CN101912757B - Preparation method of fluorescent-magnetic dual-coded microspheres - Google Patents
Preparation method of fluorescent-magnetic dual-coded microspheres Download PDFInfo
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Abstract
The invention relates to a preparation method of fluorescent-magnetic dual-coded microspheres. The method comprises the following steps of: taking polystyrene-acrylamide copolymeric nano microspheres as templates, assembling luminescent quantum dots and magnetic nano garma-Fe2O3 onto the surfaces of the microspheres by a layer-by-layer self-assembly method, and controlling the types of the quantum dots or the encapsulating quantity of two types of nano particles in an encapsulating process by a simple method so as to obtain the dual-coded microspheres with different fluorescence-emission and magnetic response abilities. The method has better controllability and higher repeatability; and the prepared coded microspheres have uniform particle size and good monodispersity and can be massively and repeatedly prepared. The method can be more widely applied in fields of chemistry, biology, material science and the like.
Description
Technical field
The present invention relates to the preparation method of a kind of fluorescence-magnetic dual coding microballoon, belong to the biomolecular labeling technical field.
Background technology
Along with the development of bioanalysis science and biotechnology, how to realize that multi-component high throughput testing and sorting have seemed more and more important in the complex biological system.Fluorescence-encoded micro-beads has become the theme of a main research.Fluorescence-encoded micro-beads is a kind of new function microballoon that is loaded with two or more fluorescent material; It can carry out the parallel detection of different biological molecules from single sample; Can from complex target, obtain relevant information, like identification target target from a plurality of albumen or gene.Fluorescent microsphere since in single microballoon embedding the fluorescent material of multiple color, can carry out optical encoding to different fluorescent microspheres.Simultaneously, the big specific area of microballoon is capture molecules more, for bioanalysis provides a high-sensitive platform.It is with a wide range of applications in a lot of fields, like immunoassay, and the sign of gene, albumen and detection and cell classification and imaging.
Quantum dot is owing to possess superior fluorescence properties such as an elementary excitation, polynary emission, and aspect optical encoding, is with a wide range of applications.At present, mainly contain suspension polymerization, swelling investment and self-assembly method layer by layer based on the preparation method of the optical encoding microballoon of quantum dot.Wherein, layer by layer self-assembly method because it is simple to operate, have preferably controllability and used widely.
But, in the actual analysis process, when often not only will realizing a plurality of component, we detect, also to carry out gradient separations to detected components, and this has just proposed requirement to the multifunctionality of coding microball.Therefore, preparation fluorescence-magnetic dual coding microballoon is to realize that multicomponent detects and the key of separating simultaneously.
Chinese patent " preparation method of amino functional magnetic fluorescent coding microsphere with double-nucleocapsid structure " (application number 20,091,006 6652) discloses a kind of preparation method of magnetic fluorescent coding microsphere of double-nucleocapsid structure of amino functional.It is in reverse micro emulsion, to have the semiconductor-quantum-point of different fluorescence colors with two kinds and the ferric oxide nano particles of superparamagnetism is embedded in the same Nano particles of silicon dioxide, form a kind of granularity between 40～100 nm, the magnetic fluorescent coding microsphere of fluorescence intensity is big, stability is high amino functional.The kind of the quantum dot through changing different fluorescence colors and fluorescence position and the intensity that ratio is adjusted microballoon have realized different fluorescence-encoded.The adding of superparamagnetism tri-iron tetroxide makes microballoon under the effect of externally-applied magnetic field, and promptly target is assembled and moved.Amido modified through microsphere surface is carried out, it can be widely used in fields such as immunology detection, nucleic acid hybridization, genetic analysis, cell classification and imaging.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of new fluorescence-magnetic dual coding microballoon.
