CN107790075B - Magnetic mesoporous SiO with core-shell structure2Process for preparing nanoparticles - Google Patents
Magnetic mesoporous SiO with core-shell structure2Process for preparing nanoparticles Download PDFInfo
- Publication number
- CN107790075B CN107790075B CN201610804874.1A CN201610804874A CN107790075B CN 107790075 B CN107790075 B CN 107790075B CN 201610804874 A CN201610804874 A CN 201610804874A CN 107790075 B CN107790075 B CN 107790075B
- Authority
- CN
- China
- Prior art keywords
- sio
- magnetic
- ethanol
- mesoporous
- edps
- 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
-
- 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
- B01J13/06—Making microcapsules or microballoons by phase separation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0002—Galenical forms characterised by the drug release technique; Application systems commanded by energy
- A61K9/0009—Galenical forms characterised by the drug release technique; Application systems commanded by energy involving or responsive to electricity, magnetism or acoustic waves; Galenical aspects of sonophoresis, iontophoresis, electroporation or electroosmosis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/51—Nanocapsules; Nanoparticles
- A61K9/5107—Excipients; Inactive ingredients
- A61K9/5115—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/51—Nanocapsules; Nanoparticles
- A61K9/5107—Excipients; Inactive ingredients
- A61K9/5123—Organic compounds, e.g. fats, sugars
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
Abstract
The invention discloses a magnetic mesoporous SiO with a core-shell structure2Method for producing nanoparticles from Fe3O4Is used as a magnetic carrier, tetraethoxysilane is used as a silicon source, hexadecyl trimethyl ammonium chloride is used as a surfactant, and the Fe with a radial mesoporous core-shell three-layer structure is obtained3O4@SiO2@mSiO2Magnetic mesoporous nanoparticles with N- [3- (trimethoxysilyl) propyl group]The ethylenediamine is amino-group loaded on the surface and in the pore channels of the amino-silane coupling agent. In addition, the invention also uses triethylamine and cyclohexane as organic swelling agent, get the mesoporous layer with bigger aperture. The magnetic mesoporous SiO prepared by the method of the invention2The nano particles have good magnetism, high dispersibility and unique pore channel structure, and have wide application prospect in the aspects of drug release, biology, materials science and the like.
Description
Technical Field
The invention belongs toThe mesoporous material preparation field, in particular to a magnetic mesoporous SiO with a core-shell structure2A method for preparing nanoparticles.
Background
Mesoporous SiO2The nano particles are nano materials with radial vertical pore canals on the surfaces. Due to mesoporous SiO2The microsphere has larger specific surface area and unique pore channel structure, so that the microsphere can be widely applied in the fields of composite materials, biology, medicine and the like, in particular to the aspects of adsorption application and drug release. Magnetic mesoporous SiO2The nano particles are magnetic particles embedded in mesoporous SiO2Inside, a core-shell two-layer structure is formed, so that the magnetic material has magnetism while keeping a unique pore channel structure. The core-shell three-layer structure has larger grain diameter and more complete spherical structure, and more molecules can be loaded on the surface and in the pore channels.
Magnetic mesoporous SiO prepared by the existing method2The nano particles can not see a complete and uniform pore channel structure, and have a plurality of defects in the aspects of morphology structure and application (document 1: Wang Miao, et al2/Fe3O4Laccase immobilization of hollow magnetic microspheres [ J]Chemical journal of higher school, 2013 (2): 299 to 305, reference 2: weiwei Zha.et. al Novel Method To investate the Interaction Force between Etoposide and APTES-Functionalized Fe3O4@nSiO2@mSiO2Nanocarrier for Drug Loading and Release processes, Phys, chem.C 2015,119,4379-4386). Therefore, it is necessary to develop a method for preparing magnetic mesoporous nanoparticles with good dispersibility, complete structural layering, and clear and uniform pore structure, so as to further meet the requirements of practical applications.
Disclosure of Invention
The invention aims to provide magnetic mesoporous SiO with a core-shell structure2The preparation method of the nano particles is simple, and the prepared magnetic mesoporous SiO is2The nano particles have uniform particle size distribution, clear and visible pore channel structure, and obviously improved adsorption capacity and drug loading capacity.
