CN102198385B - Preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres - Google Patents
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Abstract
The invention relates to a preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres, comprising the steps of: preparing magnetic nanometer particles by a coprecipitation method; diffusing the magnetic nanometer particles in long-chain alkane after the surfaces of the magnetic nanometer particles are modified by oleic acid; mixing the oil phase composed of alkane dispersion consisting of a styrene monomer, a superhydrophobic agent and magnetic nanometer particles, and the orthosilicic acid alkyl ester with water phase in which a surface active agent is dissolved; pre-emulsifying and finely emulsifying the mixture to obtain a fine emulsion drop system; when the drops are in free radical polymerization, adding an alkali catalyst to control the generation of silicon oxide and the phase separation of the organic and inorganic components of the system; in the reaction process, adding proper ammonia water and a silane coupling agent which is marked by fluorescein to obtain the hollow compound microspheres which are different in sizes, inorganic shell thicknesses and magnetic particle solid content and have stable fluorescence signals. The preparation method disclosed by the invention is simple, the raw materials are low in cost and easy to obtain; and the obtained fluorescence dual-functional hollow silicon oxide microspheres are narrow in size distribution, high in magnetic substance content and stable in fluorescence performance.
Description
Invention field
The invention belongs to the preparing technical field of magnetic coupling functional material, be specifically related to a kind of preparation method with silica magnetic coupling tiny balloon of fluorescent characteristic, high magnetisable material content.
Background technology
Silica tiny balloon with magnetic kernel, owing to have simultaneously hollow-core construction, magnetic responsiveness and be easy to the silicon oxide surface of functional modification, thereby can be widely used in cell separation, enzyme immunity magnetic analysis, the biomedical sectors such as medicine controlled release carrier, thereby receive researcher's concern, become new study hotspot.The thinking that conventional method prepares silica magnetic hollow microballoon is basic identical with the thinking of not magnetic pure silica tiny balloon preparation, the basic template auxiliary law that adopts prepares, the material category that consists of template is various, comprise the micella that polymer microballoon, surfactant molecule consist of (appoint happy, Liu Kailang, Yu Zhufang, Lu Yan, Wang Xudong, Li Chenxi, Chinese patent, publication number: CN101792149A), hard template or the soft template such as Amphiphilic Block Polymers, bubble.Wherein report the most widely method to adopt exactly the macromolecule microballoon such as polystyrene be template, Caruso etc. [Caruso F., et al.,
Chem. Mater.,2001,13,109-116.] to adopt the positively charged polystyrene microsphere be template, when the layer upon layer electrostatic self assembly forms multilayer silica shell, interval group is loaded onto the magnetic nanoparticle layer, remove polymer template after, just obtained the tiny balloon of the coated magnetic nanoparticle of silica.[the Sun Kang such as Sun Kang, Dou Hongjing, Ma Wuwei, Chinese patent, publication number: CN101183588.] utilize the high molecular micro nanometer ball with negative electrical charge to be template, by generating with the magnetic nano particle subshell at the template surface reaction in-situ, can also wrap up again one deck silica shell at this microsphere surface, further obtain the hollow magnetic micro-nano ball by burning the removal template again.Above method or operating process are very complicated, need separately preparation and remove template, or the magnetisable material content of parcel is limited, and the magnetic responsiveness of microballoon is not good.
In addition, the people such as Kim [Kim J., et al.,
J. Am. Chem. Soc.2006,128,688-689.] be template when preparing silicon oxide mesoporous microballoon adopting the CTAB micella, add the magnetic nanoparticle of a certain amount of oleic acid modified, thereby by the hydrophobic effect power of magnetic-particle and surfactant hydrophobic side a small amount of magnetic-particle is wrapped in the mesoporous material, but, the size adjustable extent of the magnetic mesoporous structure of silica that obtains is less, and the magnetisable material content that can wrap up is lower, and the magnetic responsiveness of microballoon is not good.Wu etc. (
J. Appl. Phys.2006,99,1) adopting calcium carbonate granule is template, use sol-gel process to synthesize calcium carbonate/magnetic nanoparticle/silica complex microsphere, adopt again the processes such as acid is molten to remove template, obtain a kind of novel magnetic silicon oxide tiny balloon, because the particle diameter of used nano-calcium carbonate template own is inhomogeneous, affected the uniformity of tiny balloon, in addition, acid dissolution may destroy magnetic nanoparticle, affects the magnetic property of tiny balloon.