In order to realize the preparation of fluorescence-magnetic dual coding microballoon, the present invention is a template with polystyrene-acrylamide compolymer/nano microballoon, and the method through self assembly layer by layer is with fluorescence quantum and magnetic Nano γ-Fe
2O
3Be assembled into microsphere surface, encapsulate the kind of quantum dot in the process or the package amount of two kinds of nano particles, obtain the dual coding microballoon of different fluorescent emission and magnetic response ability through regulation and control; In turn include the following steps particularly:
1. adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, and transform surface amino groups as carboxyl with hydrazine hydrate and succinic anhydride successively;
2. utilize 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide/N-succinimide (EDC/NHS) activation method at carboxylated microsphere surface assembling layer of polyethylene imines (PEI);
3. remove unreacted polymine, in n-hexyl alcohol, utilize the coordination of metallic element and nitrogen then, quantum dot or magnetic Nano γ-Fe
2O
3Be assembled into microsphere surface;
4. remove unreacted quantum dot or magnetic Nano γ-Fe
2O
3, then at microsphere surface assembling second layer polymine;
5. repeating step 3.-4.;
6. under the effect of polyvinylpyrrolidone, encapsulate SiO at microsphere surface
2
Further technical scheme with additional technical feature is:
In the technique scheme, the assembling polymine described in the step 2 is specially the microballoon of getting carboxylated, adds polymine, adds 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide and N-succinimide again, and reaction is 12 hours under the room temperature.
In the technique scheme, the unreacted polymine of removing described in the step 3 is specially successively and removes the PEI on the unreacted with NaCl solution and ultra-pure water centrifuge washing, sloughs the water that microsphere surface adheres to the ethanol centrifuge washing again.
In the technique scheme, described in the step 3 with quantum dot or magnetic Nano γ-Fe
2O
3Being assembled into microsphere surface is specially and gets quantum dot or magnetic Nano γ-Fe
2O
3Behind precipitation with alcohol, disperse with n-hexyl alcohol, add in the hexanol dispersion liquid of microballoon, on shaking table, reacted 2 hours under the room temperature.
In the technique scheme, remove unreacted quantum dot or magnetic Nano γ-Fe described in the step 4
2O
3Be specially and react the centrifugal n-hexyl alcohol of removing that finishes, unreacted quantum dot or magnetic Nano γ-Fe are removed in the n-hexane washing
2O
3, more successively with ethanol and ultra-pure water washing.
In the technique scheme, being specially removing unreacted quantum dot or magnetic Nano γ-Fe described in the step 4 at microsphere surface assembling second layer polymine
2O
3Microballoon be scattered in the polyethyleneimine: amine aqueous solution, under the room temperature on shaking table the reaction 2 hours.
In the technique scheme, can allocate the kind of quantum dot or the package amount of two kinds of nano particles in the step 5 arbitrarily.
In the technique scheme, encapsulate SiO at microsphere surface described in the step 6
2Process be specially the ethanolic solution that adds polyvinylpyrrolidone (PVP) in the microballoon after washing successively with ultra-pure water and ethanol, reacted 12-24 hour; The ethanolic solution that in reactant liquor, adds ammoniacal liquor and tetraethoxy silica alkane (TEOS) then; After reacting 12 hours on the shaking table, drip the ethanolic solution of tetraethoxy silica alkane under the room temperature once more; Continue reaction adds 3-aminopropyl triethoxysilane (APTES) after 12 hours ethanolic solution, reaction is spent the night.
The present invention encapsulates the kind of quantum dot in the process or the package amount of two kinds of nano particles through simple control, thereby obtains the dual coding microballoon of different fluorescent emission and magnetic response ability.This method has controllability and higher repeatability preferably, and the coding microball uniform particle diameter, the monodispersity that prepare are good, and can repeat preparation in a large number.The present invention can be applied even more extensively in fields such as chemistry, biology and material science.
Description of drawings
Fig. 1 the present invention prepares the schematic flow sheet of fluorescence-magnetic dual coding microballoon.
Assemble the fluorescence spectrum of microballoon of the quantum dot of different fluorescent emission when Fig. 2 embodiment of the invention 1,2,3 is prepared at individual layer.
The assembling that Fig. 3 embodiment of the invention 4,5,6 is prepared the fluorescence spectrum of microballoon of quantum dot of the different fluorescent emission of multilayer.
