CN113066657B - Hedgehog-shaped magnetic microsphere and preparation method thereof - Google Patents
Hedgehog-shaped magnetic microsphere and preparation method thereof Download PDFInfo
- Publication number
- CN113066657B CN113066657B CN202110472059.0A CN202110472059A CN113066657B CN 113066657 B CN113066657 B CN 113066657B CN 202110472059 A CN202110472059 A CN 202110472059A CN 113066657 B CN113066657 B CN 113066657B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- hedgehog
- preparing
- shaped magnetic
- microsphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0018—Diamagnetic or paramagnetic materials, i.e. materials with low susceptibility and no hysteresis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
- H01F1/0311—Compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
- H01F1/0311—Compounds
- H01F1/0313—Oxidic compounds
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compounds Of Iron (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a preparation method of hedgehog-shaped magnetic microspheres, which is based on magnetic nano particles wrapped by silicon dioxide, takes a silicon dioxide layer as a template, enables the silicon dioxide layer to be completely etched to generate a hedgehog-shaped shell structure by a one-step hydrothermal method, cleans the hedgehog-shaped shell structure by deionized water after reaction, and collects magnets to obtain the hedgehog-shaped magnetic microspheres. The microsphere is characterized by comprising an inner core and a magnesium silicate shell, wherein the magnesium silicate shell is in a nano needle-like structure, is similar to a hedgehog in shape and has a strong surface function; the kernel is magnetic ferroferric oxide nano particles, and the micro-spheres are endowed with rapid magnetic responsiveness, so that the controllable motion of the hedgehog-shaped magnetic micro-spheres can be realized under the action of an external magnetic field. The hedgehog-shaped magnetic microsphere preparation method based on the magnetic nanoparticles has the advantages of low cost, easiness in operation, convenience, reliability and the like.
Description
Technical Field
The invention relates to the field of biological materials, in particular to hedgehog-shaped magnetic microspheres and a preparation method thereof.
Background
The magnetic nano material has wide attention on good dispersibility and biocompatibility due to superparamagnetism, and has excellent application prospects in the field of biotechnology, including magnetic target administration, medical imaging, cancer diagnosis, sewage treatment, cell separation and the like. The magnetic separation technology becomes a core technology in the field of separation and analysis due to the unique magnetic response performance of the magnetic microspheres, magnetic beads cannot be magnetically polymerized under the condition of no external magnetic field, and when the external magnetic field appears, the magnetic beads can quickly respond to realize the enrichment of a separation target. The enrichment and separation of the magnetic microspheres for the biomolecules has the advantages of simple and convenient operation, rapid enrichment and separation, recycling, no introduction of new substances in the separation process and the like.
Common preparation methods of magnetic nano materials comprise a microemulsion method, an embedding method, a solvothermal method, a coprecipitation method and the like, but the preparation processes are complex and have high technical requirements. In addition, the surface structure of the magnetic beads prepared conventionally is often simpler, and although complex surface group modification can be performed, the magnetic beads still have greater limitation in the enrichment of biomolecules and cannot meet the application requirements of people. Therefore, the magnetic microspheres which have larger surface functions, are easy to prepare and can be used for selective and efficient separation of biomolecules have great significance in the field of biomedicine.
The hedgehog-shaped magnetic microsphere prepared based on the magnetic nano particles coated by the silicon dioxide has larger specific surface area and adjustable size, and contains magnetic beads. When a magnetic field is applied, the hedgehog shaped magnetic microsphere can realize the controllable movement, and is flexible, time-saving and convenient.
