CN108864699B - Method for preparing magnetic dendrimer nanocomposite material with assistance of silane coupling agent - Google Patents
Method for preparing magnetic dendrimer nanocomposite material with assistance of silane coupling agent Download PDFInfo
- Publication number
- CN108864699B CN108864699B CN201810464224.6A CN201810464224A CN108864699B CN 108864699 B CN108864699 B CN 108864699B CN 201810464224 A CN201810464224 A CN 201810464224A CN 108864699 B CN108864699 B CN 108864699B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- water
- stirring
- drying
- coupling agent
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing 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
- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
- H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
- H01F1/0054—Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Power Engineering (AREA)
- Polymers & Plastics (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing a magnetic dendrimer nanocomposite material with the assistance of a silane coupling agent KH560, which comprises the following steps: 1) adding the magnetic nano powder into the alcohol-water mixed solution, and then adding strong ammonia water for stirring; 2) adding tetraethoxysilane and KH560 into the obtained suspension, and stirring; 3) magnetically separating, cleaning and drying a product obtained by the reaction in the step 2) to obtain KH560 modified and activated magnetic nanoparticles; 4) firstly, dissolving polyamide amine in methanol by ultrasonic to obtain polyamide amine methanol solution; dispersing the KH560 modified and activated magnetic nanoparticles into methanol, adding the magnetic nanoparticles into the polyamide amine methanol solution, and stirring for reaction; 5) and magnetically separating, cleaning and drying the product obtained by the reaction in the step 4) to obtain the KH560 assisted grafted magnetic dendrimer nanocomposite. The preparation method has the advantages of simple preparation process, easily obtained raw materials and good grafting effect.
Description
Technical Field
The invention belongs to the technical field of functional materials, and relates to a preparation method of a magnetic dendrimer nanocomposite.
Background
The magnetic dendrimer nanocomposite takes nano magnetic particles as a core, and dendrimers are grafted on the surface by utilizing molecular bonds to form the core-shell structure composite. The material has the performance advantages of two materials, namely magnetic particles and dendritic macromolecules, and has the characteristics of a large number of active functional groups, good biological activity, superparamagnetism, easy surface functionalization and the like.
Take ferroferric oxide/Polyamidoamine (PAMAM) magnetic dendrimers as an example. The PAMAM has the characteristics of precise molecular structure, a large number of surface end group functional groups, controllable relative molecular weight, nano-size molecules, good biocompatibility and the like, so that the PAMAM becomes a tree-shaped macromolecule which is most widely researched at present, and is the focus of attention in various fields. The nano ferroferric oxide has the characteristics of high saturation magnetization, ultralow coercive force, superparamagnetism, good biocompatibility, nano size effect, extremely high specific surface area and the like, so that the nano ferroferric oxide has wide application prospect. If the two can be combined to form a core-shell structure nano composite material, the nano composite material has huge application potential in the fields of biomedicine, medical diagnosis, drug slow release, sewage treatment, catalysts and the like, and in many biomedical and industrial engineering fields.
However, the dendritic macromolecule and the magnetic core can not be directly grafted, and other substances are needed for assistance, so that an active group is introduced to the surface of the magnetic core.
At present, 3-aminopropyltriethoxysilane, polystyrene, chloroauric acid, cysteamine, 1, 4-diaminobutane and other substances are used for assisting grafting of the dendritic macromolecules and the magnetic cores, but the methods for assisting grafting by using the substances have the technical defects of more or less complex preparation process, difficult obtainment of reactants, high reaction condition requirement, poor environmental pollution or biocompatibility, weak activity of groups after magnetic particles are grafted with active groups and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel method for preparing a magnetic dendrimer nanocomposite.