Two-layer, (c) three layers of magnetic Nano γ-Fe of assembling (a) one deck, (b) that Fig. 4 embodiment of the invention 7,8,9 is prepared
2O
3The hysteresis curve of microballoon.
Assembling multi-layer quantum point and magnetic Nano γ-Fe when Fig. 5 embodiment of the invention 10,11,12 is prepared
2O
3The fluorescence spectrum of microballoon.
Fig. 6 embodiment of the invention 10 has been assembled quantum dot and magnetic Nano γ-Fe in the time of prepared
2O
3The transmission electron microscope photo of microballoon.
Fig. 7 embodiment of the invention 13 prepared to having assembled quantum dot and magnetic Nano γ-Fe simultaneously
2O
3The microballoon silanization after the transmission electron microscope photo.
The specific embodiment
The present invention is a template with polystyrene-acrylamide compolymer/nano microballoon, and the method through self assembly layer by layer is with fluorescence quantum and magnetic Nano γ-Fe
2O
3Be assembled into microsphere surface, encapsulate the kind of quantum dot in the process or the package amount of two kinds of nano particles, obtain the dual coding microballoon of different fluorescent emission and magnetic response ability through regulation and control; In turn include the following steps particularly:
1. adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, and transform surface amino groups as carboxyl with hydrazine hydrate and succinic anhydride successively;
2. utilize 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide/N-succinimide (EDC/NHS) activation method at carboxylated microsphere surface assembling layer of polyethylene imines (PEI);
3. remove unreacted polymine, in n-hexyl alcohol, utilize the coordination of metallic element and nitrogen then, quantum dot or magnetic Nano γ-Fe
2O
3Be assembled into microsphere surface;
4. remove unreacted quantum dot or magnetic Nano γ-Fe
2O
3, then at microsphere surface assembling second layer polymine;
5. repeating step 3.-4.;
6. under the effect of polyvinylpyrrolidone, encapsulate SiO at microsphere surface
2
Through embodiment the preparation method of fluorescence-magnetic dual coding Nano microsphere is done detailed explanation below.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) respectively get the green quantum dot with the yellow fluorescence emission of 200 L and disperse with n-hexyl alcohol after with precipitation with alcohol, mix, join in the step microballoon dispersion liquid 3., place on the shaking table and reacted 2 hours;
5) react the centrifugal n-hexyl alcohol of removing that finishes; Unreacted quantum dot is removed in the n-hexane washing; Be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, on shaking table, reacted 2 hours under the room temperature, assembling second layer PEI;
6) product that obtains of reaction with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) quantum dot of quantum dot and the emission of 400 L yellow fluorescences of getting 200 L green fluorescences emissions disperses with n-hexyl alcohol after with precipitation with alcohol, mixes, and joins in the step microballoon dispersion liquid 3., places on the shaking table reaction 2 hours;
5) react the centrifugal n-hexyl alcohol of removing that finishes; Unreacted quantum dot is removed in the n-hexane washing; Be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, on shaking table, reacted 2 hours under the room temperature, assembling second layer PEI;
6) product that obtains of reaction with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
Embodiment 3 individual layers assembling multicolor fluorescence coding microball, the rate of charge of the quantum dot of its medium green, Huang, red three kinds of fluorescent emission is respectively 1:1:1.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) get respectively that 200 L are green, the quantum dot of yellow and red fluorescence emission disperses with n-hexyl alcohol after with precipitation with alcohol, mixes, and joins in the step microballoon dispersion liquid 3., places on the shaking table reaction 2 hours;
5) react the centrifugal n-hexyl alcohol of removing that finishes; Unreacted quantum dot is removed in the n-hexane washing; Be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, on shaking table, reacted 2 hours under the room temperature, assembling second layer PEI;
6) product that obtains of reaction with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