Patent publication No. is that the Chinese patent of CN 101195085 discloses " preparation method of magnetic hollow silicon dioxide particle ", this invention has proposed a kind of based on the stable emulsion system of solid magnetic nano particle, and original position prepares the method for magnetic hollow silicon oxide particle.The interfacial film that forms in the oil-water interfaces self assembly by means of the magnetic particle of chemical synthesis, make again silica sol obtain magnetic oxygenated silicon composite structure in the interfacial film reaction, the organic solvent of introducing before removing by heated drying at last, thus make the magnetic hollow silicon oxide microsphere.The method is placed on the preparation of magnetic-particle and the acquisition of subsequent oxidation silicon composite structure in the process, advantage is to adopt whole process relatively simple, but, the saturation magnetization of the magnetic nanoparticle for preparing is very low, less than 15emu/g, so that the magnetic property of tiny balloon also is affected, need in addition heated drying to remove organic solvent, can cause to a certain extent the reunion of tiny balloon, affect its dispersion stabilization.
In addition, can adopt the thinking of in the silicon oxide microsphere of pore structure, introducing magnetic nanoparticle.Bibliographical information is arranged, utilize the silica tiny balloon than macropore, magnetic nanoparticle is filled into [Dechao Niu, et al.,
J. Am. Chem. Soc., 2010,132,15144-15147.].[the Chen Y. such as Chen, et al., 2010 3RD INTERNATIONAL NANOELECTRONICS CONFERENCE, 2010,1,959-960.] reported employing vacuum impregnation technology, with magnetic nanoparticle by surperficial duct structure filling in the silicon oxide mesoporous hollow-core construction for preparing in advance, but, use the silica tiny balloon with magnetic-particle of these method preparations, for the size of the magnetic nanoparticle of load and the aperture size that quantity can be subject to tiny balloon, the restriction of quantity, so the microballoon saturation magnetization for preparing is generally less, magnetic responsiveness is not good.Yuan etc. [Yuan J., et al.,
J. Magn. Magn. Mater.2010,322,2172-2176.] modifying sulfonic silica tiny balloon surface, by adsorbing 2,3 valency molysite, impel again the molysite coprecipitation reaction to grow at silica tiny balloon surface nucleation, obtain the hollow-core construction of magnetic nanoparticle parcel silica shell, this structure has good magnetic responsiveness, but the silica shell is not because outside being exposed to, and can not be by further finishing, therefore this material system is difficult to the carrier as the biomolecule connection, has limited follow-up biomedical applications.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres.
The present invention proposes and utilize first the coprecipitation preparation to have the hydrophobicity superparamagnetic nano particle of high saturation and magnetic intensity, then in the mini-emulsion polymerization process of organic unit that the nano particle that is magnetic exists, introduce the one kettle way method of the sol gel reaction of silica, utilize and engage the silane coupler that fluorescence molecule is arranged participates in silica as the copolymerization molecule polycondensation reaction, and utilize the alkali original position in the reaction to remove the polymer kernel that polymerization produces, thereby obtain having fluorescent characteristic, the tiny balloon of the silicon oxide-wrapped magnetic nanoparticle of high magnetisable material content.Because, not needing separately preparation and remove template, whole process is simple, and is efficient, do not need heated drying, and tiny balloon can keep good dispersiveness.