Disclosure of Invention
In order to overcome the defects of simple surface structure and complex preparation of the traditional magnetic microsphere, the invention provides a hedgehog shaped magnetic microsphere and a preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of hedgehog shaped magnetic microsphere comprises the following steps:
(1) Preparing magnetic nanoparticles:
adding anhydrous ferric trichloride, sodium acetate, poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, L-ascorbic acid and a proper amount of water into an ethylene glycol solution in sequence, and stirring to form a mixed solution; adding sodium hydroxide into the mixed solution, and continuously stirring to obtain a brown transparent solution; transferring the magnetic nanoparticles into a reaction kettle, and obtaining magnetic nanoparticles by a one-step hydrothermal method;
(2) Preparing the silicon dioxide coated magnetic nanoparticles:
dispersing the magnetic nanoparticles in ethanol, adding ammonia water, performing ultrasonic dispersion, slowly dropwise adding tetraethyl orthosilicate in a water bath condition at 50 ℃, stirring for 1h, and collecting to obtain silicon dioxide-coated magnetic nanoparticles;
(3) Preparing hedgehog-shaped magnetic microspheres:
preparing a mixed solution of magnesium chloride and ammonium chloride, uniformly mixing the mixed solution with the magnetic nano particles wrapped by the silicon dioxide, adding ammonia water, and performing ultrasonic dispersion; transferring the hedgehog magnetic microsphere into a reaction kettle, and obtaining the hedgehog magnetic microsphere by a one-step hydrothermal method.
Further, the volume ratio of the ethylene glycol solution in the step (1) to a proper amount of water is 160:1 to 800:1.
further, the size of the magnetic nanoparticles prepared in the step (1) can be changed by adjusting the water addition amount: by reducing or increasing the amount of water added, the magnetic nanoparticles will correspondingly shrink or grow.
Further, the hedgehog shaped magnetic microspheres of step (3) can change the size of the microspheres by adjusting the addition amount of tetraethyl orthosilicate of step (2): by decreasing or increasing tetraethyl orthosilicate, the hedgehog shaped magnetic microspheres will shrink or enlarge accordingly.
Further, the hydrothermal method in the step (1) is carried out for 9 hours at 190 ℃.
Further, the hydrothermal method in the step (3) has the condition of reaction at 140 ℃ for 14h.
The hedgehog-shaped magnetic microsphere prepared by the method has a shell of magnesium silicate, is in a nano needle-shaped structure and is similar to a hedgehog; the inner core is magnetic ferroferric oxide nano particles and has good magnetic responsiveness.
The particle size of the inner core magnetic ferroferric oxide nano particle is 60-90nm, and the particle size of the magnetic microsphere is 250-300nm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The hedgehog magnetic microspheres prepared based on the magnetic nanoparticles coated by the silicon dioxide have the advantages of low cost, high repeatability, no need of high technical requirements and easiness in controlling the size of the hedgehog magnetic microspheres.
(2) The hedgehog-shaped magnetic microsphere designed by the invention has the advantages of high specific surface area, strong adhesiveness, capability of realizing efficient selective enrichment of biomolecules and strong practicability.
(3) The hedgehog shaped magnetic microsphere prepared by the invention can move controllably under an external magnetic field, is suitable for direct separation after biomolecule enrichment, has good biocompatibility, and has excellent application value in the technical fields of targeted drug delivery, cell culture and the like except magnetic separation.
Drawings
FIG. 1 is a schematic diagram of a process for preparing hedgehog shaped magnetic microspheres.
FIG. 2 is a scanning electron microscopy topography of a sample prepared under the conditions of example 1 in accordance with the present invention. The figure a is magnetic nano particles, the figure b is magnetic nano particles coated by silicon dioxide, and the figure c is hedgehog shaped magnetic microspheres. The scale in the figure is 100nm.
FIG. 3 is a transmission electron microscopy topographic map of a sample prepared under the conditions of example 1 in accordance with the present invention. The figure a is magnetic nano particles, the figure b is magnetic nano particles coated by silicon dioxide, and the figure c is hedgehog shaped magnetic microspheres. The scale in the figure is 100nm.
Detailed Description
The foregoing aspects of the present invention are described in further detail below by way of examples, but it should not be construed that the scope of the subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above aspects of the present invention are within the scope of the present invention.
