CN1215902C - Magnetic fluorescent double functional microballoon with core-shell structure and preparation method thereof - Google Patents
Magnetic fluorescent double functional microballoon with core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a magnetic and fluorescent double-functional microsphere with a core-shell structure and a preparation method thereof. Firstly, the surface of inorganic magnetic nanometer particles are modified by strong acid and trisodium citrate dihydrate; then, with ortho silicate alkyl ester as a precursor, a silicon dioxide magnetic microsphere with a core-shell structure is prepared by a gel-sol method; finally, a silicon dioxide fluorescent microsphere with magnetism is prepared by a method of copolycondensation of ortho silicate alkyl ester and silane coupling agent of bonding fluorescein. The microsphere with magnetic response can send out fluorescence through the excitation of ultraviolet light and visual light. The present invention has the advantages of simple method and easy acquirement of raw materials. The diameter of the prepared composite microsphere is distributed narrowly, and the size of the microsphere is controllable.
Description
Technical field
The invention belongs to technical field of inorganic material, be specifically related to a kind of magnetic fluorescent dual-function microballoon and preparation method thereof with nucleocapsid structure.
Technical background
Functional microsphere is that a class comprises various microballoons with specific function, such as the many magnetic microspheres of Recent study, and fluorescent microsphere, the responsive microballoon of pH, the responsive to temperature microballoon, and the surface is easy to be modified into the microballoon that has various functional groups etc.
Fluorescent microsphere is a kind of functional microsphere that is loaded with fluorescence molecule, and in recent years, along with going deep into of fluorescent probe technique research, people can prepare the fluorescent microsphere of various particle diameters from the nanoscale to the submicron order.Fluorescent microsphere since in single microballoon enrichment organic molecule that can emitting fluorescence, be with a wide range of applications in a lot of fields, as biological medicine, material science, environment measuring, clinical medicine, genetic analysis and cell imaging etc.
With regard to the preparation method of fluorescent microsphere, present mainly can being divided three classes of bibliographical information, the one, the mode by physical absorption (mainly being electrostatic interaction) is downloaded to the organic fluorescence molecule on the microballoon; The 2nd, the mode by physically trapping is downloaded to the organic fluorescence molecule on the microballoon; The 3rd, the mode by chemical bonding is downloaded to the organic fluorescence molecule on the microballoon.Thereby Renault etc. have prepared surperficial fluorescent microsphere (the Renault R.M that has fluorescence molecule by the method for Electrostatic Absorption with the microsphere surface that fluorescence molecule is connected to functionalization, Denjean P, Pansu R.B, Sensors Actuators, 1999 (59): 108).Campbell etc. utilize the polar interaction between fluorescence molecule and polymer molecule, the mode of fluorescence molecule by physically trapping prepared fluorescent microsphere (the Campbell A.I that includes fluorescence molecule, Bartlett P, J.Colloid Inter.Sci., 2002 (256): 325).Jardine etc. are by being bonded to fluorescence molecule on a kind of polymerisable monomer, and then have prepared fluorescent microsphere (Jardine R.S, Bartlett P, Colloids Surf.A, 2002 (211): 127) that include fluorescence molecule with another kind of monomer copolymerization.
Magnetic microsphere is owing to its distinctive magnetic responsiveness and be easy to functionalization, has a wide range of applications in a lot of fields.In fact, as far back as the seventies in 20th century, Dutch scientist Ugelstad has just prepared the micron order polystyrene magnetic microsphere of monodispersity first, and has successfully developed the magnetic microsphere series of products based on polystyrene.Exploitation polystyrene microspheres such as Ugelstad successfully have been applied in fields such as cell separation, clinical diagnosis.Many in the world subsequently research groups join in the research of the preparation of magnetic microsphere and application one after another, along with going deep into of research, the many new application of magnetic microsphere or is developed, the application of magnetic microsphere is extended to other bioengineering, medical science, field of medicaments from original separation, diagnosis, as targeting drug administration preparation, immunoassay, cell culture medium or the like.
With regard to present present Research, the main of magnetic microsphere develops to several directions once: the one, and the magnetic microsphere of preparation smaller szie promptly prepares submicron order even nano-scale magnetic microballoon; The 2nd, preparation biocompatibility and biodegradable magnetic microsphere (especially preparing the target administration system); The 3rd, further magnetic microsphere is carried out functionalization to expand its application.