The preparation method of a kind of magnetic fluorescence dual-function silicon oxide hollow microspheres that the present invention proposes, magnetic nanoparticle adopts the coprecipitation preparation, through being dispersed in the long chain alkane after the oleic acid finishing; By styrene monomer, super-hydrophobic dose, the alkane dispersion liquid of magnetic nanoparticle, the oil phase of the mini-emulsion polymerization of tetraalkyl orthosilicate, the oil phase mixing is stated in the water front of having dissolved surfactant, obtain miniemulsion drop system through pre-emulsification and thin emulsion process, it is characterized in that when drop carries out radical polymerization, control in the formation of silica and the system organic by adding base catalyst, the phase separation of inorganic component, obtain the coated magnetic-particle of silica as the Core-Shell Particles of shell polymer as kernel, and by can original position removal polymer kernel to the control of opportunity of adding alkali lye and consumption; In reaction system, add again the organo silane coupling agent that fluorochrome label crosses the silica shell is carried out finishing, can obtain different-grain diameter, different inorganic shell layer thicknesses, different magnetic-particle solid contents have the hollow compound microsphere of stable fluorescence signal,
Concrete steps are as follows:
(1) use coprecipitation to prepare magnetic nanoparticle, be dispersed in an amount of long chain alkane the gained magnetic nanoparticle is ultrasonic, rotary evaporation evaporate to dryness alkane is for subsequent use again;
(2) proper amount of surfactant is dissolved in a certain amount of deionized water obtains water; the magnetic nanoparticle of styrene monomer, super-hydrophobic dose, tetraalkyl orthosilicate and step (1) gained is mixed the ultrasonic uniform oil phase of making; then mixed with water, ultrasonic thin emulsification a period of time under 500 W.Adding is with respect to the initator of styrene monomer 1-2%, and stirring at room is led to N
2Then 25-35 min changes reaction system in the heated water bath over to, and initiated polymerization adds appropriate bases, and system pH is adjusted between the 8.0-10.0; Whole system is according to weight percent meter, the inorganic magnetic nano particle accounts for 0.04-0.15 %, styrene monomer accounts for 12.6-15.1%, surfactant accounts for 0.19-0.43 %, super-hydrophobic dose accounts for 0.76-0.84 %, and initator accounts for 0.1-0.3 %, and tetraalkyl orthosilicate accounts for 2.1-7.6 %, all the other are deionized water, and its gross weight satisfies 100%;
(3) after 20-80 min is carried out in polymerization in the step (2), add the ammoniacal liquor of 0.035-0.1 mL, at 50-80 ℃ of lower reaction 3-6 h; Add 20 mL alcohol to reaction system, 2.0-8.0 mL ammoniacal liquor at 50-70 ℃ of lower mechanical agitation 3-5 h, is removed the polystyrene kernel with original position;
(4) in step (3) reaction system, add again 40 g deionized waters, then add the organo silane coupling agent 20-60 μ L that crosses with 0.8-4.0 mg fluorochrome label in advance, under lucifuge, room temperature condition, carry out 18 h upset reaction; After the reaction end, absolute ethyl alcohol repeatedly fully washed and removes various reagent and the unconjugated fluorescent dyes that fully do not react in the system under magnetic separated, and obtained tiny balloon.
Among the present invention, magnetic nanoparticle can be Fe described in the step (1)
3O
4Particle or γ-Fe
2O
3In the particle any.
Among the present invention, long chain alkane described in the step (1) can be in n-hexane, cyclohexane, normal octane or the decane any.
Among the present invention, surfactant described in the step (2) can be in lauryl sodium sulfate (SDS), neopelex (SDBS) or the softex kw (CTAB) etc. any.
Among the present invention, super-hydrophobic dose can be wherein a kind of such as alcohol of hexadecane long chain alkane or hexadecanol band long-chain described in the step (2).
Among the present invention, alkali described in the step (2) can be wherein a kind of such as ammoniacal liquor, potassium hydroxide, NaOH or TMAH.
