiO
3Do the silicon source, the magnetic Fe after peptization is handled
3O
4Nano particle is put into Na
2SiO
3Fully stir in the aqueous solution, form SiO
2Coat Fe
3O
4Nano particle, the about 1nm of the thickness of coating layer.It is to do the silicon source with tetraethoxysilane that said organosilicon source coats, and is solvent with ethanol, and the concentrated ammonia liquor that with the mass percent concentration is 25-28% is that catalyst adds the magnetic Fe that coats through the inorganic silicon source
3O
4Stir behind the nano particle, prepare Fe
3O
4-silica core-shell particulate.Will be in the preparation process by the magnetic Fe of dialysis to coating through the inorganic silicon source
3O
4Nano particle is purified, the Fe for preparing at last
3O
4-silica core-shell particulate will be purified with the magnetic splitter of special use.
The Fe of background technology
3O
4The coating layer of-silica core-shell particulate is inorganic silicon dioxide, thereby particulate has excellent biological compatibility, better chemical stability, and can carry out various finishinges by different silylating reagents, the particulate after modified can combine with various biomaterials.But because this Fe
3O
4The magnetic Fe that coats in particle-silica core-shell particulate
3O
4Nano particle has only 6 or be less than 6, the magnetic kernel number very little, particulate magnetic a little less than, a little less than the external magnetic field responding ability, need to use special-purpose magnetic splitter and apply the enrichment that the high strength external magnetic field could realize this particle, this has just limited the application of this magnetic particle.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art exactly, proposes a kind of magnetic ferrites-silica core-shell particulate with high-intensity magnetic field responding ability and preparation method thereof.This magnetic ferrites-silica core-shell particulate has coenocytism, magnetisable material content height, has very strong external magnetic field responding ability, do not need special-purpose magnetic splitter just can realize the fast enriching of particulate under lower magnetic field intensity, coated with silica densification simultaneously, chemical stability be good, do not have exposed magnetic particle, the easy functionalization in surface; Do not need among the preparation method that the magnetic ferrites nano particle is carried out peptization and handle, technical process is simpler, and equipment needed thereby is because particulate magnetic also becomes simple by force.
Magnetic ferrites-silica core-shell particulate with high-intensity magnetic field responding ability of the present invention, its kernel is the magnetic ferrites nano particle of coated with silica, shell is a silicon dioxide.Said magnetic ferrites nano particle refers to Fe
3O
4Nano particle, γ-Fe
2O
3Nano particle or mix transition metal and the magnetic ferrites nano particle of compound, they have superparamagnetism, and particle diameter is 3～12nm.Described particulate has coenocytism, and particle diameter is 0.2～10 μ m, is surrounded by 20～1000 magnetic ferrites nano particles in each particulate.The quality percentage composition of magnetic ferrites nano particle is 10～60% in the particulate.
The magnetic responsiveness ability of described particulate is: to the hydrosol of this core-shell particle of 10ml, under the externally-applied magnetic field of 0.05T, the particle enrichment time is in 1 minute.Can see that by transmission electron microscope the number of the magnetic ferrites nano particle that this core-shell particle with high-intensity magnetic field responding ability contains is 20～1000.
Preparation method with magnetic ferrites-silica core-shell particulate of high-intensity magnetic field responding ability of the present invention, the technical process that has preparation magnetic ferrites nano particles---coating of inorganic silicon source---organosilicon source to coat.That is:
At first utilize known coprecipitation to prepare the magnetic ferrites nano particle, the particle diameter of the magnetic ferrites nano particle that makes can utilize tilt-pour process to carry out the pure water cleaning under permanent magnetic field and remove impurity at 3～12nm;
Washed magnetic ferrites nano particle directly is distributed to without any surface treatment contains SiO
2The aqueous solution of water-soluble inorganic salt in stir and carry out the coated with silica first time, be coated on the magnetic ferrites nanoparticle surface through current inorganic silicon source and form the thick silicon dioxide layer of 1～2nm, the magnetic ferrites nano particle that utilizes tilt-pour process that the inorganic silicon source is coated again under permanent magnetic field carries out the pure water cleaning and removes impurity;
The magnetic ferrites nano particle of coated with silica is distributed in the mixed solvent of alcohol and water to finishing for the first time, under alkali condition, carries out the coated with silica second time by the teos hydrolysis reaction.Can obtain being of a size of multinuclear magnetic ferrites-silica core-shell particulate of 0.2～10 μ m by the control of reaction condition.
Wherein said magnetic ferrites nano particle is meant the nanometer Fe with superparamagnetism
3O
4Particle, γ-Fe
2O
3Nano particle or mix transition metal and the magnetic ferrites nano particle of compound.