Fig. 2 assembles the fluorescence spectrum of microballoon of the quantum dot of different fluorescent emission prepared the time at individual layer for embodiment 1,2,3: (a) embodiment 1; (b) embodiment 2; (c) embodiment 3.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) quantum dot of getting 0.5 mL green fluorescence emission also is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the step microballoon dispersion liquid 3. reaction 2 hours on shaking table under the room temperature;
5) react the centrifugal n-hexyl alcohol of removing that finishes; Unreacted quantum dot is removed in the n-hexane washing; Be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, on shaking table, reacted 2 hours under the room temperature, assembling second layer PEI;
6) repeating step 3.;
7) quantum dot of getting 0.5 mL yellow fluorescence emission is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the step microballoon dispersion liquid 6. reaction 2 hours on shaking table under the room temperature;
8) 5. repeating step assembles the 3rd layer of PEI;
9) product that obtains of reaction at last with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
Embodiment 5 multilayers assembling multicolor fluorescence coding microball comprises the quantum dot that emission of one deck green fluorescence and two-layer yellow fluorescence are launched.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) quantum dot of getting 0.5 mL green fluorescence emission is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the step microballoon dispersion liquid 3. reaction 2 hours on shaking table under the room temperature;
5) react the centrifugal n-hexyl alcohol of removing that finishes; Unreacted quantum dot is removed in the n-hexane washing; Be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, on shaking table, reacted 2 hours under the room temperature, assembling second layer PEI;
6) repeating step 3.;
7) quantum dot of getting 0.5 mL yellow fluorescence emission also is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the step microballoon dispersion liquid 6. reaction 2 hours on shaking table under the room temperature;
8) 5. repeating step assembles the 3rd layer of PEI;
9) repeating step 3.;
10) quantum dot of getting 0.5 mL yellow fluorescence emission also is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the step microballoon dispersion liquid 9. reaction 2 hours on shaking table under the room temperature;
11) 5. repeating step assembles the 4th layer of PEI;
12) product that obtains of reaction at last with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
Embodiment 6 multilayers assembling multicolor fluorescence coding microball comprises the quantum dot that the emission of one deck green fluorescence, the emission of one deck yellow fluorescence and two-layer red fluorescence are launched.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) quantum dot of getting 0.5 mL green fluorescence emission also is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the step microballoon dispersion liquid 3. reaction 2 hours on shaking table under the room temperature;
5) react the centrifugal n-hexyl alcohol of removing that finishes; Unreacted quantum dot is removed in the n-hexane washing; Be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, on shaking table, reacted 2 hours under the room temperature, assembling second layer PEI;
6) repeating step 3.;
7) quantum dot of getting 0.5 mL yellow fluorescence emission also is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the step microballoon dispersion liquid 6. reaction 2 hours on shaking table under the room temperature;
8) 5. repeating step assembles the 3rd layer of PEI;
9) repeating step 3.;
10) quantum dot of getting 0.5 mL red fluorescence emission also is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the step microballoon dispersion liquid 9. reaction 2 hours on shaking table under the room temperature;
11) 5. repeating step assembles the 4th layer of PEI;
12) repeating step 3.;
13) quantum dot of getting 0.5 mL red fluorescence emission also is scattered in the n-hexyl alcohol after with precipitation with alcohol, joins in the microballoon dispersion liquid of step 12 reaction 2 hours on shaking table under the room temperature;
14) 5. repeating step assembles layer 5 PEI;
15) product that obtains of reaction at last all with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
Fig. 3 has assembled the fluorescence spectrum of microballoon of the quantum dot of the different fluorescent emission of multilayer for the embodiment of the invention 4,5,6: (a) embodiment 4; (b) embodiment 5; (c) embodiment 6.