In order to solve the technical problem, the invention provides a method for preparing a magnetic dendrimer nanocomposite material with the assistance of a silane coupling agent KH560, which comprises the following steps:
1) adding magnetic nano powder (ferroferric oxide) into an alcohol-water mixed solution, performing ultrasonic dispersion (the dispersion time is about 15 +/-5 minutes), adding concentrated ammonia water (25-28% by mass concentration) until the pH value is 11 +/-0.5, and continuously stirring for 0.4-0.6 hours (preferably 0.5 hour); obtaining a suspension (black suspension);
2) adding tetraethoxysilane into the suspension (black suspension) obtained in the step 1) according to the dosage ratio of 0.8-1.2 ml (preferably 1ml) tetraethoxysilane matched with each 0.2 g of magnetic nano powder, stirring for 0.8-1.2 hours (preferably 1 hour), then adding KH560 (gamma-glycidyl ether oxypropyl trimethoxysilane), and continuously stirring for reaction for 11-13 hours (preferably 12 hours); the volume ratio of the KH560 to the tetraethoxysilane is 1: 0.9-1.1 (preferably 1: 1);
3) magnetically separating, cleaning and drying (freeze drying) a product (black product) obtained by the reaction in the step 2) to obtain KH560 modified and activated magnetic nanoparticles;
4) firstly, dissolving polyamide amine (PAMAM) in methanol by ultrasonic to obtain a polyamide amine (PAMAM) methanol solution; dispersing the KH560 modified and activated magnetic nanoparticles into methanol, adding the dispersed magnetic nanoparticles into the polyamide amine (PAMAM) methanol solution, and stirring to react for 22-26 hours (preferably 24 hours);
KH560 modifies activated magnetic nanoparticles: the mass ratio of polyamide amine (PAMAM) is 0.18-0.22: 1 (preferably 0.2: 1);
remarking: polyamidoamine (PAMAM), i.e., polyamidoamine dendrimers;
5) and magnetically separating, cleaning and drying (freeze drying) the product (black product) obtained by the reaction in the step 4) to obtain the KH560 assisted grafted magnetic dendrimer nanocomposite.
The improvement of the method for preparing the magnetic dendrimer nanocomposite assisted by the silane coupling agent KH560, which is disclosed by the invention, comprises the following steps:
in the step 1), the magnetic nano powder is monodisperse ferroferric oxide nanoflower with the grain diameter of 40-60 nanometers.
The silane coupling agent KH560 is used as a further improvement of the method for preparing the magnetic dendrimer nanocomposite material by assisting the silane coupling agent KH 560:
in the step 1), the alcohol-water mixed solution is prepared by mixing an alcohol-water mixed solution and a water-alcohol mixed solution in a volume ratio of 7-8: 1 (preferably 7.5: 1) the ethanol and the water;
each 0.2 g of the magnetic nano powder is mixed with 150-200 ml (preferably 170ml) of alcohol-water mixed solution.
The silane coupling agent KH560 is used as a further improvement of the method for preparing the magnetic dendrimer nanocomposite material by assisting the silane coupling agent KH 560:
dissolving polyamide amine (PAMAM) in methanol by ultrasonic according to the dosage ratio of 25-35 ml (preferably 30ml) of methanol for each gram of polyamide amine (PAMAM);
the KH560 modified and activated magnetic nanoparticles are dispersed in methanol in an amount of 80-120 ml (preferably 100ml) of methanol per 0.2 g of KH560 modified and activated magnetic nanoparticles.
The Polyamidoamine (PAMAM) is a whole generation polyamidoamine, i.e., the polyamidoamine macromolecule is a whole generation macromolecule.
The silane coupling agent KH560 is used as a further improvement of the method for preparing the magnetic dendrimer nanocomposite material by assisting the silane coupling agent KH 560: the cleaning in the step 3) and the step 5) are both as follows: washing with ethanol and water in sequence.
The silane coupling agent KH560 is used as a further improvement of the method for preparing the magnetic dendrimer nanocomposite material by assisting the silane coupling agent KH 560: the drying in the step 3) and the step 5) is freeze drying.
The step 3) is as follows: magnetically separating and cleaning products correspondingly obtained from every 0.2 g of magnetic nano powder, keeping 20 +/-5 ml of water, and drying at minus 86 +/-5 ℃ for 24 +/-2 hours;
the step 5) is as follows: every 0.2 g of magnetic nano particles after KH560 activation are magnetically separated and washed, 20 +/-5 ml of water is reserved, and the magnetic nano particles are dried for 24 +/-2 hours at minus 86 +/-5 ℃.
KH560 is commonly known as gamma-glycidoxypropyltrimethoxysilane, a common silane coupling agent, and its organic active groups are epoxy groups and ether bonds. KH560 can be coated on the surface of the magnetic particles after hydrolysis in water, so that the surface of the magnetic particles is rich in epoxy groups and ether bonds, and the groups with high activity are easy to react with the macromolecular amino terminal groups, thereby facilitating subsequent reaction grafting. Due to the characteristics of KH560, the material is a good auxiliary material for grafting ferroferric oxide nano magnetic cores and polyamidoamine dendritic macromolecules.