Among the present invention, initator described in the step (2) can be wherein a kind of such as azodiisobutyronitrile or potassium peroxydisulfate.
Among the present invention, alcohol described in the step (3) can be one to several in methyl alcohol, ethanol or the isopropyl alcohol etc.
Among the present invention, tetraalkyl orthosilicate described in the step (2) can be in methyl silicate or the ethyl orthosilicate etc. any.
Among the present invention, organo silane coupling agent described in the step (4) is can be by the silane coupler of fluorochrome label, can be in trimethoxy γ-aminopropylsilane, triethoxy γ-aminopropylsilane (APS) or N-(β-aminoethyl)-γ-propyl-triethoxysilicane etc. any.
Among the present invention, fluorescent dye described in the step (4) can be fluorescein isothiocynate (FITC), in tetramethyl rhodamine-FITC (TRITC) or the rhodamine B-isocyanates etc. any.
The silica magnetic hollow microballoon with fluorescent characteristic of the present invention's preparation, its particle diameter can change between 180-400 nm, can regulate the overall dimensions of tiny balloon by the consumption of control aqueous phase surfactant; The wall thickness of tiny balloon can change in 15-40 nm scope in addition, and by the ratio of control St monomer and TEOS, the consumption of ammoniacal liquor can be regulated the wall thickness of tiny balloon; By changing the consumption of inorganic iron ferrite nano particle, can regulate the magnetisable material content of tiny balloon; By changing the consumption of amino silicane coupling agent and fluorescent dye, can regulate the fluorescence signal intensity of tiny balloon.The inventive method is simple, and cost of material is low, be easy to get.The narrow diameter distribution of prepared fluorescence silica magnetic hollow complex microsphere, and have high magnetisable material content, fluorescent characteristic is stable.
Description of drawings
The transmission electron microscope photo of Fig. 1 silica magnetic hollow microballoon.
The photo of Fig. 2 fluorescence silica magnetic hollow microballoon, wherein: (a) fluorescence microscope photo, (b) optical microscope photograph.
The magnetic property curve of Fig. 3 silica magnetic hollow microballoon.
The specific embodiment
Further specify the present invention below by embodiment.
Embodiment 1.With 24 g FeCl
36H
2O and 9.82 g FeCl
27H
2O is dissolved in the suitable quantity of water, adds proper ammonia, logical N
2Gas at 80 ℃ of lower heating 30min, then adds 3.76 g oleic acid, continues heating stirring reaction 1h, then stops logical N
2Volatilization ammoniacal liquor, until have a large amount of black precipitate to occur after stopping to stir, then reaction can stop, and magnetic is washed till neutrality with deionized water with precipitation respectively under separating, and respectively washes 3 times with deionized water and ethanol again, the magnetic-particle that obtains, be dispersed in an amount of normal octane magnetic-particle is ultrasonic, rotary evaporation evaporate to dryness normal octane is for subsequent use again; 0.092 g SDS is dissolved in the 40 g deionized waters, the dispersion liquid of 8 g styrene monomers, 0.4 g hexadecane, 1 g TEOS and 55 mg magnetic-particles is mixed the ultrasonic uniform oil phase of making, then with the aqueous solution of surfactant, ultrasonic thin emulsification 10 min under 500 W.Adding is with respect to the AIBN of styrene monomer 1.0 %, and stirring at room is led to N
2Then 30 min change reaction system over to the water-bath of 70 ℃ of temperature ranges, and the beginning initiated polymerization after 60 min are carried out in polymerization, adds the ammoniacal liquor of 0.05 mL, and 6 h are carried out in reaction again under 70 ℃; Add 20 mL absolute ethyl alcohols to reaction system, 5.0 mL ammoniacal liquor, at 60 ℃ of lower mechanical agitation 3 h, remove the polystyrene kernel with original position, add again 40 g deionized waters, then add organo silane coupling agent (APS) the 40 μ L that crossed by 1.5 mg fluorochrome labels, under lucifuge, room temperature condition, carry out 18 h upset reaction.After the reaction end, absolute ethyl alcohol repeatedly fully washed and removes various reagent and the unconjugated fluorescent dyes that fully do not react in the system under magnetic separated, and obtained tiny balloon; Microballoon overall size 360 nm, silica shell 15 nm, the surface fluorescence signal is good, keeps in Dark Place.