With regard to prepared magnetic microsphere, mainly contain two big classes, the one, the magnetic microsphere for preparing with synthetic high polymer or natural polymer parcel inorganic magnetic particle.This class is studied often at present, and the technology that adopts microcyst is a kind of more original method of preparation magnetic microsphere.This method is simple to operate, but the out-of-shape of microballoon of preparation and size be mostly at micron order even bigger, and it is generally all very wide that another characteristics are that its particle diameter distributes, and these all cause prepared magnetic microsphere to be difficult to play a role in field widely.Dekker is suspended in magnetic-particle in polymine (PEI) solution, by filtering, dry handle the magnetic microsphere that makes outsourcing PEI (Dekker R F M.Appl.Biotech., 1989,22:289).Cuyper etc. handle magnetic nanoparticle with phosphatide, make the magnetic liposome microballoon (Cuyper MD, JonianM.Langmuir, 1990,7:647).Monomer polymerization method is the preparation method who studies at most behind Ugelstad, wherein mainly contains suspension polymerization, dispersion copolymerization method, emulsion polymerization (comprising emulsifier-free emulsion polymerization, seeding polymerization) etc.People such as Margel have prepared particle size range in the presence of oil-soluble initiator, suspension stabilizer and inorganic magnetic particle be the magnetic polypropylene aldehydes microballoon (Margel S, Beitler U.USP 4,783,336,1988) of 0.03um-80um.It is the hydrophobic magnetic polymer microsphere (Daniel J C, SchuppsierJ L.USP 4,358,388.1982) of 0.03um-5um that employing microsuspension polymerizations such as Daniel have obtained particle size range.The microspherulite diameter of suspension polymerization is also bigger, the particle diameter wider distribution.Emulsion polymerisation is the more a kind of method for preparing magnetic polymer microsphere of using at present.Furusawa etc. deposit to magnetic-particle on the high molecular emulsion particle that has functional group, adopt seeded emulsion polymerization to make magnetic microsphere (Furusawa K, the Nagashima K of sandwich structure then, Anzai C, Colloid Polym.Sci, 1994,272:1104).Domestic grandson Zong Hua etc. with magnetic fluid as nuclear, adopt improved emulsion polymerization prepared particle size range be magnetic polystyrene microsphere (Qiu Guangming, Sun Zonghua, chemical reagent, 1993,15 (4): 324) of 0.06um-10um.Ugelstad etc. at first propose in-situ method and prepare the monodisperse magnetic polymer microsphere, its characteristics are to prepare with two step swelling methods earlier the polystyrene microsphere of porous, in the duct of polystyrene microsphere, use the alkali precipitation molysite then, thereby monodispersed magnetic polystyrene microsphere (Ugelstad J, Mork P C, Schmid R have been made, et al, Polym.Int, 1993,30:15.).
The 2nd, be prepared into magnetic microsphere with inorganic material parcel nano magnetic particle, or the inorganic magnetic particle deposited to the magnetic microsphere of inorganic material surface preparation by the method for absorption.Therefore wherein inorganic material mainly is a silica, because silica is a kind of bio-inert material, and this inorganic composite microsphere is easy to surface-functionalizedly, can be widely used in fields such as biological medicine, clinical diagnosis and immunoassay.Domestic Zhu with China etc. with monodispersed silicon dioxide microsphere as template, utilize the static self assembly, prepared that nucleocapsid is silica, the centre is the silicone dioxide magnetic microsphere (Zhu Yihua of multi-layered magnetic nano particle, answer letter, Yang Xiaoling, Chinese patent, publication number: CN1380133A).Wang Kemin etc. have synthesized the magnetic fluorescence particle (Tan Weihong of coated magnetic particle water soluble fluorescence material respectively by teos hydrolysis in the reverse microemulsion liquid system, Wang Kemin, Xiao Dan, Chinese patent, publication number CN 1342515A), Ramesh etc. are by Fe (CO)
5Phonochemistry deposit and prepare magnetic silica magnetic microsphere (Ramesh S, Prozorov R, and Gedanken A, Chem.Mater., 1997,9 (12:2996)).
Therefore magnetic fluorescent microspheres is a kind of difunctional microballoon that integrates magnetic responsiveness and emitting fluorescence characteristic, and this microballoon not only can respond to externally-applied magnetic field, and can also send fluorescence under exciting light, can be applied at wide spectrum more.
Among the present invention, we have proposed the method that a kind of simple preparation has the magnetic fluorescent dual-function microballoon of nucleocapsid structure, the preparation process good reproducibility, and the microballoon shape that makes is regular, and particle diameter is easy to control.