According to the invention, a layer of active groups is grafted on the surface of the magnetic nanoparticles by virtue of hydrolytic polymerization of KH560, and the active groups are reacted and grafted with later-added amino-terminated dendritic macromolecules to prepare the magnetic dendritic macromolecule nanocomposite. The ferroferric oxide/polyamidoamine magnetic dendrimer nanocomposite prepared by the method has good magnetism and a stable and uniform core-shell structure, and the ferroferric oxide and the polyamidoamine phases are well reacted and grafted. The magnetic dendrimer nanocomposite prepared by the method has great application potential in the fields of biomedicine, medical diagnosis, drug sustained release, sewage treatment, catalysts and the like and industrial engineering.
The preparation method of the invention is obtained by the inventor through earnest research and experiments. The invention has the following beneficial effects: compared with other methods, the preparation method has the advantages of simple preparation process, easily obtained raw materials and better grafting effect; the prepared magnetic dendritic macromolecular nanocomposite material has a stable structure and good dispersibility, and not only keeps the excellent magnetic property of magnetic core particles, but also keeps good group activity of macromolecules.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a transmission electron micrograph of the magnetic dendrimer nanocomposite prepared in example 1.
FIG. 2 is an IR spectrum of the magnetic dendrimer nanocomposite prepared in example 1.
FIG. 3 is a magnetic hysteresis loop diagram of the magnetic dendrimer nanocomposite prepared in example 1.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Selecting SK2200HP ultrasonic cleaner of Shanghai Ke ultrasonic apparatus Co., Ltd, with working frequency of 53kHz and power of 100 w; the stirring speed is 500-600 revolutions per minute;
the 2.0 generation polyamidoamine dendrimer can be prepared according to the published production process of the dendrimer polyamidoamine (publication No. CN 103601895B).
Example 1, a method for preparing a magnetic dendrimer nanocomposite assisted by a silane coupling agent KH560, sequentially performing the following steps:
1) adding 0.2 g of ferroferric oxide (monodisperse ferroferric oxide nanoflowers with the particle size of 40-60 nanometers) into a mixed solution of 20ml of water and 150 ml of ethanol, performing ultrasonic dispersion for 15 minutes, adding about 1ml of concentrated ammonia water (ammonia water with the mass concentration of 25-28%), adjusting the pH value of the system to be 11, and continuing stirring for 0.5 hour; obtaining a suspension (black suspension);
2) adding 1ml of ethyl orthosilicate into the black suspension obtained in the step (1), stirring and reacting for 1 hour, then adding 1ml of KH560, and continuously stirring and reacting for 12 hours;
3) magnetically separating a black product obtained by the reaction, sequentially and respectively washing with 50 ml of ethanol and 50 ml of water, and freeze-drying (retaining about 20ml of water and drying at-86 ℃ for 24 hours) to obtain KH560 modified and activated magnetic nanoparticles;
4) dispersing 0.2 g of magnetic nanoparticles activated by KH560 in 100ml of methanol, adding a solution obtained by dissolving 1 g of 2.0-substituted polyamidoamine macromolecules in 30ml of methanol, and stirring for reacting for 24 hours;
5) and magnetically separating a black product obtained by the reaction, sequentially and respectively washing with 50 ml of ethanol and 50 ml of water, and freeze-drying (retaining about 20ml of water and drying at-86 ℃ for 24 hours) to obtain the KH560 assisted grafted magnetic dendrimer nanocomposite.
Experiment I, the magnetic dendritic macromolecule nano composite material prepared by the invention has a stable structure and good dispersibility, and not only keeps the excellent magnetic property of magnetic core particles, but also keeps good group activity of macromolecules.
FIG. 1 is a transmission electron microscope image taken by a Japanese Electron JEM-2100 type transmission electron microscope, in which it can be seen that the surface coating thickness of the magnetic core is uniform, the structure of the magnetic core is not destroyed, and good dispersibility is maintained.
FIG. 2 is an infrared spectrum of magnetic dendrimer measured by ThermoFisher Nicolet 5700 type infrared spectrometer, in which the infrared characteristic peaks of KH560 and PAMAM can be clearly seen, which indicates that PAMAM macromolecule is successfully grafted on the surface of magnetic core with the assistance of KH560, and at 3400cm-1The infrared absorption peak with strong amino end group nearby shows that the material is provided withThe surface has a large number of amino groups.