The experimental procedures used in the examples below are conventional procedures unless otherwise specified, and the reagents, methods and equipment used therein are conventional in the art unless otherwise specified.
Example 1
(1) Preparing magnetic nanoparticles:
a brown mixed solution was obtained by adding 0.26g of anhydrous ferric chloride, 1.2g of sodium acetate, 0.4g of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (molar ratio 1), 0.004g of L-ascorbic acid and 40ul of ultrapure water to 16ml of ethylene glycol solution in this order and vigorously stirring them. 0.24g of sodium hydroxide was added to the mixed solution, and stirring was continued for 30min to obtain a brown transparent solution. Transferring the magnetic nanoparticles into a 20ml reaction kettle, calcining for 9h at 190 ℃ by a hydrothermal method to obtain magnetic nanoparticles, and mixing the magnetic nanoparticles with ethanol and water in a ratio of (1): 1, mixing and cleaning for three times, and then cleaning for three times by using ultrapure water.
(2) Preparing the magnetic nano particles coated by the silicon dioxide:
dispersing 6ml of the magnetic nanoparticles in 40ml of ethanol, adding 2ml of ammonia water, ultrasonically dispersing for 15min, slowly dropwise adding tetraethyl orthosilicate 200ul under the condition of 50 ℃ water bath, stirring for 1h at 600r, collecting the magnetic nanoparticles coated by silicon dioxide, and respectively washing with ethanol and water for three times.
(3) Preparing hedgehog magnetic microspheres:
0.0714g of magnesium chloride and 0.5349g of ammonium chloride are weighed and dispersed in 30ml of ultrapure water, and the mixture is uniformly mixed with 0.05g of the magnetic nano particles wrapped by the silicon dioxide, 350ul of ammonia water is added, and ultrasonic dispersion is carried out for 30min. Transferring the mixture into a 20ml reaction kettle, and calcining the mixture for 14 hours at 140 ℃ to obtain the hedgehog shaped magnetic microspheres.
Example 2
(1) Preparing magnetic nanoparticles:
a brown mixed solution was obtained by adding 0.26g of anhydrous ferric chloride, 1.2g of sodium acetate, 0.4g of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (molar ratio 1), 0.004g of L-ascorbic acid and 100ul of ultrapure water to 16ml of ethylene glycol solution in this order and vigorously stirring them. 0.24g of sodium hydroxide was added to the mixed solution, and stirring was continued for 30min to obtain a brown transparent solution. Transferring the magnetic nanoparticles into a 20ml reaction kettle, calcining the magnetic nanoparticles for 9 hours at 190 ℃ by a hydrothermal method to obtain magnetic nanoparticles, and mixing the magnetic nanoparticles with ethanol and water in a ratio of 1:1, mixing and cleaning for three times, and then cleaning for three times by using ultrapure water.
(2) Preparing the magnetic nano particles coated by the silicon dioxide:
dispersing 6ml of the magnetic nanoparticles in 40ml of ethanol, adding 2ml of ammonia water, performing ultrasonic dispersion for 15min, slowly dropwise adding tetraethyl orthosilicate 200ul under the condition of 50 ℃ water bath, stirring 600r for 1h, collecting the magnetic nanoparticles coated by silicon dioxide, and respectively washing the magnetic nanoparticles with ethanol and water for three times.
(3) Preparing hedgehog magnetic microspheres:
0.0714g of magnesium chloride and 0.5349g of ammonium chloride are weighed and dispersed in 30ml of ultrapure water, and the mixture is uniformly mixed with 0.05g of the magnetic nano particles wrapped by the silicon dioxide, 350ul of ammonia water is added, and ultrasonic dispersion is carried out for 30min. Transferring the mixture into a 20ml reaction kettle, and calcining the mixture for 14 hours at 140 ℃ to obtain the hedgehog shaped magnetic microspheres.