In order to achieve the purpose, the technical solution of the invention is as follows:
magnetic mesoporous SiO with core-shell structure2The preparation method of the nano-particles comprises the following steps:
step 1, adding Fe3O4Dispersing magnetic nanoparticles in mixed solution of ethanol and water, Tetraethoxysilane (TEOS) as silicon source, and ammonia water (NH)3·H2O) as an alkali source, and reacting at 30-40 ℃ to obtain Fe with a core-shell structure3O4@SiO2Magnetic nanoparticles;
step 2, according to Fe3O4@SiO2、H2The molar ratio of O, ammonia water, CTAC and EDPS is 1.4-2.1: 125-130: 1: 0.2-0.3: 0.15-0.2, the volume ratio of an ethanol solution of TEOS to water and ethanol is 1:11:5, and Fe in the step 1 is added3O4@SiO2Dispersing in mixed solution of ethanol, water and cetyltrimethylammonium chloride (CTAC), adding NH3·H2Taking O as an alkali source and a catalyst, dropwise adding 1.2-1.4M TEOS ethanol solution into a reaction system under the stirring condition, adding an aminosilane reagent N- [3- (trimethoxysilyl) propyl group after particles are formed]Stirring Ethylenediamine (EDPS) overnight, magnetically separating the product, refluxing the product in acetone to remove CTAC (cetyltrimethyl ammonium chloride) as surfactant, and obtaining Fe with three-layer structure3O4@SiO2@mSiO2EDPS magnetic nanoparticles, i.e. magnetic mesoporous SiO in core-shell structure2Nanoparticles.
In step 1, said Fe3O4The molar ratio of ammonia water to TEOS is 0.35-0.45: 57-86: 9.6-19.2, and the volume ratio of ethanol to water is 4: 1.
In the step 2, the acetone reflux time is 10-14 h, and the acetone reflux is repeated for 1-2 times.
Further preferably, in step 2, 10% by volume of Triethylamine (TEA) in ammonia is added before EDPS is added, and TEOS is dissolved in an equimolar amount of cyclohexane instead, so that a mesoporous layer with larger pore diameter can be obtained.
Compared with the prior art, the invention has the following remarkable effects: book (I)Fe prepared by the invention3O4@SiO2@mSiO2-EDPS magnetic mesoporous SiO2The nano particles have uniform particle size distribution, good dispersibility, obvious three-layer core-shell structure, clear and visible pore channel structure and good colloid stability, are not easy to aggregate in a solution and are loaded with a large number of amino groups on the surface; fe as a core of a particle3O4The magnetic nano-particles have good magnetic response property, can realize the rapid separation and the controlled migration of the magnetic mesoporous nano-particles under the action of an external magnetic field, simultaneously have unique pore channel structure, large specific surface area and pore volume, obviously improve the adsorption capacity and the drug loading capacity, and can reach 218.43mg/g for the adsorption capacity of DNA.
Drawings
FIG. 1 shows Fe prepared in example 13O4@SiO2(a) And Fe3O4@SiO2@mSiO2EDPS (edPS) (b) transmission electron microscopy of magnetic mesoporous nanoparticles.
FIG. 2 shows N of the magnetic mesoporous nanoparticles prepared in example 12Adsorption and desorption curve graphs and aperture distribution graphs.
FIG. 3 is a hysteresis loop diagram of the magnetic mesoporous nanoparticles prepared in example 1.
FIG. 4 is a transmission electron microscope image of the large-aperture magnetic mesoporous nanoparticles prepared in example 2.
FIG. 5 is a transmission electron microscope image of the magnetic mesoporous nanoparticles prepared in comparative examples 1 to 3.
FIG. 6 is Fe prepared in example 33O4@SiO2@mSiO2EDPS isolated DNA uv-spectrum.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1: magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2Preparation of EDPS
Mixing Fe3O4Dispersing 100mg of magnetic nanoparticles in a mixed solution of 160mL of ethanol and 40mL of water by ultrasonic treatment for 40min, and adding 2mL of NH under vigorous mechanical stirring3·H2O, then toDropwise adding 2.5mL TEOS within 10min, continuously stirring at 35 deg.C for 6h, washing with ethanol and deionized water for three times, magnetically separating, and vacuum drying at 40 deg.C for 10h to obtain SiO2Coated uniform-sized, core-shell structure of Fe3O4@SiO2Magnetic microspheres.