FIG. 3 is a room temperature magnetic hysteresis loop of magnetic dendrimers measured by a Lakeshore 7410 model vibration magnetometer (VSM), from which it can be seen that the coercivity of the material is only about 12Oe (low coercivity is helpful for the dispersion and reuse of the material in water), and the saturation magnetization is 44.164emu/g, indicating that the magnetic core still maintains high magnetic response characteristics after the surface is grafted with the dendrimers.
Comparative examples 1-1,
The step 2) is changed into the following steps: 2) adding only 1ml of tetraethoxysilane into the black suspension obtained in the step 1), and stirring to react for 12 hours;
the rest is equivalent to embodiment 1.
Comparative examples 1 to 2,
The step 2) is changed into the following steps: 2) adding 1ml of ethyl orthosilicate into the black suspension obtained in the step 1), stirring and reacting for 1 hour, then adding 2ml of KH560, and continuously stirring and reacting for 12 hours;
the rest is equivalent to embodiment 1.
Comparative examples 2,
Changing the step 2) of adding 1ml of KH560 into the step of adding 1ml of amino group silane coupling agent KH550,
changing the 2.0 generation polyamidoamine macromolecules in the step 4) into 2.5 generation polyamidoamine macromolecules with unchanged dosage;
the rest is equivalent to embodiment 1.
Comparative examples 3-1,
The step 2) is changed into the following steps: 2) adding only 1ml of KH560 into the black suspension obtained in the step 1), and stirring to react for 12 hours;
the rest is equivalent to embodiment 1.
Comparative examples 3-2,
The step 2) is changed into the following steps: 2) adding 1ml of methyl orthosilicate into the black suspension obtained in the step 1), stirring and reacting for 1 hour, then adding 1ml of KH560, and continuously stirring and reacting for 12 hours;
the rest is equivalent to embodiment 1.
Comparative examples 4,
The step 1) is changed into the following steps: 1) adding 0.2 g of ferroferric oxide (monodisperse ferroferric oxide nanoflower with the particle size of 40-60 nanometers) into a mixed solution of 20ml of water and 150 ml of ethanol, performing ultrasonic dispersion for 15 minutes, and then stirring for 0.5 hour;
the rest is equivalent to embodiment 1.
Comparative examples 5,
The freeze drying of the step 3) is changed into: drying at 60 ℃ to constant weight;
the freeze drying of the step 5) is changed into: drying at 60 ℃ to constant weight;
the rest is equivalent to embodiment 1.
Comparative experiment, all the above comparative examples were tested for performance according to the method described in experiment one, and the results are shown in table 1 below.
TABLE 1
And example 1 is: monodisperse, uniform coating and good grafting with macromolecules.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (1)
1. A method for preparing a magnetic dendrimer nanocomposite material with the assistance of a silane coupling agent KH560 is characterized by sequentially carrying out the following steps:
1) adding 0.2 g of ferroferric oxide into a mixed solution of 20ml of water and 150 ml of ethanol, ultrasonically dispersing for 15 minutes, then adding 1ml of concentrated ammonia water, adjusting the pH value of the system to 11, and continuously stirring for 0.5 hour; obtaining black suspension;
the ferroferric oxide is monodisperse ferroferric oxide nanoflower with the particle size of 40-60 nanometers;
the concentrated ammonia water is ammonia water with the mass concentration of 25-28%;
2) adding 1ml of ethyl orthosilicate into the black suspension obtained in the step 1), stirring and reacting for 1 hour, then adding 1ml of KH560, and continuously stirring and reacting for 12 hours;
3) magnetically separating the black product obtained by the reaction in the step 2), sequentially and respectively washing with 50 ml of ethanol and 50 ml of water, and freeze-drying to obtain KH560 modified and activated magnetic nanoparticles;
the freeze drying comprises the following steps: keeping 20ml of water, and drying at-86 ℃ for 24 hours;
4) dispersing 0.2 g of KH560 modified and activated magnetic nanoparticles into 100ml of methanol, adding a solution obtained by dissolving 1 g of 2.0-substituted polyamidoamine macromolecules into 30ml of methanol, and stirring for reacting for 24 hours;
5) magnetically separating the black product obtained by the reaction in the step 4), sequentially and respectively washing with 50 ml of ethanol and 50 ml of water, and freeze-drying to obtain the magnetic dendrimer nanocomposite prepared by the aid of the silane coupling agent KH 560;