Example 3
(1) Preparing magnetic nanoparticles:
a brown mixed solution was obtained by adding 0.26g of anhydrous ferric chloride, 1.2g of sodium acetate, 0.4g of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (molar ratio 1), 0.004g of L-ascorbic acid and 40ul of ultrapure water to 16ml of ethylene glycol solution in this order and vigorously stirring them. 0.24g of sodium hydroxide was added to the mixed solution, and stirring was continued for 30min to obtain a brown transparent solution. Transferring the magnetic nanoparticles into a 20ml reaction kettle, calcining the magnetic nanoparticles for 9 hours at 190 ℃ by a hydrothermal method to obtain magnetic nanoparticles, and mixing the magnetic nanoparticles with ethanol and water in a ratio of 1:1, mixing and cleaning for three times, and then cleaning for three times by using ultrapure water.
(2) Preparing the magnetic nano particles coated by the silicon dioxide:
dispersing 6ml of the magnetic nanoparticles in 40ml of ethanol, adding 2ml of ammonia water, performing ultrasonic dispersion for 15min, slowly dropwise adding 200ul of tetraethyl orthosilicate under the condition of water bath at 50 ℃, stirring vigorously for 20min, slowly dropwise adding 200ul of tetraethyl orthosilicate again, stirring for 1h at 600r, collecting the magnetic nanoparticles coated by silicon dioxide, and respectively cleaning with ethanol and water for three times.
(3) Preparing hedgehog magnetic microspheres:
0.0714g of magnesium chloride and 0.5349g of ammonium chloride are weighed and dispersed in 30ml of ultrapure water, and the mixture is uniformly mixed with 0.05g of the magnetic nano particles wrapped by the silicon dioxide, 350ul of ammonia water is added, and ultrasonic dispersion is carried out for 30min. Transferring the mixture into a 20ml reaction kettle, and calcining the mixture for 14 hours at 140 ℃ to obtain the hedgehog shaped magnetic microspheres.
Example 4
(1) Preparing magnetic nanoparticles:
to a 16ml ethylene glycol solution were added 0.26g of anhydrous ferric trichloride, 1.2g of sodium acetate, 0.4g of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (molar ratio 1), 0.004g of L-ascorbic acid and 40ul of ultrapure water in this order, and vigorously stirred to form a brown mixed solution. 0.24g of sodium hydroxide was added to the mixed solution, and stirring was continued for 30min to obtain a brown transparent solution. Transferring the magnetic nanoparticles into a 20ml reaction kettle, calcining the magnetic nanoparticles for 9 hours at 190 ℃ by a hydrothermal method to obtain magnetic nanoparticles, and mixing the magnetic nanoparticles with ethanol and water in a ratio of 1:1, mixing and cleaning for three times, and then cleaning for three times by using ultrapure water.
(2) Preparing the magnetic nano particles coated by the silicon dioxide:
dispersing 6ml of the magnetic nanoparticles in 40ml of ethanol, adding 2ml of ammonia water, ultrasonically dispersing for 15min, slowly dropwise adding 200ul of tetraethyl orthosilicate under the condition of 50 ℃ water bath, stirring vigorously for 20min, slowly dropwise adding 200ul of tetraethyl orthosilicate again, stirring for 1h at 600r, collecting the magnetic nanoparticles coated by silicon dioxide, and respectively washing with ethanol and water for three times.