Embodiment 2.With 24 g FeCl
36H
2O and 9.82 g FeCl
27H
2O is dissolved in the suitable quantity of water, adds proper ammonia, logical N
2Gas at 80 ℃ of lower heating 30min, then adds 3.76 g oleic acid, continues heating stirring reaction 1h, then stops logical N
2Volatilization ammoniacal liquor, until have a large amount of black precipitate to occur after stopping to stir, then reaction can stop, and magnetic is washed till neutrality with deionized water with precipitation respectively under separating, and respectively washes 3 times with deionized water and ethanol again, the magnetic-particle that obtains, be dispersed in an amount of normal octane magnetic-particle is ultrasonic, rotary evaporation evaporate to dryness normal octane is for subsequent use again; 0.12 g SDBS is dissolved in the 40 g deionized waters, the dispersion liquid of 8 g styrene monomers, 0.4 g hexadecane, 2 g methyl silicates and 80 mg magnetic-particles is mixed the ultrasonic uniform oil phase of making, then with the aqueous solution of surfactant, ultrasonic thin emulsification 10 min under 500 W.Adding is with respect to the potassium peroxydisulfate of styrene monomer 1.0 %, and stirring at room is led to N
2Then 30 min change reaction system over to the water-bath of 70 ℃ of temperature ranges, and the beginning initiated polymerization after 60 min are carried out in polymerization, adds the ammoniacal liquor of 0.1 mL, and 6 h are carried out in reaction again under 70 ℃; Add 20 mL absolute ethyl alcohols to reaction system, 5.0 mL ammoniacal liquor, at 60 ℃ of lower mechanical agitation 3 h, remove the polystyrene kernel with original position, add again 40 g deionized waters, then add the trimethoxy γ-aminopropylsilane 40 μ L that crossed by 1.5 mg fluorochrome labels, under lucifuge, room temperature condition, carry out 18 h upset reaction.After the reaction end, absolute ethyl alcohol repeatedly fully washed and removes various reagent and the unconjugated fluorescent dyes that fully do not react in the system under magnetic separated, and obtained tiny balloon; Microballoon overall size 400 nm, silica shell 40 nm, the surface fluorescence signal is good, keeps in Dark Place.
Embodiment 3.With 24 g FeCl
36H
2O and 9.82 g FeCl
27H
2O is dissolved in the suitable quantity of water, adds proper ammonia, logical N
2Gas at 80 ℃ of lower heating 30min, then adds 3.76 g oleic acid, continues heating stirring reaction 1h, then stops logical N
2Volatilization ammoniacal liquor, until have a large amount of black precipitate to occur after stopping to stir, then reaction can stop, and magnetic is washed till neutrality with deionized water with precipitation respectively under separating, and respectively washes 3 times with deionized water and ethanol again, the magnetic-particle that obtains, be dispersed in an amount of normal octane magnetic-particle is ultrasonic, rotary evaporation evaporate to dryness normal octane is for subsequent use again; 0.23 g SDS is dissolved in the 40 g deionized waters, the dispersion liquid of 8 g styrene monomers, 0.4 g hexadecanol, 1 g TEOS and 55 mg magnetic-particles is mixed the ultrasonic uniform oil phase of making, then with the aqueous solution of surfactant, ultrasonic thin emulsification 10 min under 500 W.Adding is with respect to the AIBN of styrene monomer 1.0 %, and stirring at room is led to N
2Then 30 min change reaction system over to the water-bath of 70 ℃ of temperature ranges, and the beginning initiated polymerization after 60 min are carried out in polymerization, adds the sodium hydrate aqueous solution of 0.05 mL1%, and 6 h are carried out in reaction again under 70 ℃; Add 20 mL absolute methanols to reaction system, 5.0 mL ammoniacal liquor, at 60 ℃ of lower mechanical agitation 3 h, remove the polystyrene kernel with original position, add again 40 g deionized waters, then add the triethoxy γ-aminopropylsilane 40 μ L that crossed by 1.5 mg fluorochrome labels, under lucifuge, room temperature condition, carry out 18 h upset reaction.After the reaction end, absolute ethyl alcohol repeatedly fully washed and removes various reagent and the unconjugated fluorescent dyes that fully do not react in the system under magnetic separated, and obtained tiny balloon; Microballoon overall size 180 nm, silica shell 18 nm, the surface fluorescence signal is good, keeps in Dark Place.