the freeze drying comprises the following steps: 20ml of water were retained and dried at-86 ℃ for 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810464224.6A CN108864699B (en) | 2018-05-15 | 2018-05-15 | Method for preparing magnetic dendrimer nanocomposite material with assistance of silane coupling agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810464224.6A CN108864699B (en) | 2018-05-15 | 2018-05-15 | Method for preparing magnetic dendrimer nanocomposite material with assistance of silane coupling agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108864699A CN108864699A (en) | 2018-11-23 |
| CN108864699B true CN108864699B (en) | 2020-12-04 |
Family
ID=64334419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810464224.6A Active CN108864699B (en) | 2018-05-15 | 2018-05-15 | Method for preparing magnetic dendrimer nanocomposite material with assistance of silane coupling agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108864699B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110379577B (en) * | 2019-07-09 | 2020-07-07 | 中国科学院化学研究所 | Switch type emulsion based on magnetic particles and preparation method thereof |
| CN115073755B (en) * | 2021-03-12 | 2024-05-14 | 中国石油化工股份有限公司 | Dendritic macromolecule coupling agent and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864167A (en) * | 2007-11-13 | 2010-10-20 | 中国科学院金属研究所 | Magnetic iron oxide-dendritic polyamide core-shell nano complex and preparation thereof |
| CN101955231B (en) * | 2010-10-20 | 2012-07-04 | 华东师范大学 | Preparation method of surface dendritic macromolecule modified superparamagnetism ferroferric oxide nano particle |
| CN103553181B (en) * | 2013-10-31 | 2014-09-03 | 东南大学 | Preparation method of magnetic antiphase demulsifier |
-
2018
- 2018-05-15 CN CN201810464224.6A patent/CN108864699B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108864699A (en) | 2018-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A molecularly imprinted polymer-coated nanocomposite of magnetic nanoparticles for estrone recognition | |
| CN101256864B (en) | Superparamagnetism mesoporous silicon dioxide composite ball and preparing method thereof | |
| Ding et al. | Synthesis and magnetic properties of biocompatible hybrid hollow spheres | |
| Dung et al. | Preparation and characterization of magnetic nanoparticles with chitosan coating | |
| CN108711480B (en) | Magnetic mesoporous silica nanochain with core-shell structure and preparation method thereof | |
| CN102161729B (en) | Preparation method of water-soluble polysaccharide/hydrophobic monomer formed nanoparticles | |
| Pan et al. | Poly (2-hydroxypropylene imines) functionalized magnetic polydopamine nanoparticles for high-efficiency DNA isolation | |
| CN112516956A (en) | Preparation method and application of magnetic composite nano material | |
| CN102623125B (en) | A kind of Fe containing many magnetic kernels 3o 4/ SiO 2the preparation method of nanoparticle | |
| CN106323935B (en) | Magnetic composite SERS substrate with core-shell-satellite three-dimensional structure and preparation method thereof | |
| JP2019509975A (en) | Method for producing superparamagnetic nanocomposite and superparamagnetic nanocomposite produced using the same | |
| CN108864699B (en) | Method for preparing magnetic dendrimer nanocomposite material with assistance of silane coupling agent | |
| CN110665465B (en) | Magnetic covalent organic framework material for glycopeptide enrichment and preparation method and application thereof | |
| CN105885354A (en) | Preparing method of polyhedral oligomeric silsesquioxane modified carbon nano tubes and application | |
| Dayyani et al. | Synthesis and characterization of the first generation of polyamino-ester dendrimer-grafted magnetite nanoparticles from 3-aminopropyltriethoxysilane (APTES) via the convergent approach | |
| CN102517020B (en) | Superparamagnetic fluorescent multifunctional mesoporous nanometer spherical material and preparation method thereof | |
| CN105399987A (en) | Surface-modified silica/oxidized graphene nanocomposite and preparation method thereof | |
| CN102794140A (en) | Preparation method of grain size-controllable nuclear shell Fe3O4/SiO2 nanoparticle | |
| CN101521067A (en) | Core/shell type magnetic particle product and preparing method thereof | |
| CN114591726A (en) | Method for preparing stable single-dispersion crosslinked polystyrene magnetic microspheres | |
| CN109464969A (en) | A kind of functional method of ferroso-ferric oxide/Nano particles of silicon dioxide surface richness nitrogen polymer | |
| CN107802845B (en) | Method for phase conversion of hydrophobic nanoparticles by using silk fibroin molecules | |
| CN1193383C (en) | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method | |
| Li et al. | Preparation of superparamagnetic β-cyclodextrin-functionalized composite nanoparticles with core–shell structures | |
| CN1747078A (en) | Modified water-base magnetic liquid of polymer and production 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 |