Summary of the invention
The objective of the invention is to propose a kind of magnetic fluorescent dual-function microballoon and preparation method thereof with nucleocapsid structure.
The magnetic fluorescent dual-function microballoon that the present invention proposes with nucleocapsid structure, be a kind ofly to be nuclear, to be the magnetic microsphere of the nucleocapsid structure of shell with the silica of organic fluorescence molecular dopant with (as inorganic iron oxysome etc.) nano magnetic particle, its particle size be nanoscale to submicron order, little to 20 nanometers, arrive the 200-400 nanometer greatly.Owing to added the organic fluorescence molecule in preparation process, so this microballoon not only has the magnetic correspondence, and issues out fluorescence in the UV, visible light optical excitation, so we are called magnetic fluorescent microspheres.
The shell of above-mentioned microballoon is to be the silica of presoma preparation with the tetraalkyl orthosilicate, wherein the organic fluorescence molecule of Can Zaing can be one or more of the fluorescence molecule (as isothiocyanates fluorescein FITC) that has the isothiocyanates group, and the silane coupler that is used for bonding organic fluorescence molecule is that trimethoxy amine propyl silane, triethoxy amine propyl silane etc. have one or more of amino silane coupler.
The above-mentioned magnetic fluorescent microspheres with nucleocapsid structure that the present invention proposes adopts the preparation of gel-sol method.Earlier the inorganic magnetic particle is carried out surface modification with strong acid (as nitric acid, hydrochloric acid) and natrium citricum, utilizing the preparation of gel-sol method then in alcohol/aqueous systems is that shell, inorganic magnetic particle are the inorganic compounding magnetic microsphere of nuclear with silica, be seed at last with the magnetic silica microballoon, the method for the silane coupler copolycondensation by tetraalkyl orthosilicate and bonding fluorescein makes the silica fluorescent microballoon with magnetic.
Concrete preparation process is as follows:
1, use strong acid that the inorganic magnetic particle is activated: nano magnetic particle to be dispersed in the deionized water, to utilize the magnet separating, washing, be dispersed in then in the 2.0-4.0mol/L strong acid solution, stirred 5-20 minute; Utilize magnet to isolate the magnetic-particle of process strong acid treatment again, and spend deionised water 3-5 time;
2, modify inorganic magnetic particle after the activation with the citric acid hydrochlorate: in the slurry of the inorganic magnetic particle of step (1) gained, add citrate solution, dispersed with stirring, separate with magnet then, and spend deionised water 2-4 time, be dispersed in the deionized water at last, obtain the dispersion liquid of the magnetic-particle after the modification, magnetic-particle concentration is 0.5-3.0wt%;
3, preparation is that shell, inorganic magnetic particle are the inorganic compounding magnetic microsphere of nuclear with silica: the dispersion liquid of the magnetic-particle after the modification is joined in alcohol/water mixed liquid, under agitation add alkali lye and tetraalkyl orthosilicate, keep and stirred 4-12 hour, entire reaction is carried out at 20 ℃-40 ℃; Whole system is calculated according to weight, and the magnetic-particle after the modification accounts for 0.3-3.0%, and alkali lye accounts for 0.8-3.0%, and water accounts for 10-20%, and alcohol accounts for 70-75%, and all the other are tetraalkyl orthosilicate;
4, preparation has the magnetic fluorescent microspheres of nucleocapsid structure: the ethanolic solution and the tetraalkyl orthosilicate that add the silane coupler of bonding fluorescein in the reacted system of above-mentioned steps (3), 20 ℃ of-40 ℃ of lucifuge stirring reactions 12-48 hour, wherein, the silane coupler ethanolic solution of tetraalkyl orthosilicate and bonding fluorescein by volume 1: 1-1: 4 add.
The silane coupler of bonding fluorescein can be made by following method among the above-mentioned preparation method:
With the fluorescence molecule of band isothiocyanate group and the silane coupler that has an amido according to mol ratio 1: 9-1: 5 ratio joined in the absolute ethyl alcohol room temperature lucifuge stirring reaction 24-48 hour.
The magnetic fluorescent microspheres with nucleocapsid structure of above method preparation separates under can the magnet effect and spends deionised water.Because this microballoon has the inorganic magnetic kernel, therefore have magnetic responsiveness, owing to mixing in its shell silica the organic fluorescence molecule is arranged simultaneously, therefore can issue out fluorescence in the UV, visible light optical excitation.