Embodiment 4.With 24 g FeCl
36H
2O and 9.82 g FeCl
27H
2O is dissolved in the suitable quantity of water, adds proper ammonia, logical N
2Gas at 80 ℃ of lower heating 30min, then adds 3.76 g oleic acid, continues heating stirring reaction 1h, then stops logical N
2Volatilization ammoniacal liquor, until have a large amount of black precipitate to occur after stopping to stir, then reaction can stop, and magnetic is washed till neutrality with deionized water with precipitation respectively under separating, and respectively washes 3 times with deionized water and ethanol again, the magnetic-particle that obtains, be dispersed in an amount of normal octane magnetic-particle is ultrasonic, rotary evaporation evaporate to dryness normal octane is for subsequent use again; 0.08 g CTAB is dissolved in the 40 g deionized waters, the dispersion liquid of 8 g styrene monomers, 0.4 g hexadecane, 2 g methyl silicates and 20 mg magnetic-particles is mixed the ultrasonic uniform oil phase of making, then with the aqueous solution of surfactant, ultrasonic thin emulsification 10 min under 500 W.Adding is with respect to the potassium peroxydisulfate of styrene monomer 1.0 %, and stirring at room is led to N
2Then 30 min change reaction system over to the water-bath of 70 ℃ of temperature ranges, and the beginning initiated polymerization after 60 min are carried out in polymerization, adds the ammoniacal liquor of 0.1 mL, and 6 h are carried out in reaction again under 70 ℃; Add 20 mL isopropyl alcohols to reaction system, 5.0 mL ammoniacal liquor, at 60 ℃ of lower mechanical agitation 3 h, remove the polystyrene kernel with original position, add again 40 g deionized waters, then add organo silane coupling agent (APS) the 40 μ L that crossed by 1.5 mg fluorochrome labels, under lucifuge, room temperature condition, carry out 18 h upset reaction.After the reaction end, absolute ethyl alcohol repeatedly fully washed and removes various reagent and the unconjugated fluorescent dyes that fully do not react in the system under magnetic separated, and obtained tiny balloon; Microballoon overall size 380 nm, silica shell 36 nm, magnetisable material content is relatively low, and the surface fluorescence signal is good, keeps in Dark Place.