In aforesaid cladding process process, process conditions are to need control.When the inorganic silicon source coated, the concentration of magnetic ferrites nano particle was 0.05～25g/L in the reaction solution, SiO
2Concentration be 0.1～50g/L.The pH of reaction solution is transferred between 8～11.Mixing speed is to react 5～24 hours under the condition of 50～800rpm.When the organosilicon source coats, alcohol in the mixed solvent of alcohol and water can be methyl alcohol, ethanol, propyl alcohol, butanols etc., the volumn concentration of alcohol is 30～100% in the mixed solvent, the volumn concentration of water is 0～70%, the adding mass percent concentration is 25～28% concentrated ammonia liquor in above-mentioned solution, in the mixed solution of Xing Chenging, the concentration of magnetic ferrites nano particle is 0.05～1g/L thus, and the molar concentration of ammoniacal liquor in reaction solution is 0.5～1mol/L.Under the mixing speed of 50～500rpm, dropwise add tetraethoxysilane 0.5～5ml/L then, reacted 3～30 hours.
Dropwise adding tetraethoxysilane during above-mentioned organosilicon source coats, tetraethoxysilane can add in batches, and each addition is 0.5～1.5ml/L, and wherein the time interval of adjacent twice adding is 2～6h, after tetraethoxysilane all adds, continue reaction 3～24h again.By the addition of control tetraethoxysilane, can regulate the thickness of coated with silica layer of magnetic ferrites-silica core shell particles of last formation and the size of resulting core-shell particle.
The aforesaid tilt-pour process that utilizes under steady magnetic field cleans when removing impurity with pure water, can working strength be the permanent magnet of 0.05～0.15T.
As mentioned above, the present invention is under the reaction condition of gentleness, synthesized magnetic ferrites-silica core-shell particulate by simple technical process, this particulate has following characteristics: (1) magnetisable material content height, very strong external magnetic field responding ability is arranged, under very low external magnetic field effect, get final product rapid enrichment; (2) compact structure of coated with silica layer, thereby chemical stability height, oxidation resistance is strong; (3) do not have exposed magnetic particle, and good leak integrity is arranged; (4) Biao Mian chemical composition is a silicon dioxide, and easily further functionalization utilizes the silylating reagent that has groups such as amino, sulfydryl, epoxy that silica surface is modified, the surface of can obtain having amino, dredging functional groups such as base, epoxy.
Magnetic ferrites described in the invention-the good dispersion of silica core-shell particulate in water, can connect various bioactivators (as cell, antibody, antigen, enzyme or nucleic acid) and drug molecule after the surface is modified, be specially adapted to separating and purifying of various biomaterials and pharmaceutical products, and can be as biomolecule and the directed carrier of carrying of drug molecule magnetic control.
The preparation method of magnetic ferrites of the present invention-silica core-shell particulate, technical process is simple, and is lower to equipment requirements.
Embodiment
Embodiment 1:Fe
3O
4The preparation of nano particle
Take by weighing the FeCl of 27.45g
36H
2The FeCl of O and 10.10g
24H
2O, water-soluble the separating of passing through letting nitrogen in and deoxidizing with 100ml obtains mixed solution.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 25ml is the concentrated ammonia liquor of 25-28%, rapidly to wherein pouring above-mentioned molysite mixed solution into, reacts 1h down at 80 ℃ under vigorous stirring.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction solution, the gained solid promptly gets the Fe that particle diameter is 6～10nm 3～5 times with the high purity water cleaning
3O
4Nano particle.
Embodiment 2: γ-Fe
2O
3The preparation of nano particle
Take by weighing the FeCl of 27.45g
36H
2The FeCl of O and 10.10g
24H
2O, water-soluble the separating of passing through letting nitrogen in and deoxidizing with 100ml obtains mixed solution.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 25ml is the concentrated ammonia liquor of 25-28%, rapidly to wherein pouring above-mentioned molysite mixed solution into, reacts 1h down at 80 ℃ under vigorous stirring.Aerating oxygen 2h in reaction solution then.After reaction finishes, isolate red solid with the permanent magnet of 0.1T from reaction solution, the gained solid cleans with high purity water and promptly gets γ-Fe that particle diameter is 6～10nm 3～5 times
2O
3Nano particle.
Embodiment 3:CoFe
2O
4The preparation of nano particle
Take by weighing the CoCl of 27.86g
36H
2The FeCl of O and 10.10g
24H
2O, water-soluble the separating of passing through letting nitrogen in and deoxidizing with 100ml obtains mixed solution.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 25ml is the concentrated ammonia liquor of 25-28%, rapidly to wherein pouring above-mentioned mixing salt solution into, reacts 1h down at 50 ℃ under vigorous stirring.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction solution, the gained solid promptly gets the CoFe that particle diameter is 3～13nm 3～5 times with the high purity water cleaning
2O
4Nano particle.