(3) Preparing hedgehog-shaped magnetic microspheres:
0.0714g of magnesium chloride and 0.5349g of ammonium chloride are weighed and dispersed in 30ml of ultrapure water, and the mixture is uniformly mixed with 0.1g of the magnetic nano particles wrapped by the silicon dioxide, 350ul of ammonia water is added, and ultrasonic dispersion is carried out for 30min. Transferring the mixture into a 20ml reaction kettle, and calcining the mixture for 14 hours at 140 ℃ to obtain the hedgehog shaped magnetic microspheres.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of hedgehog shaped magnetic microsphere is characterized in that: the method comprises the following steps:
(1) Preparing magnetic nanoparticles:
adding anhydrous ferric trichloride, sodium acetate, poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, L-ascorbic acid and a proper amount of water into an ethylene glycol solution in sequence, and stirring to form a mixed solution; adding sodium hydroxide into the mixed solution, and continuously stirring to obtain a brown transparent solution; transferring the magnetic nanoparticles into a reaction kettle, and obtaining magnetic nanoparticles by a one-step hydrothermal method;
(2) Preparing the silica-coated magnetic nanoparticles:
dispersing the magnetic nanoparticles in ethanol, adding ammonia water, performing ultrasonic dispersion, slowly dropwise adding tetraethyl orthosilicate under the condition of a water bath at 50 ℃, stirring for 1h, and collecting the magnetic nanoparticles coated by silicon dioxide;
(3) Preparing hedgehog magnetic microspheres:
preparing a mixed solution of magnesium chloride and ammonium chloride, uniformly mixing the mixed solution with the magnetic nano particles wrapped by the silicon dioxide, adding ammonia water, and performing ultrasonic dispersion; transferring the hedgehog magnetic microsphere into a reaction kettle, and obtaining the hedgehog magnetic microsphere by a one-step hydrothermal method.
2. The method of preparing the hedgehog shaped magnetic microsphere of claim 1, wherein: the volume ratio of the glycol solution in the step (1) to a proper amount of water is 160:1 to 800:1.
3. the method of preparing the hedgehog shaped magnetic microsphere of claim 1, wherein: the size of the magnetic nanoparticles prepared in the step (1) can be changed by adjusting the water adding amount: when the water addition amount is reduced or increased, the magnetic nano particles can be correspondingly reduced or enlarged.
4. The method of preparing the hedgehog shaped magnetic microsphere of claim 1, wherein: the hedgehog shaped magnetic microspheres of the step (3) can change the size of the microspheres by adjusting the adding amount of the tetraethyl orthosilicate of the step (2): by decreasing or increasing tetraethyl orthosilicate, the hedgehog shaped magnetic microspheres will shrink or enlarge accordingly.
5. The method of preparing the hedgehog shaped magnetic microsphere of claim 1, wherein: the hydrothermal method in the step (1) is carried out for 9 hours at 190 ℃.
6. The method of preparing the hedgehog shaped magnetic microsphere according to claim 1, wherein: the hydrothermal method in the step (3) is carried out for 14 hours at 140 ℃.
7. The hedgehog-shaped magnetic microsphere prepared by the method according to any one of claims 1 to 6, wherein the shell is magnesium silicate, has a nano needle structure, and is shaped like hedgehog; the inner core is magnetic ferroferric oxide nano particles and has good magnetic responsiveness.
8. The hedgehog shaped magnetic microsphere of claim 7, wherein: the particle size of the core magnetic ferroferric oxide nano particle is 60-90nm, and the particle size of the magnetic microsphere is 250-300nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110472059.0A CN113066657B (en) | 2021-04-29 | 2021-04-29 | Hedgehog-shaped magnetic microsphere and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110472059.0A CN113066657B (en) | 2021-04-29 | 2021-04-29 | Hedgehog-shaped magnetic microsphere and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113066657A CN113066657A (en) | 2021-07-02 |
| CN113066657B true CN113066657B (en) | 2022-10-11 |
Family
ID=76568200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110472059.0A Active CN113066657B (en) | 2021-04-29 | 2021-04-29 | Hedgehog-shaped magnetic microsphere and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113066657B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113856573B (en) * | 2021-11-08 | 2023-09-01 | 国科温州研究院(温州生物材料与工程研究所) | Light-responsive gel microsphere for dPCR method nucleic acid detection and application of light-responsive gel microsphere in Proteus mirabilis detection |