Claims (8)
1. the preparation method of a magnetic fluorescence dual-function silicon oxide hollow microspheres is characterized in that concrete steps are as follows:
(1) use coprecipitation to prepare magnetic nanoparticle, be dispersed in an amount of long chain alkane the gained magnetic-particle is ultrasonic, rotary evaporation evaporate to dryness long chain alkane is for subsequent use again;
(2) proper amount of surfactant is dissolved in a certain amount of deionized water obtains water, the alkane dispersion liquid of the magnetic nanoparticle of styrene monomer, super-hydrophobic dose, tetraalkyl orthosilicate and step (1) gained is mixed the ultrasonic uniform oil phase of making, then mixed with water, ultrasonic thin emulsification a period of time under 500 W; Adding is with respect to the initator of styrene monomer 1-2%, and stirring at room is led to N
2Then 25-35 min changes reaction system in the heated water bath over to, and initiated polymerization adds appropriate bases, and system pH is adjusted between the 8.0-10.0; Whole system is according to weight percent meter, the inorganic magnetic nano particle accounts for 0.04-0.15 %, styrene monomer accounts for 12.6-15.1%, surfactant accounts for 0.19-0.43 %, super-hydrophobic dose accounts for 0.76-0.84 %, and initator accounts for 0.1-0.3 %, and tetraalkyl orthosilicate accounts for 2.1-7.6 %, all the other are deionized water, and its gross weight satisfies 100%; Described alkali is a kind of in ammoniacal liquor, potassium hydroxide, NaOH or the TMAH;
(3) after 20-80 min is carried out in polymerization in the step (2), add the ammoniacal liquor of 0.035-0.1 mL, at 50-80 ℃ of lower reaction 3-6 h; Add 20 mL alcohol to reaction system, 2.0-8.0 mL ammoniacal liquor at 50-70 ℃ of lower mechanical agitation 3-5 h, is removed the polystyrene kernel with original position;
(4) in step (3) reaction system, add again 40 g deionized waters, then add the organo silane coupling agent 20-60 μ L that crosses with 0.8-4.0 mg fluorochrome label in advance, under lucifuge, room temperature condition, carry out 18 h upset reaction; After the reaction end, absolute ethyl alcohol repeatedly fully washed and removes various reagent and the unconjugated fluorescent dyes that fully do not react in the system under magnetic separated, and obtained tiny balloon; Described organo silane coupling agent be in trimethoxy γ-aminopropylsilane, triethoxy γ-aminopropylsilane or N-(β-aminoethyl)-γ-propyl-triethoxysilicane any; Described fluorescent dye be in fluorescein isothiocynate, tetramethyl rhodamine-FITC or the rhodamine B-isocyanates any.
2. preparation method according to claim 1 is characterized in that magnetic nanoparticle is Fe described in the step (1)
3O
4Particle or γ-Fe
2O
3In the particle any.
3. preparation method according to claim 1, it is characterized in that long chain alkane described in the step (1) be in n-hexane, cyclohexane, normal octane or the decane any.
4. preparation method according to claim 1, it is characterized in that surfactant described in the step (2) be in lauryl sodium sulfate, neopelex or the softex kw any.
5. preparation method according to claim 1 is characterized in that described in the step (2) that super-hydrophobic dose is a kind of in the alcohol of hexadecane long chain alkane or hexadecanol band long-chain.
6. preparation method according to claim 1 is characterized in that initator described in the step (2) is a kind of in azodiisobutyronitrile or the potassium peroxydisulfate.
7. preparation method according to claim 1 is characterized in that alcohol described in the step (3) is one to several in methyl alcohol, ethanol or the isopropyl alcohol.
8. preparation method according to claim 1, it is characterized in that tetraalkyl orthosilicate described in the step (2) be in methyl silicate or the ethyl orthosilicate any.
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| CN102660255B (en) * | 2012-04-20 | 2013-11-20 | 北京化工大学 | Magnetic fluorescent nanoparticle with biological activity and method for preparing magnetic fluorescent nanoparticle |
| CN103861534A (en) * | 2012-12-17 | 2014-06-18 | 中国科学院大连化学物理研究所 | Functional superparamagnetic fluorescence labeled microcapsule and preparation and application thereof |
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| CN103272541B (en) * | 2013-05-17 | 2014-11-19 | 同济大学 | Method for preparing magnetic silicon oxide polymer composite microspheres with asymmetrical structure and surface anisotropic bifunctional groups |
| CN103495369B (en) * | 2013-09-30 | 2016-07-13 | 常州大学 | A kind of nanometer C/Si composite hollow ball material and preparation method thereof |
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| CN112745833B (en) * | 2020-12-18 | 2024-01-05 | 华侨大学 | Preparation method of time-resolved fluorescence magnetic nanoparticle |
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