80mg of Fe is taken3O4@SiO2The magnetic microspheres were dispersed in a mixed solution containing 95mL of water, 43mL of ethanol, 2.5mL of ammonia and 0.3g of CTAC by sonication for 30 min. Subsequently, 2.5mL of TEOS was mixed in 6mL of ethanol, and added dropwise to the reaction system with stirring. After reacting for 15min, particles are formed, 2.5mL EDPS is added into the system drop by drop, after reacting for 18h at room temperature, products are collected by magnetic separation, and ethanol and water are respectively washed for three times. Finally, re-dispersing the product in 60mL of acetone, refluxing for 12h at 70 ℃ to remove CTAC, repeating the process once to ensure that CTAC is completely removed, thoroughly cleaning the product with ethanol, and drying in vacuum at 40 ℃ to obtain the magnetic mesoporous nano particle Fe with complete structure, uniform particle size and radial pore canal3O4@SiO2@mSiO2-EDPS。
Fe3O4@SiO2The transmission electron micrograph of the magnetic microspheres is shown in FIG. 1(a), and Fe can be seen3O4@SiO2The microsphere has the grain diameter of about 325nm, regular structure, uniform grain diameter and high dispersity, particularly Fe3O4@SiO2The microsphere core-shell structure is complete, and the shell thickness is about 60 nm. The prepared magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2EDPS is a distinct core-shell three-layer structure, as shown in FIG. 1(b), with the middle layer being solid SiO2The outermost layer is SiO with a radial pore canal structure2The overall nanoparticle size was approximately 415 nm.
Magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2N of EDPS2The adsorption-desorption curve is shown in FIG. 2, and it can be seen from FIG. 2 that N of the magnetic mesoporous nanoparticles2The adsorption and desorption curve belongs to type IV and is matched with the characteristic curve of the mesoporous structure. Simultaneously, the BET specific surface area of the obtained mesoporous nano particles is 217.8m2Per g, pore volume 0.161m3The concentration of the pores in the sample was 3.3nm as seen from the pore size distribution.
Magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2The magnetic response intensity of EDPS is shown in FIG. 3, and it can be seen from FIG. 3 that the magnetic mesoporous SiO is2The saturation magnetic moment of the nano particles is 8.73emu/g compared with the naked Fe3O4If the concentration is much smaller, the separation and enrichment can be achieved within 30s by fully utilizing the action of an external magnetic field in the separation process.
Example 2: large-aperture magnetic mesoporous Fe3O4@SiO2@mSiO2Preparation of EDPS nanoparticles
Fe3O4@SiO2The preparation method of the magnetic microspheres is the same as that of example 1.
80mg of Fe is taken3O4@SiO2The magnetic microspheres were dispersed by sonication for 30min in a mixed solution containing 95mL of water, 49mL of ethanol, 2.5mL of ammonia, 0.18mL of Triethylamine (TEA) and 0.3g of CTAC. Subsequently, 2.5mL of TEOS was dissolved in 6mL of cyclohexane and added dropwise to the reaction system with stirring. After reacting for 15min, particles are formed, 2.5mL EDPS is also added into the system drop by drop, after reacting for 18h at room temperature, products are collected by magnetic separation, and ethanol and water are respectively washed for three times. Finally, the nano particles are re-dispersed in 60mL of acetone, and the mixture is refluxed for 12h at 70 ℃ to remove CTAC, in order to ensure that CTAC is completely removed, the process is repeated once, the product is thoroughly cleaned by ethanol, and vacuum drying is carried out at 40 ℃ to obtain the large-aperture magnetic mesoporous Fe3O4@SiO2@mSiO2EDPS nanoparticles, the product being subjected to transmission electron microscopy as shown in FIG. 4.
FIG. 4 shows large-aperture magnetic mesoporous Fe3O4@SiO2@mSiO2An EDPS nano particle transmission electron microscope picture shows that TEOS is dissolved in an organic solvent cyclohexane and then added into a reaction system, when oligomers hydrolyzed by TEOS and CTAC form micelles, pores are supported to be larger due to the swelling effect of cyclohexane, the problem that the pore size is small due to the limitation of the chain length of CTAC is solved, and the pore size is further increased to 9-10 nm.
Comparative example 1: magnetic mesoporous nano particle Fe with NaOH as alkali source3O4@SiO2@mSiO2Preparation of EDPS
Fe3O4@SiO2The preparation method of the magnetic microspheres is the same as that of example 1.
80mg of Fe is taken3O4@SiO2The magnetic microspheres were dispersed ultrasonically for 30min in a mixed solution containing 95mL of water, 43mL of ethanol, 0.013 g of NaOH and 0.3g of CTAC. Subsequently, 2.5mL of TEOS was mixed in 6mL of ethanol, and added dropwise to the reaction system with stirring. After reacting for 15min, particles are formed, 2.5mL EDPS is also added into the system drop by drop, after reacting for 18h at room temperature, products are collected by magnetic separation, and ethanol and water are respectively washed for three times. Finally, the nano particles are re-dispersed in 60mL of acetone, and the mixture is refluxed for 12h at 70 ℃ to remove CTAC, in order to ensure that CTAC is completely removed, the process is repeated once, the product is thoroughly cleaned by ethanol, and the product is dried in vacuum at 40 ℃ to obtain the magnetic mesoporous nano particles Fe taking NaOH as an alkali source3O4@SiO2@mSiO2-EDPS。
Magnetic mesoporous nano particle Fe with NaOH as alkali source3O4@SiO2@mSiO2The transmission electron microscopy image of the-EDPS is shown in fig. 5a, and it can be seen that when NaOH is selected to replace ammonia water as an alkali source, the prepared magnetic mesoporous nanoparticles cannot see obvious pore channel structures, but the ammonia water in the invention also plays a role of a catalyst besides being used as the alkali source.
Comparative example 2: magnetic mesoporous nano particle Fe prepared by adding TEOS (tetraethyl orthosilicate) independently3O4@SiO2@mSiO2-EDPS
Fe3O4@SiO2The preparation method of the magnetic microspheres is the same as that of example 1.
80mg of the above Fe was taken3O4@SiO2The magnetic microspheres were dispersed in a mixed solution containing 95mL of water, 49mL of ethanol, 2.5mL of ammonia and 0.3g of CTAC by sonication for 30 min. Subsequently, 2.5mL of TEOS was added dropwise to the reaction system with stirring. After reacting for 15min, forming particles, adding 2.5mL EDPS into the system drop by drop, reacting for 18h at room temperature, magnetically separating and collecting the product, and washing with ethanol and water for three times. Finally, the nano particles are re-dispersed in 60mL of acetone, and the mixture is refluxed for 12h at 70 ℃ to remove CTAC, in order to ensure that CTAC is completely removed, the process is repeated once, the product is thoroughly cleaned by ethanol, vacuum drying is carried out at 40 ℃, TEOS is independently added into the prepared magnetic mesoporous nano particles Fe3O4@SiO2@mSiO2-EDPS。
Magnetic mesoporous nano particle Fe prepared by adding TEOS (tetraethyl orthosilicate) independently3O4@SiO2@mSiO2Transmission electron microscopy of EDPS As shown in FIG. 5b, it can be seen that TEOS alone, when added, tends to nucleate homogeneously rather than coat Fe due to the faster hydrolysis rate3O4@SiO2The surface of the particles. The method has the advantages that TEOS is dissolved in ethanol and added, so that the hydrolysis speed of TEOS is effectively controlled, and the method plays a great role in obtaining the three-layer mesoporous magnetic microspheres with complete structures and uniform particle sizes.
Comparative example 3: magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2Preparation of EDPS
Fe3O4@SiO2The preparation method of the magnetic microspheres is the same as that of example 1.
Taking 80mgFe3O4The magnetic microspheres were dispersed in a mixed solution containing 95mL of water, 43mL of ethanol, 2.5mL of ammonia and 0.3g of CTAC by sonication for 30 min. Subsequently, 2.5mL of TEOS was mixed in 6mL of ethanol, and added dropwise to the reaction system with stirring. After reacting for 15min, particles are formed, an additional 2.5mL of EDPS is also added into the system drop by drop, after reacting for 18h at room temperature, products are collected by magnetic separation, and ethanol and water are respectively washed for three times. Finally, the nanoparticles were redispersed in 60mL acetone and refluxed at 70 ℃ for 12h to remove CTAC, the process was repeated once to ensure complete removal of CTAC, the product was thoroughly washed with ethanol, dried at 40 ℃ in vacuo, and the product was subjected to transmission electron microscopy as shown in fig. 5 c.
As can be seen from FIG. 5c, in the presence of exposed Fe3O4Mesoporous SiO is directly coated on the magnetic microsphere2In the process, a complete core-shell mesoporous structure is not obtained, and the mesoporous structure is not uniform, so that the coated solid SiO is selected2Making on layerA layer of mesoporous structure.
Example 3: magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2Preparation of EDPS
Mixing Fe3O4Dispersing 80mg of magnetic nanoparticles in a mixed solution of 160mL of ethanol and 40mL of water by ultrasonic treatment for 40min, and adding 3mL of NH under vigorous mechanical stirring3·H2O, dropwise adding 4mL TEOS within 10min, continuously stirring at 35 ℃ for 6h, washing with ethanol and deionized water for three times, magnetically separating, and vacuum drying at 40 ℃ for 10h to obtain SiO2Coated uniform-sized, core-shell structure of Fe3O4@SiO2Magnetic microspheres.
80mg of Fe is taken3O4@SiO2The magnetic microspheres were dispersed in a mixed solution containing 95mL of water, 43mL of ethanol, 4mL of ammonia and 0.3g of CTAC by sonication for 30 min. Subsequently, 2mL of TEOS was mixed in 7.5mL of ethanol and added dropwise to the reaction system with stirring. After reacting for 15min, particles are formed, 2.5mL EDPS is added into the system drop by drop, after reacting for 18h at room temperature, products are collected by magnetic separation, and ethanol and water are respectively washed for three times. Finally, re-dispersing the product in 60mL of acetone, refluxing for 12h at 70 ℃ to remove CTAC, repeating the process once to ensure that CTAC is completely removed, thoroughly cleaning the product with ethanol, and drying in vacuum at 40 ℃ to obtain the magnetic mesoporous nano particle Fe with complete structure, uniform particle size and radial pore canal3O4@SiO2@mSiO2-EDPS。
Example 4: magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2Preparation of EDPS
Fe3O4@SiO2The preparation method of the magnetic microspheres is the same as that of example 1.
80mg of Fe is taken3O4@SiO2The magnetic microspheres were dispersed in a mixed solution containing 95mL of water, 43mL of ethanol, 2.5mL of ammonia and 0.4g of CTAC by sonication for 30 min. Subsequently, 2.5mL of TEOS was mixed in 6mL of ethanol, and added dropwise to the reaction system with stirring. After reacting for 15min, forming particles, adding 3.5mL EDPS into the system drop by drop, reacting for 18h at room temperature, and performing magnetic reactionThe product was collected by sexual separation and washed three times with ethanol and water, respectively. Finally, re-dispersing the product in 60mL of acetone, refluxing for 12h at 70 ℃ to remove CTAC, repeating the process once to ensure that CTAC is completely removed, thoroughly cleaning the product with ethanol, and drying in vacuum at 40 ℃ to obtain the magnetic mesoporous nano particle Fe with complete structure, uniform particle size and radial pore canal3O4@SiO2@mSiO2-EDPS。
Example 5: magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2Preparation of EDPS
Fe3O4@SiO2The preparation method of the magnetic microspheres is the same as that of example 1.
60mg of Fe are taken3O4@SiO2The magnetic microspheres were dispersed in a mixed solution containing 95mL of water, 43mL of ethanol, 2mL of ammonia and 0.3g of CTAC by sonication for 30 min. Subsequently, 4mL of TEOS was mixed in 6mL of ethanol, and added dropwise to the reaction system with stirring. After reacting for 15min, particles are formed, 2mL EDPS is added into the system drop by drop, after reacting for 18h at room temperature, products are collected by magnetic separation, and ethanol and water are washed for three times respectively. Finally, re-dispersing the product in 60mL of acetone, refluxing for 12h at 70 ℃ to remove CTAC, repeating the process once to ensure that CTAC is completely removed, thoroughly cleaning the product with ethanol, and drying in vacuum at 40 ℃ to obtain the magnetic mesoporous nano particle Fe with complete structure, uniform particle size and radial pore canal3O4@SiO2@mSiO2-EDPS。
Example 6: magnetic mesoporous nano particle Fe3O4@SiO2@mSiO2Use of EDPS for DNA extraction experiments
Preparing 1mg/mL standard DNA solution (the initial absorbance at 260nm is 0.880), adding 250 μ L into a 1.5 mL centrifuge tube, and adding different amounts of Fe to obtain the maximum DNA adsorption capacity of the prepared magnetic mesoporous nanoparticles3O4@SiO2@mSiO2EDPS suspension (100. mu.L, 150. mu.L, 200. mu.L, 250. mu.L, 300. mu.L) was added, followed by addition of a buffer (10mM Tris-HCl, 1mM EDTA) at pH 4.0 to 1mL of the reaction system, and after the adsorption process continued for 20min, magnetic separation was carried outThe ultraviolet absorbance at 260nm was measured after diluting the microspheres and the supernatant, and the ultraviolet spectrum was shown in FIG. 6.
As can be seen from FIG. 6, with Fe3O4@SiO2@mSiO2The increase of the amount of EDPS microspheres and the increase of the total amount of DNA adsorbed indicate that Fe is produced3O4@SiO2@mSiO2The EDPS microspheres have strong adsorption capacity on DNA, when the particle suspension is 300 mu L, the adsorption efficiency reaches 90 percent, and meanwhile, the maximum adsorption capacity of the DNA is calculated to be 218.43 mg/g.
Claims (1)
1. Magnetic mesoporous SiO with core-shell structure2The preparation method of the nano particles is characterized by comprising the following steps:
step 1, adding Fe3O4Dispersing magnetic nanoparticles in the mixture of ethanol and water, TEOS as silicon source, NH3·H2O is used as an alkali source and reacts at the temperature of 30-40 ℃ to obtain Fe with a core-shell structure3O4@SiO2Magnetic nanoparticles;
step 2, taking 80mg of Fe3O4@SiO2The magnetic microspheres are dispersed in a mixed solution containing 95mL of water, 49mL of ethanol, 2.5mL of ammonia water, 0.18mL of triethylamine and 0.3g of CTAC by ultrasonic treatment for 30 min; then, 2.5mL TEOS is dissolved in 6mL cyclohexane and added into the reaction system drop by drop under the stirring condition, the particles are formed after reacting for 15min, 2.5mL EDPS is also added into the system drop by drop, after reacting for 18h at room temperature, the product is collected by magnetic separation, and ethanol and water are respectively washed for three times; finally, the nano particles are re-dispersed in 60mL of acetone, and the mixture is refluxed for 12h at 70 ℃ to remove CTAC, in order to ensure that CTAC is completely removed, the process is repeated once, the product is thoroughly cleaned by ethanol, and vacuum drying is carried out at 40 ℃ to obtain the large-aperture magnetic mesoporous Fe3O4@SiO2@mSiO2-EDPS nanoparticles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610804874.1A CN107790075B (en) | 2016-09-06 | 2016-09-06 | Magnetic mesoporous SiO with core-shell structure2Process for preparing nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610804874.1A CN107790075B (en) | 2016-09-06 | 2016-09-06 | Magnetic mesoporous SiO with core-shell structure2Process for preparing nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107790075A CN107790075A (en) | 2018-03-13 |
| CN107790075B true CN107790075B (en) | 2020-12-11 |
Family
