CN102198385A - Preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres - Google Patents
Preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres Download PDFInfo
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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 composite functional material, be specifically related to a kind of preparation method with silica magnetic compound hollow microballoon of fluorescent characteristic, high magnetisable material content.
Background technology
The silica tiny balloon that has magnetic kernel, owing to have hollow-core construction, magnetic responsiveness simultaneously and be easy to the silicon oxide surface of functional modification, thereby can be widely used in cell separation, enzyme immunity magnetic analysis, biomedical sectors such as medicine controlled release carrier, thereby receive researcher's concern, become new research focus.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 constitutes template is various, comprise the micella that polymer microballoon, surfactant molecule constitute (appoint happy, Liu Kailang, Yu Zhufang, Lu Yan, Wang Xudong, Li Chenxi, Chinese patent, publication number: CN101792149A), hard template or soft template such as Amphiphilic Block Polymers, bubble.Wherein report the most widely method to adopt macromolecule microballoon such as polystyrene exactly 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 silica bag by the tiny balloon of magnetic nanoparticle.[Sun Kang such as Sun Kang, Dou Hongjing, Ma Wuwei, Chinese patent, publication number: CN101183588.] utilize the high molecular micro nanometer ball that has 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 one deck silica shell again at this microsphere surface, further obtain the hollow magnetic micro-nano ball again by burning the removal template.Above method or operating process are very complicated, need preparation separately and remove template, or the magnetisable material content of parcel is limited, and the magnetic responsiveness of microballoon is not good.
In addition, 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 a small amount of magnetic-particle is wrapped in the mesoporous material by the hydrophobic effect power of magnetic-particle and surfactant hydrophobic side, but, the size adjustable scope 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 processes such as acid is molten to remove template again, obtain a kind of novel magnetic silicon oxide tiny balloon, because the particle diameter of used nano-calcium carbonate template own is inhomogeneous, influenced the uniformity of tiny balloon, in addition, sour molten process may be destroyed magnetic nanoparticle, influences 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, the method for in-situ preparing 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, silica sol is reacted on interfacial film obtain magnetic oxygenated silicon composite structure, the organic solvent of introducing before removing by heated drying at last, thus make the magnetic hollow silicon oxide microsphere.This 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 simple relatively, but, the saturation magnetization of the magnetic nanoparticle for preparing is very low, less than 15emu/g, make the magnetic property of tiny balloon also be affected, need heated drying to remove organic solvent in addition, can cause the reunion of tiny balloon to a certain extent, influence its dispersion stabilization.
In addition, can adopt the thinking of in having 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.].[Chen Y. such as Chen, et al., 2010 3RD INTERNATIONAL NANOELECTRONICS CONFERENCE, 2010,1,959-960.] reported employing vacuum impregnation technology, be filled into magnetic nanoparticle in the silicon oxide mesoporous hollow-core construction for preparing in advance by surperficial pore passage structure, but, use the silica tiny balloon that has magnetic-particle of these method preparations, for the size of the magnetic nanoparticle of load and the aperture size that quantity can be subjected 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 the molysite coprecipitation reaction to grow again 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 fluorescent dual-function silica tiny balloon.
The present invention proposes and utilize the coprecipitation preparation to have the hydrophobicity superparamagnetic nano particle of high saturation and magnetic intensity earlier, 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 then, 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 silica coated magnetic nano particle of high magnetisable material content.Because, not needing preparation separately 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 fluorescent dual-function silica tiny balloon 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 fashionable to it is characterized in that carrying out radical polymerization at drop, control in the formation of silica and the system organic by adding base catalyst, the behavior that is separated of inorganic component, obtain the silica bag by magnetic-particle as the nucleocapsid structure microballoon of shell polymer, and by to the opportunity that adds alkali lye and the control of consumption can original position removing the polymer kernel as kernel; The organo silane coupling agent that the adding fluorochrome label is crossed in reaction system carries out finishing to the silica shell again, 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 standby 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; mixed with water then, 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
225-35 min changes reaction system in the heated water bath over to then, 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 comprise 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, react 3-6 h down at 50-80 ℃; Add 20 mL alcohol to reaction system, 2.0-8.0 mL ammoniacal liquor at 50-70 ℃ of following mechanical agitation 3-5 h, is removed the polystyrene kernel with original position;