| CN115254036B (en) * | 2022-09-26 | 2023-01-06 | 苏州浦隆生物有限公司 | Millimeter-scale solid-phase microsphere with 3D micro-nano structure surface and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215902C (en) * | 2003-09-11 | 2005-08-24 | 复旦大学 | Magnetic fluorescent double functional microballoon with core-shell structure and preparation method thereof |
| US7879625B1 (en) * | 2008-12-03 | 2011-02-01 | The United States Of America As Represented By The Secretary Of The Navy | Preparation of SERS substrates on silica-coated magnetic microspheres |
| CN101707106B (en) * | 2009-12-04 | 2011-12-28 | 陕西北美基因股份有限公司 | Method for preparing silicon dioxide magnetic composite microballoon with core-shell structure |
| CN101804990B (en) * | 2010-03-19 | 2012-11-07 | 中科院广州化学有限公司 | Preparation method of hedgehog SiO2 hollow microsphere |
| CN102319564B (en) * | 2011-06-15 | 2013-02-27 | 北京科技大学 | Preparation method of urchin-like titanium dioxide magnetic microspheres having double-layer cavity structures |
| CN102380335B (en) * | 2011-09-15 | 2014-03-12 | 东南大学 | Core-shell hydrogel colloid crystal microballoon, its preparation method and its purpose |
| CN111495344B (en) * | 2020-03-23 | 2023-02-17 | 江苏大学 | Photoresponse type molecularly imprinted polymer based on magnetic mesoporous silicon nanoparticles, preparation method and application |
-
2021
- 2021-04-29 CN CN202110472059.0A patent/CN113066657B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113066657A (en) | 2021-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113066657B (en) | Hedgehog-shaped magnetic microsphere and preparation method thereof | |
| CN106047290B (en) | A kind of method of nanometer Fe 3 O 4 magnetic uniform particle enveloped carbon nanometer tube | |
| JP5353004B2 (en) | Method for producing spherical ferrite nanoparticles | |
| CN103183374B (en) | Method for preparing monodisperse indium oxide nanometer porous microsphere | |
| CN101289314A (en) | Method for preparing nano hollow microballoons of spinelle type ferrite | |
| CN102623125B (en) | A kind of Fe containing many magnetic kernels 3o 4/ SiO 2the preparation method of nanoparticle | |
| CN107519501B (en) | Ferromagnetic nano material, preparation method and application | |
| CN102517020B (en) | Superparamagnetic fluorescent multifunctional mesoporous nanometer spherical material and preparation method thereof | |
| CN108658108A (en) | A kind of preparation method of hollow aluminum oxide microspheres | |
| CN105858706A (en) | Method for preparing yttrium oxide powder | |
| CN110665465A (en) | Magnetic covalent organic framework material for glycopeptide enrichment and preparation method and application thereof | |
| CN106328336A (en) | Method for preparing magnetic carbon nanotubes based on charge effect | |
| CN112957371A (en) | Preparation method of magnetic nanowire | |
| CN107802845B (en) | Method for phase conversion of hydrophobic nanoparticles by using silk fibroin molecules | |
| CN106115795B (en) | A kind of preparation method of functionalized carbon coated magnetic nano-particle | |
| CN108971509A (en) | A kind of preparation method of the iron-nickel alloy nano material of controllable grain size | |
| CN110550666B (en) | Monodisperse and superparamagnetic ferroferric oxide nanoflower and preparation method thereof | |
| Shao et al. | Characterization of Fe 3 O 4/SiO 2 composite core-shell nanoparticles synthesized in isopropanol medium | |
| CN103214026A (en) | Preparation method of CaO/ZnO core-shell structure nanometer material | |
| CN107601576B (en) | Ferroferric oxide hollow magnetic nano-particles and preparation method thereof | |
| CN110745813A (en) | Graphene-loaded ferroferric oxide magnetic powder particle and preparation method thereof | |
| CN110739110B (en) | Spherical nano magneton with stable solution dispersibility and preparation method thereof | |
| CN102910684A (en) | G-scale mould synthesis method of monodisperse ferroferric oxide nanometer particles | |
| CN112007605A (en) | Hydroxyl nano magnetic bead for nucleic acid extraction and preparation method thereof | |
| CN103219118A (en) | High-stability magnetic functional particles and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |