CN109908859A - A kind of magnetic nano-particle/radial duct silica core-shell complex microsphere and preparation method thereof - Google Patents
A kind of magnetic nano-particle/radial duct silica core-shell complex microsphere and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to advanced nanocomposite technical fields, to solve the problems, such as that existing core-shell composite material can not meet preferable magnetic response and biggish pore capacities simultaneously, a kind of magnetic nano-particle/radial duct silica core-shell complex microsphere and preparation method thereof is provided, the magnetic nano-particle/radial duct silica core-shell complex microsphere coats radial duct silicon dioxide layer by magnetic nano-particle surface layer and constitutes；The magnetic nano-particle/radial duct silica core-shell complex microsphere partial size is 100 ~ 1000nm, and it is the pore structure of 10 ~ 100nm that the radial duct silica core-shell, which has aperture,.Complex microsphere of the invention has both preferable magnetic response and biggish pore capacities, and surface silica dioxide aperture is big, being capable of separating-purifying high molecular weight protein, such as antigen-antibody；Enzyme can also be loaded, carries out targeted therapy in vivo, additionally it is possible to which High Density Packaging nano particle has broad application prospects.
Description
Technical field
The present invention relates to advanced nanocomposite technical field more particularly to a kind of magnetic nano-particle/radial holes
Road silica core-shell complex microsphere and preparation method thereof.
Background technique
In recent years, as people are in terms of bioanalysis separation, enzyme immobilization, medical diagnosis on disease, target drug-carrying, sewage treatment
Needs, using magnetic nanoparticle as core, silica gets more and more people's extensive concerning as the complex microsphere of shell.It is with magnetism
Material is kernel, the aspect separating-purifying under magnetic fields, additionally it is possible to carry out magnetic targeted and magnetic resonance imaging.Silica is made
For Shell Materials, the toxicity of nanoparticle is reduced, so that the nanoparticle easily facilitates modification, and possesses good biofacies
Capacitive increases its application range.
Compared to traditional magnetic nano-particle/silicon dioxide composite material, magnetic nano-particle/mesoporous silicon oxide tool
There are bigger specific surface area, higher pore capacities, thus is usually used to drug delivery.However traditional Metaporous silicon dioxide material
It when synthesis, is limited by template molecule micellar size, aperture is only 3nm or so, high molecular weight protein (such as antigen, antibody, enzyme
Deng), polypeptide, nano particle (such as quantum dot, golden cluster, gold nano grain) cannot be introduced into mesopore orbit, limit silica
Load capacity.Therefore it needs to improve mesopore size by reaming.
Up to the present, using magnetic nanoparticle as core, larger mesoporous composite nano materials is coated with and are rarely reported.It is existing
(ACS Cent. Sci. 2018,4,484 492 in some reports；J. Am. Chem. Soc. 2015, 137, 13282
13289), be not magnetic response it is weaker be exactly that mesoporous pore size is smaller, preferable magnetic response and biggish mesoporous can not be met simultaneously.
Disclosed in Chinese patent literature " magnetic inorganic nano corpuscle/large aperture ordered meso-porous oxide core shell microballoon and
Preparation method ", notification number are CN 102989398A, and the invention is first with sol-gel chemistry synthetic method, in magnetism
Inorganic nano-particle surface coats upper one layer of amorphous silica, forms magnetic inorganic nano corpuscle/dioxy of size uniformity
SiClx core-shell particles；Then organic carbon forerunner is packed into the gap of above-mentioned core-shell particles by the method for " nanometer casting "
Liquid, processing carbonization；Mesoscopic structure is formed in three-dimensional ordered macroporous carbon by the method for " nanometer casting " again, and magnetic is obtained after roasting
Property inorganic nano-particle/large aperture ordered meso-porous oxide core shell microballoon.But magnetic inorganic nano-particle made from the invention
Son/large aperture ordered meso-porous oxide core shell microballoon mesoporous pore size size only has 2 ~ 30nm, and the load capacity of silica is simultaneously
It is not improved significantly, and duct is long and narrow, is non-radioactive shape structure, duct filling capacity is limited, cannot still expire simultaneously
The load of sufficient high molecular weight protein, polypeptide, nano particle.
Summary of the invention
The present invention is in order to overcome existing core-shell composite material that can not meet preferable magnetic response and biggish pore capacities simultaneously
Problem, provides that a kind of magnetic response is preferable, shape is uniform, the magnetic nano-particle with larger pore capacities/radial duct two
Silica nucleocapsid complex microsphere.
The present invention also provides a kind of magnetic nano-particle/radial duct silica core-shell complex microsphere preparation sides
Method, this method step is simple, effective, and raw material is easy to get, and synthetic method is stablized, synthesized nanoparticle good dispersion, is suitble to big
Technical scale metaplasia produces.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of magnetic nano-particle/radial duct silica core-shell complex microsphere, the magnetic nano-particle/radial hole
Road silica core-shell complex microsphere coats radial duct silicon dioxide layer by magnetic nano-particle surface layer and constitutes；The magnetism
Nanoparticle/radial duct silica core-shell complex microsphere partial size is 100 ~ 1000nm, the radial duct dioxy
It is the pore structure of 10 ~ 100nm that SiClx nucleocapsid, which has aperture,.
Magnetic nano-particle of the invention/radial duct silica core-shell complex microsphere shape is uniform, has both preferably
Magnetic response and biggish pore capacities, surface silica dioxide aperture is big, and duct is radial, being capable of separating-purifying macromolecular egg
It is white, such as antigen-antibody；Enzyme can also be loaded, carries out targeted therapy in vivo, additionally it is possible to which High Density Packaging nano particle has wide
Wealthy application prospect.
Preferably, the magnetic nano-particle is selected from ferroso-ferric oxide, γ-di-iron trioxide, NiFe2O4, CoFe2O4,
One or more of nano iron particles, nano nickel and nanometer cobalt；The partial size of the magnetic nano-particle is 60 ~ 600nm.
The present invention larger, magnetic relatively strong and easily dispersible magnetic nano-particle in polar solvent using size, effectively
Improve magnetic nano-particle/radial duct silica core-shell complex microsphere Magneto separate ability.
A kind of preparation method of magnetic nano-particle/radial duct silica core-shell complex microsphere, including following step
It is rapid:
(1) magnetic nano-particle is dispersed in polar solvent, surfactant, expanding agent and catalyst, stirring is added
After uniformly, silicon source presoma is added dropwise, obtains mixed reaction solution；Mixing time is controlled in 10 ~ 60min；
(2) mixed reaction solution that step (1) obtains is reacted under stirring condition, obtains magnetic nano-particle@after the reaction was completed and expands
Hole agent/surfactant/silica composite；The thickness of the expanding agent/surfactant/silica composite clad
Degree is 20 ~ 200nm；Whipping temp is controlled at 5 ~ 80 DEG C；Mixing time is controlled in 2 ~ 12h；
(3) magnetic nano-particle@expanding agent/surfactant/silica composite that step (2) obtains is dispersed in
Expanding agent and surfactant are eluted in eluent, alternately washed with dehydrated alcohol and water to get magnetic nano-particle/radiation
Shape duct silica core-shell complex microsphere.
Preferably, eluent described in step (3) is the ammonium nitrate ethanol solution of 0.4wt%.
The present invention is coated using the principle of sol-gal process on magnetic nano-particle surface layer using magnetic nano-particle as core
Radioactivity duct silicon dioxide layer, specific reaction mechanism are as follows: using surfactant as structure directing agent, expanding agent is added,
Hydrolysis is occurred through catalyst using silicon source presoma, one layer of expansion is coated on magnetic nano-particle surface by self assembly
Hole agent/surfactant/silica composite, then using template removal solution come eluting surface activating agent and expanding agent,
Magnetic nano-particle/radial duct silica core-shell complex microsphere can be obtained.
Preferably, the polar solvent is alkylol and water quality ratio is 1:(2 ~ 30 in step (1)) mixing it is molten
Liquid.It is below the utility model has the advantages that surfactant forms micella in system that the present invention selects polar solvent to have, and alkylol can
As chaotropic agent, increases content of the expanding agent in micella and obtain radial duct to further increase duct.
Preferably, the alkylol is selected from one or more of methanol, ethyl alcohol and isopropanol.
Preferably, the surfactant is nonionic surface active agent or ionic surfactant in step (1)
Agent.
Preferably, the nonionic surface active agent is selected from the small molecule C containing polyethersnH2n+1EOm(n=10-20, m=
One or more of 10-25)；
The ionic surfactant is selected from alkyl quaternaries surfactant CnTAB(n=12-18) or CnTAC(n=12-
One or more of 18).
Preferably, the expanding agent is straight chain small organic molecule in step (1)；The straight chain small organic molecule is selected from
One or both of ethyl acetate and ether；
The catalyst is sodium hydroxide, one or more of potassium hydroxide and concentrated ammonia liquor (25 ~ 28wt%).
Preferably, in step (2), the silicon source presoma is selected from sodium metasilicate, tetraethyl orthosilicate, methyl orthosilicate,
3- aminopropyl-trimethoxy silane, one of 3- aminopropyl-triethoxysilane and 3- mercaptopropyl-trimethoxy silane
Or it is several.
Preferably, on the basis of polar solvent gross mass, each component adds in the mixed reaction solution in step (1)
Dosage are as follows: 0.02 ~ 2wt% of magnetic nano-particle, 0.1 ~ 2wt% of surfactant, expanding agent 5 ~ 40wt %, silicon source presoma 0.1 ~
3 wt %, 0.5 ~ 5 wt % of catalyst.
The present invention must be prepared in strict accordance with the component of above-mentioned mass percentage, can just be formed aperture be 10 ~
It is independent that the radial pore structure of 100nm, very few magnetic nano-particle or excessive silicon source presoma will cause silica
Balling-up；Surfactant is very few, and will lead to the silica to be formed does not have large hole or duct narrow and irregular, excessively then
It equally will cause the unordered of duct；When expanding agent is added very few, the pore structure aperture of formation is narrow, is added excessively, then pore structure
It will be destroyed.
Therefore, the invention has the following beneficial effects:
(1) magnetic nano-particle of the invention/radial duct silica core-shell complex microsphere have both preferable magnetic response and compared with
Big pore capacities, larger using size, magnetic stronger magnetic nano-particle, improve magnetic nano-particle/radial duct
The Magneto separate ability of silica core-shell complex microsphere；Its surface silica dioxide aperture is big, can separating-purifying high molecular weight protein,
Such as antigen-antibody；Enzyme can also be loaded, carries out targeted therapy in vivo, additionally it is possible to which High Density Packaging nano particle has wide
Application prospect；
(2) preparation method step is simple, raw material is easy to get, and synthetic method is stablized, synthesized nanoparticle good dispersion, is suitble to big
Technical scale metaplasia produces.
Detailed description of the invention
Magnetic nano-particle made from Fig. 1 embodiment 1/radial duct silica core-shell complex microsphere TEM figure.
Magnetic nano-particle made from Fig. 2 embodiment 1/radial duct silica core-shell complex microsphere VSM figure.
Magnetic nano-particle made from Fig. 3 embodiment 2/radial duct silica core-shell complex microsphere TEM figure.
Magnetic nano-particle made from Fig. 4 embodiment 3/radial duct silica core-shell complex microsphere TEM figure.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, the technical solutions of the present invention will be further described.
In the present invention, if not refering in particular to, all devices and raw material is commercially available or the industry is common are following
Method in embodiment is unless otherwise instructed conventional method in that art.
Embodiment 1
(1) by 0.1g size be about 300nm magnetic ferroferric oxide even particulate dispersion contain 80ml water, 10ml ethyl alcohol,
In the solution of 20ml ether, 1g concentrated ammonia liquor (25wt%) and 0.5g cetyl trimethylammonium bromide (CTAB), 30min is stirred
Afterwards, 1g tetraethyl orthosilicate (TEOS) is added dropwise, obtains mixed reaction solution；
(2) after the mixed reaction solution for obtaining step (1) stirs 6h under the conditions of 50 DEG C, obtain magnetic nano-particle@expanding agent/
Surfactant/silica composite is collected product with magnet, and is alternately washed three times with dehydrated alcohol and water；Expanding agent/
Surfactant/silica composite clad is with a thickness of 100nm；
(3) magnetic nano-particle@expanding agent/surfactant/silica composite that step (2) obtains is dispersed in
2h is stirred in the ammonium nitrate ethanol solution of 0.4wt%, removes surfactant and expanding agent, is finally replaced with dehydrated alcohol and water
Washing three times, obtains magnetic nano-particle/radial duct silica core-shell complex microsphere.
Magnetic nano-particle made from the present embodiment/radial duct silica core-shell complex microsphere TEM figure such as Fig. 1
Shown, the magnetic nano-particle/radial duct silica core-shell complex microsphere shape is uniform, good dispersion, and partial size is about
500nm, aperture are about 50 ~ 100nm.Fig. 2 shows magnetic nano-particle made from the embodiment/radial duct silica
The VSM of nucleocapsid complex microsphere schemes, and as can be seen from the figure the magnetic nano-particle/radial duct silica core-shell is compound micro-
Ball specific saturation magnetization with higher has preferable magnetic property.
Embodiment 2
(1) γ-ferric oxide particle that 0.1g size is about 200nm is dispersed in containing 100ml water, 20ml methanol,
20ml ethyl acetate, the small molecule Brij35(C of 2.5g concentrated ammonia liquor (25%) and 0.2g containing polyethers12H25EO23) solution in, stir
After mixing 60min, 1g tetraethyl orthosilicate (TEOS) is added dropwise, obtains mixed reaction solution；
(2) after the mixed reaction solution for obtaining step (1) stirs 12h under the conditions of 5 DEG C, γ-di-iron trioxide@reaming is obtained
Agent/surfactant/silica composite is collected product with magnet, and is washed with the mixed solution of second alcohol and water；Reaming
Agent/surfactant/silica composite clad is with a thickness of 20nm；
(3) γ-di-iron trioxide@expanding agent/surfactant/silica composite that step (2) obtains is dispersed in
2h is stirred in the ammonium nitrate ethanol solution of 0.4wt%, removes surfactant and expanding agent, it is finally molten with the mixing of second alcohol and water
Liquid washing, obtains γ-di-iron trioxide/radial duct silica core-shell complex microsphere.
Magnetic nano-particle made from the present embodiment/radial duct silica core-shell complex microsphere TEM figure such as Fig. 3
Shown, the magnetic nano-particle/radial duct silica core-shell complex microsphere shape is uniform, good dispersion, and partial size is about
600nm, aperture are about 40 ~ 80nm.
Embodiment 3
(1) CoFe for being about 300nm by 0.05g size2O4Even particulate dispersion is containing 70ml water, 10ml ethyl alcohol, 20ml second
Ether, the small molecule Brij56(C of 3g concentrated ammonia liquor (25%) and 0.2g containing polyethers16H33EO10) solution in, stir 10min after, by
It is added dropwise to the positive quanmethyl silicate of 1g (TMOS) and 0.1g 3- mercaptopropyl-trimethoxy silane, obtains mixed reaction solution；
(2) after the mixed reaction solution for obtaining step (1) stirs 2h under the conditions of 80 DEG C, CoFe is obtained2O4@expanding agent/surface
Activating agent/silica composite is collected product with magnet, and is washed with the mixed solution of second alcohol and water；Expanding agent/surface is living
Property agent/silica composite clad is with a thickness of 200nm；
(3) CoFe for obtaining step (2)2O4@expanding agent/surfactant/silica composite is dispersed in 0.4% nitre
2h is stirred in sour ammonium ethanol solution, is removed surfactant and expanding agent, is finally washed, obtained with the mixed solution of second alcohol and water
CoFe2O4/ radial duct silica core-shell complex microsphere.
Magnetic nano-particle made from the present embodiment/radial duct silica core-shell complex microsphere TEM figure such as Fig. 4
Shown, the magnetic nano-particle/radial duct silica core-shell complex microsphere shape is uniform, good dispersion, and partial size is about
400nm, aperture are about 30 ~ 90nm.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, and is not surpassing
There are also other variations and modifications under the premise of technical solution documented by claim out.
Claims (10)
1. a kind of magnetic nano-particle/radial duct silica core-shell complex microsphere, which is characterized in that the magnetic Nano
Particle/radial duct silica core-shell complex microsphere coats radial duct silicon dioxide layer by magnetic nano-particle surface layer
It constitutes；The magnetic nano-particle/radial duct silica core-shell complex microsphere partial size is 100 ~ 1000nm, described to put
Penetrate the pore structure that shape duct silica core-shell is 10 ~ 100nm with aperture.
2. a kind of magnetic nano-particle according to claim 1/radial duct silica core-shell complex microsphere, special
Sign is that the magnetic nano-particle is selected from ferroso-ferric oxide, γ-di-iron trioxide, NiFe2O4, CoFe2O4, Nanoscale Iron
One or more of grain, nano nickel and nanometer cobalt；The partial size of the magnetic nano-particle is 60 ~ 600nm.
3. a kind of magnetic nano-particle as claimed in claim 1 or 2/radial duct silica core-shell complex microsphere system
Preparation Method, which comprises the following steps:
(1) magnetic nano-particle is dispersed in polar solvent, surfactant, expanding agent and catalyst, stirring is added
After uniformly, silicon source presoma is added dropwise, obtains mixed reaction solution；
(2) mixed reaction solution that step (1) obtains is reacted under stirring condition, obtains magnetic nano-particle@after the reaction was completed and expands
Hole agent/surfactant/silica composite；The thickness of the expanding agent/surfactant/silica composite clad
Degree is 20 ~ 200nm；
(3) magnetic nano-particle@expanding agent/surfactant/silica composite that step (2) obtains is dispersed in
It is in eluent that expanding agent and surfactant elution is compound to get magnetic nano-particle/radial duct silica core-shell
Microballoon.
4. magnetic nano-particle according to claim 3/radial duct silica core-shell complex microsphere preparation side
Method, which is characterized in that in step (1), the polar solvent is alkylol and water quality ratio is 1:(2 ~ 30) mixed solution.
5. magnetic nano-particle according to claim 4/radial duct silica core-shell complex microsphere preparation side
Method, which is characterized in that the alkylol is selected from one or more of methanol, ethyl alcohol and isopropanol.
6. magnetic nano-particle according to claim 3/radial duct silica core-shell complex microsphere preparation method,
It is characterized in that, the surfactant is nonionic surface active agent or ionic surfactant in step (1).
7. magnetic nano-particle according to claim 6/radial duct silica core-shell complex microsphere preparation side
Method, which is characterized in that the nonionic surface active agent is selected from the small molecule C containing polyethersnH2n+1EOm(n=10-20, m=10-
One or more of 25)；The ionic surfactant is selected from alkyl quaternaries surfactant CnTAB(n=12-
Or C 18)nOne or more of TAC(n=12-18).
8. magnetic nano-particle according to claim 3/radial duct silica core-shell complex microsphere preparation side
Method, which is characterized in that in step (1), the expanding agent is straight chain small organic molecule；The straight chain small organic molecule is selected from acetic acid
One or both of ethyl ester and ether；The catalyst is sodium hydroxide, one or more of potassium hydroxide and concentrated ammonia liquor.
9. magnetic nano-particle according to claim 3/radial duct silica core-shell complex microsphere preparation side
Method, which is characterized in that in step (2), the silicon source presoma is selected from sodium metasilicate, tetraethyl orthosilicate, methyl orthosilicate, 3- ammonia
Propyl-trimethoxysilane, one of 3- aminopropyl-triethoxysilane and 3- mercaptopropyl-trimethoxy silane or several
Kind.
10. according to any magnetic nano-particle/radial duct silica core-shell complex microsphere of claim 3-9
Preparation method, which is characterized in that in step (1), on the basis of polar solvent gross mass, each component in the mixed reaction solution
Additive amount are as follows: 0.02 ~ 2wt% of magnetic nano-particle, 0.1 ~ 2wt% of surfactant, expanding agent 5 ~ 40wt %, silicon source presoma
0.1 ~ 3 wt %, 0.5 ~ 5 wt % of catalyst.
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