(4) in step (3) reaction system, add 40 g deionized waters again, add the organo silane coupling agent 20-60 μ L that crosses with 0.8-4.0 mg fluorochrome label in advance then, under lucifuge, room temperature condition, carry out 18 h upset reaction; After the reaction end, absolute ethyl alcohol fully washed repeatedly 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 belt length 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 aminopropyl silane, triethoxy aminopropyl silane (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-5-fluorescein isothiocynate (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 heats 30min down at 80 ℃, adds 3.76 g oleic acid then, continues heating stirring reaction 1h, stops logical N then
2Volatilization ammoniacal liquor, after stopping stirring, there are a large amount of black precipitate to occur, 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 standby 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
230 min change reaction system over to the water-bath of 70 ℃ of temperature ranges then, 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 following mechanical agitation 3 h, remove the polystyrene kernel with original position, add 40 g deionized waters again, add organo silane coupling agent (APS) the 40 μ L that cross by 1.5 mg fluorochrome labels then, under lucifuge, room temperature condition, carry out 18 h upset reaction.After the reaction end, absolute ethyl alcohol fully washed repeatedly 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 heats 30min down at 80 ℃, adds 3.76 g oleic acid then, continues heating stirring reaction 1h, stops logical N then
2Volatilization ammoniacal liquor, after stopping stirring, there are a large amount of black precipitate to occur, 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 standby 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
230 min change reaction system over to the water-bath of 70 ℃ of temperature ranges then, 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 following mechanical agitation 3 h, remove the polystyrene kernel with original position, add 40 g deionized waters again, add the trimethoxy aminopropyl silane 40 μ L that cross by 1.5 mg fluorochrome labels then, under lucifuge, room temperature condition, carry out 18 h upset reaction.After the reaction end, absolute ethyl alcohol fully washed repeatedly 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 heats 30min down at 80 ℃, adds 3.76 g oleic acid then, continues heating stirring reaction 1h, stops logical N then
2Volatilization ammoniacal liquor, after stopping stirring, there are a large amount of black precipitate to occur, 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 standby 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
230 min change reaction system over to the water-bath of 70 ℃ of temperature ranges then, 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 following mechanical agitation 3 h, remove the polystyrene kernel with original position, add 40 g deionized waters again, add the triethoxy aminopropyl silane 40 μ L that cross by 1.5 mg fluorochrome labels then, under lucifuge, room temperature condition, carry out 18 h upset reaction.After the reaction end, absolute ethyl alcohol fully washed repeatedly 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 heats 30min down at 80 ℃, adds 3.76 g oleic acid then, continues heating stirring reaction 1h, stops logical N then
2Volatilization ammoniacal liquor, after stopping stirring, there are a large amount of black precipitate to occur, 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 standby 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
230 min change reaction system over to the water-bath of 70 ℃ of temperature ranges then, 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 following mechanical agitation 3 h, remove the polystyrene kernel with original position, add 40 g deionized waters again, add organo silane coupling agent (APS) the 40 μ L that cross by 1.5 mg fluorochrome labels then, under lucifuge, room temperature condition, carry out 18 h upset reaction.After the reaction end, absolute ethyl alcohol fully washed repeatedly 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 (10)
1. the preparation method of a magnetic fluorescent dual-function silica tiny balloon 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 standby 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, mixed with water then, 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
225-35 min changes reaction system in the heated water bath over to then, 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 comprise 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, react 3-6 h down at 50-80 ℃; Add 20 mL alcohol to reaction system, 2.0-8.0 mL ammoniacal liquor at 50-70 ℃ of following mechanical agitation 3-5 h, is removed the polystyrene kernel with original position;
(4) in step (3) reaction system, add 40 g deionized waters again, add the organo silane coupling agent 20-60 μ L that crosses with 0.8-4.0 mg fluorochrome label in advance then, under lucifuge, room temperature condition, carry out 18 h upset reaction; After the reaction end, absolute ethyl alcohol fully washed repeatedly and removes various reagent and the unconjugated fluorescent dyes that fully do not react in the system under magnetic separated, and obtained tiny balloon.
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 described 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 belt length chain.
6. preparation method according to claim 1 is characterized in that alkali described in the step (2) is a kind of in ammoniacal liquor, potassium hydroxide, NaOH or the TMAH.
7. 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.
8. 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.
9. 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.
10. preparation method according to claim 1, it is characterized in that organo silane coupling agent described in the step (4) be in trimethoxy aminopropyl silane, triethoxy aminopropyl silane or N-(β-aminoethyl)-γ-propyl-triethoxysilicane any; Described fluorescent dye be in fluorescein isothiocynate, tetramethyl rhodamine-5-fluorescein isothiocynate or the rhodamine B-isocyanates any.
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