Embodiment 4: the inorganic silicon source coats (coated with silica for the first time)
Take by weighing 2.5g Na
2SiO
3(SiO
2Content is 45%) be dissolved in the 500ml water, be 9.6 with the pH of resin cation regulator solution, to wherein adding the above-mentioned synthetic Fe of 1g
3O
4Nano particle.At room temperature, in the 1L round-bottomed flask, react 12h with the 150rpm mixing speed.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction solution, the gained solid promptly gets the Fe that particle diameter is the coated with silica of 7～12nm 3～5 times with the high purity water cleaning
3O
4Nano particle.
Embodiment 5: the organosilicon source coats (coated with silica for the second time)
The concentrated ammonia liquor, 0.05g that add 450ml ethanol, 50ml water, 20ml mass percent concentration successively and be 25-28% in the 1L round-bottomed flask are through the synthetic Fe of the coated with silica first time
3O
4Nano particle.At room temperature, drip the 0.3ml tetraethoxysilane, drip the 0.3ml tetraethoxysilane again behind the reaction 3h, continue reaction 12h with the 200rpm mixing speed.Isolate the solid of black with the permanent magnet of 0.1T from reaction solution, the gained solid cleans with high purity water and promptly gets the multinuclear Fe that average-size is 0.4 μ m 3～5 times
3O
4-SiO
2Core-shell particle.
Get above-mentioned core-shell particle 0.330g and be dispersed among the 10ml 1M HCl and soak 10min, the iron concentration of leakage is 4ppm; Get above-mentioned core-shell particle 0.030g and be dispersed in the 1ml water, under the magnetic field of 0.05T, the enrichment time of particulate is 10s; Get above-mentioned core-shell particle 0.030g and be dispersed in 1ml 50%HNO
3In, behind the heating 24h, under the magnetic field of 0.5T, the enrichment time of particulate still is 10s in 95 ℃ of water-baths.
Embodiment 6: with the nanometer Fe in embodiment 4,5 processes
3O
4Particle changes γ-Fe into
2O
3And/or CoFe
2O
4Nano particle, the preparation process of employing embodiment 4,5 can make γ-Fe
2O
3-silica core-shell particulate and/or CoFe
2O
4-silica core-shell particulate.
Claims (4)
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|---|---|---|---|
| CNB031113516A CN1193383C (en) | 2003-04-01 | 2003-04-01 | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method |
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|---|---|---|---|
| CNB031113516A CN1193383C (en) | 2003-04-01 | 2003-04-01 | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method |
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|---|---|
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| CN1193383C true CN1193383C (en) | 2005-03-16 |
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|---|---|---|---|---|
| CN100505116C (en) * | 2004-11-19 | 2009-06-24 | 南京大学 | Fe/(SiO-[2]+C) core-shell composite nanometer particle with high stability and method for preparing same |
| CN100366532C (en) * | 2006-06-08 | 2008-02-06 | 复旦大学 | A kind of silicon/silicon oxide core-shell structure nanocomposite material and its preparation method and application |
| CN100497186C (en) * | 2007-05-15 | 2009-06-10 | 中国科学院长春应用化学研究所 | Method for preparing Fe2O3 Nano particles clad by Fe2O3 |
| CN101318148B (en) * | 2007-06-06 | 2010-05-26 | 中国石油化工股份有限公司 | A kind of preparation method of spherical magnetic alumina carrier |
| CN101205420B (en) * | 2007-12-06 | 2012-01-18 | 复旦大学 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
| CN101388267B (en) * | 2008-07-09 | 2011-04-13 | 长春市博坤生物科技有限公司 | Silicon dioxide magnetic composite particle and preparation |
| CN101597105B (en) * | 2009-06-11 | 2011-01-19 | 浙江省环境保护科学设计研究院 | A preparation method of a magnetic carrier used in sewage biological fluidized bed treatment process |
| CN102363624B (en) * | 2010-06-18 | 2016-03-30 | 香港理工大学 | Endotoxin removal using two nucleophilic-shell nanoadsorbents |
| CN103834316B (en) * | 2012-11-26 | 2017-11-21 | 鸿富锦精密工业（深圳）有限公司 | Adhesive structure, surface conditioning agent and tear off method |
| CN107633946A (en) * | 2017-09-25 | 2018-01-26 | 常州市沃兰特电子有限公司 | A kind of preparation method of nanometer of magnet |
| WO2020018919A1 (en) * | 2018-07-19 | 2020-01-23 | Beckman Coulter, Inc. | Magnetic particles |
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2003
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