Among the present invention, used magnetic nanoparticle can be γ-Fe
2O
3Or Fe
3O
4Or in other the ferrite particle any.
Among the present invention, used strong acid is wherein a kind of such as nitric acid, sulfuric acid, hydrochloric acid.
Among the present invention, used citrate can be one or more of natrium citricum, potassium citrate.
Among the present invention, used alkali is wherein a kind of such as ammoniacal liquor, potassium hydroxide, NaOH, TMAH.
Among the present invention, used alcohol is one or more of methyl alcohol, ethanol, isopropyl alcohol etc.
Among the present invention, used presoma can be wherein a kind of such as methyl silicate or ethyl orthosilicate.
Among the present invention, used silane coupler is to have amino silane coupler, as (APS) trimethoxy amine propyl silane, triethoxy amine propyl silane, N-(β-aminoethyl)-γ-propyl-triethoxysilicane etc.
Among the present invention, used organic fluorescence molecule is the fluorescent material that FITC etc. has isothiocyanate group.
The magnetic fluorescent microspheres with nucleocapsid structure of the present invention's preparation, its particle diameter can be controlled at nano-scale to be changed to micron, send out the consumption that alcohol, water, alkali ratio and the tetraalkyl orthosilicate of answering in the system are made presoma by control, can make the silica magnetic fluorescent microsphere of different-grain diameter.This microballoon has magnetic responsiveness and can send fluorescence under ultraviolet, excited by visible light.The inventive method is simple, and raw material is easy to get.Prepared complex microsphere particle diameter is narrow distribution and controlled amount.
The research of magnetic microsphere mainly biases toward its magnetic property both at home and abroad at present, comparatively speaking, the present invention is by the silicon dioxide microsphere of preparation parcel inorganic magnetic particle, and the method for organic fluorescence molecule by copolycondensation be doped in the silica shell, thereby prepared magnetic fluorescent microspheres with nucleocapsid structure.Zhi Bei microballoon has following characteristics by this method:
(1) magnetic kernel, having magnetic responsiveness (2) microspherulite diameter size can regulate, and particle diameter is narrow distribution.(3) microballoon has nucleocapsid structure, and inorganic kernel is wrapped up by shell silica.(4) method for preparing microsphere is simple, and stability is high.
The specific embodiment
Embodiment 1: in the 500mL three-necked bottle, add 5.0g through the washed ferroferric oxide powder of deionization, add the deionized water of 200mL, after the dispersed with stirring, add 100mL salpeter solution (3.0M) then under the 600rpm rotating speed, stirring at room 10 minutes.Separate with magnet then and spend deionised water 3-5 time.With the tri-iron tetroxide mud dispersed with stirring (0.2M) in the sodium citrate solution of 400mL that obtains after the washing, then separate and spend deionised water 3-5 time with magnet, last resulting tri-iron tetroxide is dispersed in the 200mL deionized water, makes the about 2.0wt% magnetic fluid of solid content.
In single neck round-bottomed flask of a 25mL, with 10mL anhydrous alcohol solution 0.0356g fluorescein FITC, add 0.01829g triethoxy amine propyl silane (APS) then, lucifuge stirring reaction 48 hours makes the silane coupler of bonding fluorescence molecule FITC.
In the three-necked bottle of a 500mL, add the good magnetic fluid of 2.0g prepared beforehand, and with the dilution of 50mL deionized water and 200 absolute ethyl alcohols, add the 4mL concentrated ammonia liquor down in high-speed stirred (600rpm) then, add the 1mL ethyl orthosilicate after the system for the treatment of is warming up to 40 ℃, keep and stir after 4 hours, add the silane coupler of the bonding fluorescence molecule FITC of the above-mentioned preparation of 2mL, simultaneously add the 1mL ethyl orthosilicate again, continue at 40 ℃ of lucifuges and stirred 24 hours.Prepared magnetic fluorescent microspheres particle diameter is 70nm.
Embodiment 2: in the 500mL three-necked bottle, add 5.0g through the washed ferroferric oxide powder of deionization, add the deionized water of 200mL, after the dispersed with stirring, add 100mL salpeter solution (3.0M) then, stirring at room 5-8 minute under the 600rpm rotating speed.Separate with magnet then and spend deionised water 3-5 time.With the tri-iron tetroxide mud dispersed with stirring (0.2M) in the sodium citrate solution of 400mL that obtains after the washing, then separate and spend deionised water 3-5 time with magnet, last resulting tri-iron tetroxide is dispersed in the 200mL deionized water, makes the about 2.0wt% magnetic fluid of solid content.
In single neck round-bottomed flask of a 25mL, with 10mL anhydrous alcohol solution 0.0356g fluorescein FITC, add 0.01829g triethoxy amine propyl silane (APS) then, lucifuge stirring reaction 48 hours makes the silane coupler of bonding fluorescence molecule FITC.
In the three-necked bottle of a 500mL, add the good magnetic fluid of 2.0g prepared beforehand, and with the dilution of 50mL deionized water and 200 absolute ethyl alcohols, add the 4mL concentrated ammonia liquor down in high-speed stirred (600rpm) then, add the 2mL ethyl orthosilicate after the system for the treatment of is warming up to 30 ℃, keep and stir after 12 hours, add the silane coupler of the bonding fluorescence molecule FITC of the above-mentioned preparation of 2mL, simultaneously add the 1mL ethyl orthosilicate again, continue at 30 ℃ of lucifuges and stirred 12 hours.Prepared magnetic fluorescent microspheres particle diameter is 95nm.
Embodiment 3: in the 500mL three-necked bottle, add 5.0g through the washed ferroferric oxide powder of deionization, add the deionized water of 200mL, after the dispersed with stirring, add 100mL salpeter solution (3.0M) then, stirring at room 10-20 minute under the 600rpm rotating speed.Separate with magnet then and spend deionised water 3-5 time.With the tri-iron tetroxide mud dispersed with stirring (0.2M) in the sodium citrate solution of 400mL that obtains after the washing, then separate and spend deionised water 3-5 time with magnet, last resulting tri-iron tetroxide is dispersed in the 200mL deionized water, makes the about 2.0wt% magnetic fluid of solid content.
In single neck round-bottomed flask of a 25mL, with 10mL anhydrous alcohol solution 0.0356g fluorescein FITC, add 0.01829g triethoxy amine propyl silane (APS) then, lucifuge stirring reaction 48 hours makes the silane coupler of bonding fluorescence molecule FITC.
In the three-necked bottle of a 500mL, add the good magnetic fluid of 2.0g prepared beforehand, and with the dilution of 50mL deionized water and 200 absolute ethyl alcohols, add the 4mL concentrated ammonia liquor down in high-speed stirred (600rpm) then, add the 3mL ethyl orthosilicate after the system for the treatment of is warming up to 20 ℃, keep and stir after 10 hours, add the silane coupler of the bonding fluorescence molecule FITC of the above-mentioned preparation of 2mL, simultaneously add the 1mL ethyl orthosilicate again, continue at 40 ℃ of lucifuges and stirred 48 hours.Prepared magnetic fluorescent microspheres particle diameter is 135nm.
Embodiment 4: in the 500mL three-necked bottle, add 5.0g through the washed ferroferric oxide powder of deionization, add the deionized water of 200mL, after the dispersed with stirring, add 100mL salpeter solution (3.0M) then, stirring at room 5-10 minute under the 600rpm rotating speed.Separate with magnet then and spend deionised water 3-5 time.With the tri-iron tetroxide mud dispersed with stirring (0.2M) in the sodium citrate solution of 400mL that obtains after the washing, then separate and spend deionised water 3-5 time with magnet, last resulting tri-iron tetroxide is dispersed in the 200mL deionized water, makes the about 2.0wt% magnetic fluid of solid content.
In single neck round-bottomed flask of a 25mL, with 10mL anhydrous alcohol solution 0.0356g fluorescein FITC, add 0.01829g triethoxy amine propyl silane (APS) then, lucifuge stirring reaction 48 hours makes the silane coupler of bonding fluorescence molecule FITC.
In the three-necked bottle of a 500mL, add the good magnetic fluid of 2.0g prepared beforehand, and with the dilution of 50mL deionized water and 200 absolute ethyl alcohols, add the 4mL concentrated ammonia liquor down in high-speed stirred (600rpm) then, add the 4mL ethyl orthosilicate after the system for the treatment of is warming up to 40 ℃, keep and stir after 8 hours, add the silane coupler of the bonding fluorescence molecule FITC of the above-mentioned preparation of 2mL, simultaneously add the 1mL ethyl orthosilicate again, continue at 20 ℃ of lucifuges and stirred 12 hours.Prepared magnetic fluorescent microspheres particle diameter is 170nm.