ID=61530465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610804874.1A Active CN107790075B (en) | 2016-09-06 | 2016-09-06 | Magnetic mesoporous SiO with core-shell structure2Process for preparing nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107790075B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110756174A (en) * | 2018-07-27 | 2020-02-07 | 南京理工大学 | Carboxylated magnetic nano-microsphere, preparation method and application thereof in cationic dye treatment |
| CN109174033B (en) * | 2018-08-27 | 2021-07-27 | 南京师范大学 | Blood lead ion scavenger capable of safely entering and exiting red blood cells and preparation method and application thereof |
| CN109731614B (en) * | 2018-12-07 | 2021-12-14 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Magnetic solid base catalyst and application thereof in esterification reaction |
| CN113058576B (en) * | 2021-03-08 | 2024-01-26 | 中国农业科学院北京畜牧兽医研究所 | Hollow core-shell structure nano magnetic microsphere, preparation method and application thereof |
| CN112961536A (en) * | 2021-04-13 | 2021-06-15 | 中国科学院兰州化学物理研究所 | Polytetrafluoroethylene-based core-shell type mesoporous composite material, preparation method thereof, oil-impregnated mesoporous composite material and application |
| CN113797226B (en) * | 2021-09-14 | 2023-09-19 | 华东师范大学 | Ammonia borane/silicon sphere/mesoporous silica nano composite particle, preparation and application thereof |
| CN114715951B (en) * | 2022-03-11 | 2023-08-04 | 上海应用技术大学 | Magnetic core-shell structure porous silica carrier for laccase immobilization and preparation method and application thereof |
| CN114920250A (en) * | 2022-04-12 | 2022-08-19 | 苏州星谱生物科技有限公司 | Preparation method of echinoid magnetic beads and application of echinoid magnetic beads in nucleic acid extraction |
| CN114759164B (en) * | 2022-06-13 | 2022-09-02 | 新乡市中天新能源科技股份有限公司 | Preparation method and application of lithium battery negative plate |
| CN115569631A (en) * | 2022-09-28 | 2023-01-06 | 湖北千里材料科技有限公司 | Ionic liquid immobilized magnetic nano-silica material, and preparation and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117223A (en) * | 2007-05-22 | 2008-02-06 | 四川大学 | Hydrothermal synthesis method for aperture control of meso-porous V-MCM-41 molecular screen |
| CN101521067A (en) * | 2008-02-29 | 2009-09-02 | 卡南吉医药科技（上海）有限公司 | Core/shell type magnetic particle product and preparing method thereof |
| US20100056366A1 (en) * | 2008-08-27 | 2010-03-04 | Korea University Industrial & Academic Collaboration Foundation | Nanoparticles including metal oxide having catalytic activity |
| US20110150938A1 (en) * | 2007-08-17 | 2011-06-23 | University Of Florida Research Foundation, Inc. | Supercrystalline Colloidal Particles and Method of Production |
| CN102895991A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Method for preparing fluid catalytic cracking (FCC) gasoline small-molecule sulfur densification catalyst |
| CN103952147A (en) * | 2014-04-29 | 2014-07-30 | 西安交通大学 | Fluorescent magnetic nanoparticle for hypochlorous acid detection and synthetic method thereof |
| CN104069839A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院大连化学物理研究所 | Ordered mesopore core-shell structure silica gel chromatographic packing material, preparation and application of ordered mesopore core-shell structure silica gel chromatographic packing material |
| CN104692399A (en) * | 2015-02-09 | 2015-06-10 | 齐鲁工业大学 | Highly-ordered radial spherical crinkled mesoporous silicon dioxide material and preparation method thereof |
-
2016
- 2016-09-06 CN CN201610804874.1A patent/CN107790075B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117223A (en) * | 2007-05-22 | 2008-02-06 | 四川大学 | Hydrothermal synthesis method for aperture control of meso-porous V-MCM-41 molecular screen |
| US20110150938A1 (en) * | 2007-08-17 | 2011-06-23 | University Of Florida Research Foundation, Inc. | Supercrystalline Colloidal Particles and Method of Production |
| CN101521067A (en) * | 2008-02-29 | 2009-09-02 | 卡南吉医药科技（上海）有限公司 | Core/shell type magnetic particle product and preparing method thereof |
| US20100056366A1 (en) * | 2008-08-27 | 2010-03-04 | Korea University Industrial & Academic Collaboration Foundation | Nanoparticles including metal oxide having catalytic activity |