Claims (9)
1, a kind of magnetic fluorescent dual-function microballoon with nucleocapsid structure is characterized in that with the nano magnetic particle being nuclear, is shell with the silica of the organic fluorescence molecular dopant that has isothiocyanate group that its particle diameter is little to 20 nanometers, greatly to 400 nanometers; Wherein, the inorganic magnetic particle is γ-Fe
2O
3Or Fe
3O
4Or other ferrite particle is a kind of.
2, a kind of preparation method with magnetic fluorescent dual-function microballoon of nucleocapsid structure, it is characterized in that the inorganic magnetic particle being carried out surface modification with strong acid and natrium citricum, utilizing the preparation of gel-sol method then in alcohol/aqueous systems is shell with silica, the inorganic magnetic particle is the inorganic compounding magnetic microsphere of nuclear, be seed at last with the magnetic silica microballoon, the method for the silane coupler copolycondensation by tetraalkyl orthosilicate and bonding fluorescein makes the silica fluorescent microballoon with magnetic; Wherein, fluorescein is the organic fluorescence molecule that has isothiocyanate group, and the inorganic magnetic particle is γ-Fe
2O
3Or Fe
3O
4Or other ferrite particle is a kind of.
3, a kind of preparation method with magnetic fluorescent dual-function microballoon of nucleocapsid structure is characterized in that concrete steps are as follows:
(1) use strong acid that the inorganic magnetic particle is activated: the nano inorganic magnetic-particle is dispersed in the deionized water, utilize the magnet separating, washing, be dispersed in then in the strong acid solution of 2.0-4.0mol/L, stirred 5-20 minute, utilize magnet to isolate the magnetic-particle of process strong acid treatment again, and spend deionised water 3-5 time;
(2) modify inorganic magnetic particle after the activation with citrate: in the slurry of the inorganic magnetic particle of step 1 gained, add citrate solution, dispersed with stirring, separate with magnet then, and spend deionised water 2-4 time, be dispersed in the deionized water at last, obtain the dispersion liquid of the magnetic-particle after the modification, magnetic-particle concentration is 0.5-3.0wt%;
(3) preparation is that shell, inorganic magnetic particle are the inorganic compounding magnetic microsphere of nuclear with silica: the dispersion liquid of the magnetic-particle after the modification is joined in alcohol/water mixed liquid, under agitation add alkali lye and tetraalkyl orthosilicate, keep and stirred 4-12 hour, entire reaction is carried out at 20-40 ℃; Whole system is calculated according to weight, and the magnetic-particle after the modification accounts for 0.3-3.0%, and O.8-3.0% alkali lye account for, and water accounts for 10-20%, and alcohol accounts for 70-75%, and all the other are tetraalkyl orthosilicate;
(4) preparation has the magnetic fluorescent dual-function microballoon of nucleocapsid structure: add the ethanolic solution and the tetraalkyl orthosilicate of the silane coupler of bonding fluorescein in the reacted system of above-mentioned steps (3), 20-40 ℃ of following lucifuge stirring reaction 12-48 hour; Wherein, the ethanolic solution of the silane coupler of tetraalkyl orthosilicate and bonding fluorescein by volume 1: 1-1: 4 add; Here fluorescein is the organic fluorescence molecule that has isothiocyanate group, and the inorganic magnetic particle is γ-Fe
2O
3Or Fe
3O
4Or other ferrite particle is a kind of.
4, the preparation method with magnetic fluorescent dual-function microballoon of nucleocapsid structure according to claim 3 is characterized in that described strong acid is a kind of of nitric acid, sulfuric acid, hydrochloric acid.
5, the preparation method with magnetic fluorescent dual-function microballoon of nucleocapsid structure according to claim 3 is characterized in that used alkali is ammoniacal liquor or TMAH.
6, the preparation method with magnetic fluorescent dual-function microballoon of nucleocapsid structure according to claim 3 is characterized in that used citrate is one or both of natrium citricum, potassium citrate.
7, the preparation method with magnetic fluorescent dual-function microballoon of nucleocapsid structure according to claim 3 is characterized in that used alcohol is one or more of methyl alcohol, ethanol, isopropyl alcohol.
8, the preparation method with magnetic fluorescent dual-function microballoon of nucleocapsid structure according to claim 3 is characterized in that used silane coupler is the silane coupler that has amido.
9, the preparation method with magnetic fluorescent dual-function microballoon of nucleocapsid structure according to claim 3 is characterized in that used tetraalkyl orthosilicate is a kind of of methyl silicate, ethyl orthosilicate.
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