| CN102895991A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Method for preparing fluid catalytic cracking (FCC) gasoline small-molecule sulfur densification catalyst |
| CN104069839A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院大连化学物理研究所 | Ordered mesopore core-shell structure silica gel chromatographic packing material, preparation and application of ordered mesopore core-shell structure silica gel chromatographic packing material |
| CN103952147A (en) * | 2014-04-29 | 2014-07-30 | 西安交通大学 | Fluorescent magnetic nanoparticle for hypochlorous acid detection and synthetic method thereof |
| CN104692399A (en) * | 2015-02-09 | 2015-06-10 | 齐鲁工业大学 | Highly-ordered radial spherical crinkled mesoporous silicon dioxide material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Functionalized Mesoporous Silica via an Aminosilane Surfactant Ion Exchange Reaction: Controlled Scaffold Design and Nitric Oxide Release;Robert J. Soto et al.;《ACS Applied Materials & Interfaces》;20160112;第2220-2231页 * |
| Novel Method To Investigate the Interaction Force between Etoposide and APTES-FunctionalizedFe3O4@nSiO2@mSiO2 Nanocarrier for Drug Loading and Release Processes;Weiwei Zhao et al.;《The Journal of Physical Chemistry C》;20150211;第4379-4386页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107790075A (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107790075B (en) | Magnetic mesoporous SiO with core-shell structure2Process for preparing nanoparticles | |
| CN108711480B (en) | Magnetic mesoporous silica nanochain with core-shell structure and preparation method thereof | |
| Zhang et al. | Fabrication of mesoporous silica-coated CNTs and application in size-selective protein separation | |
| CN101205420B (en) | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof | |
| CN105126715B (en) | Magnetic mesoporous silica microsphere material with yolk structure and preparing method thereof | |
| Sonmez et al. | Synthesis and applications of Fe3O4/SiO2 core-shell materials | |
| Lei et al. | A novel two-step modifying process for preparation of chitosan-coated Fe3O4/SiO2 microspheres | |
| CN108046277B (en) | Preparation method of micron-sized hollow magnetic silica microspheres | |
| CN102350281A (en) | Preparation method of fluorescent mesoporous silica-based core-shell nanoscale capsule | |
| Shi et al. | Preparation and enzymatic application of flower-like hybrid microcapsules through a biomimetic mineralization approach | |
| JP2013542157A (en) | Production of irregular porous silicon dioxide material and application of fatty alcohol polyoxyethylene ether in its production | |
| Hou et al. | Formulation of robust organic–inorganic hybrid magnetic microcapsules through hard-template mediated method for efficient enzyme immobilization | |
| CN108236932B (en) | Superparamagnetic-plasma composite microsphere and preparation method thereof | |
| CN103730223B (en) | Super-paramagnetism nano ball and preparation method thereof | |
| Park et al. | Microwave enhanced silica encapsulation of magnetic nanoparticles | |
| Li et al. | Hollow organosilica nanospheres prepared through surface hydrophobic layer protected selective etching | |
| Li et al. | Preparation of graphene oxide–chitosan nanocapsules and their applications as carriers for drug delivery | |
| US20120305829A1 (en) | Method for manufacturing disordered porous silicon dioxide | |
| CN103896284A (en) | Monodisperse silica nanoparticles and preparation method thereof | |
| CN101927147B (en) | Nano-scale magnetic silicon dioxide composite microsphere and preparation method thereof | |
| Lin et al. | Synthesis of magnetic hollow periodic mesoporous organosilica with enhanced cellulose tissue penetration behaviour | |
| JP2013237601A (en) | Hollow particle composed of surface-modified silica shell and method for producing the same | |
| Vafayi et al. | Investigation of in vitro drug release from porous hollow silica nanospheres prepared of ZnS@ SiO 2 core-shell | |
| CN104485191A (en) | Magnetic hollow nanometer ball and preparation method thereof | |
| CN109502594B (en) | Silicon oxide nanotube with asymmetric internal and external surface properties and preparation method and application 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 |