Embodiment 7 individual layers assembling magnetic coding microball
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) get 0.5 mL magnetic Nano γ-Fe
2O
3With also being scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 3., on shaking table, reacted 2 hours under the room temperature;
5) react the centrifugal n-hexyl alcohol of removing that finishes, unreacted magnetic Nano γ-Fe is removed in the n-hexane washing
2O
3, be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, reaction 2 hours on shaking table under the room temperature, assembling second layer PEI;
6) product that obtains of reaction at last with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
Embodiment 8 two-layer assembling magnetic coding microballs
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) get 0.5 mL magnetic Nano γ-Fe
2O
3With also being scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 3., on shaking table, reacted 2 hours under the room temperature;
5) react the centrifugal n-hexyl alcohol of removing that finishes, unreacted magnetic Nano γ-Fe is removed in the n-hexane washing
2O
3, be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, reaction 2 hours on shaking table under the room temperature, assembling second layer PEI;
6) repeating step 3.;
7) get 0.5 mL magnetic Nano γ-Fe
2O
3With being scattered in behind the precipitation with alcohol in the n-hexyl alcohol, join in the step microballoon dispersion liquid 6., on shaking table, reacted 2 hours under the room temperature;
8) 5. repeating step assembles the 3rd layer of PEI;
9) product that obtains of reaction at last with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
9 three layers of assembling of embodiment magnetic coding microball
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) get 0.5 mL magnetic Nano γ-Fe
2O
3With also being scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 3., on shaking table, reacted 2 hours under the room temperature;
5) react the centrifugal n-hexyl alcohol of removing that finishes, unreacted magnetic Nano γ-Fe is removed in the n-hexane washing
2O
3, be scattered in 1.5mL 1 mg/mL PEI solution after washing repeatedly respectively with ethanol and ultra-pure water successively again, reaction 2 hours on shaking table under the room temperature, assembling second layer PEI;
6) repeating step 3.;
7) get 0.5 mL magnetic Nano γ-Fe
2O
3With also being scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 6., on shaking table, reacted 2 hours under the room temperature;
8) 5. repeating step assembles the 3rd layer of PEI;
9) repeating step 3.;
10) get 0.5 mL magnetic Nano γ-Fe
2O
3With being scattered in behind the precipitation with alcohol in the n-hexyl alcohol, join in the step microballoon dispersion liquid 9., on shaking table, reacted 2 hours under the room temperature;
11) 5. repeating step assembles the 4th layer of PEI;
12) product that obtains of reaction at last with the ultra-pure water washing repeatedly is scattered in the ultra-pure water of certain volume subsequent use.
Fig. 4 is prepared two-layer, (c) the three layers of magnetic Nano γ-Fe of assembling (a) one deck, (b) of embodiment 7,8,9
2O
3The hysteresis curve of microballoon.
The preparation of embodiment 10 fluorescence-magnetic dual coding microballoon comprises one deck magnetic Nano γ-Fe
2O
3, one deck green fluorescence emission, the emission of one deck yellow fluorescence and the emission of one deck red fluorescence quantum dot.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) get 0.5 mL magnetic Nano γ-Fe
2O
3With also being scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 3., on shaking table, reacted 2 hours under the room temperature;
5) the reaction centrifugal n-hexyl alcohol of removing that finishes, n-hexane washing 3 times is scattered in 1.5mL 1 mg/mL PEI solution after washing 3 times respectively with ethanol and ultra-pure water successively again, on shaking table, reacts 2 hours under the room temperature, assembles second layer PEI;
6) repeating step 3.;
7) get the quantum dot that 0.5 mL green fluorescence is launched, also be scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 6., on shaking table, reacted 2 hours under the room temperature;
8) repeating step 3. after 5. repeating step assembled the 3rd layer of PEI;
9) get the quantum dot that 0.5 mL yellow fluorescence is launched, also be scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 8., on shaking table, reacted 2 hours under the room temperature;
10) 5. repeating step assembles the 4th layer of PEI;
11) repeating step 3.;
12) get the quantum dot that 0.5 mL red fluorescence is launched, also be scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the microballoon dispersion liquid of step 11, on shaking table, reacted 2 hours under the room temperature;
13) after 5. repeating step assembled layer 5 PEI, the product that obtains of reaction with the ultra-pure water washing repeatedly was scattered in the ultra-pure water of certain volume subsequent use.
Fig. 6 is for implementing the transmission electron microscope photo of 10 made microballoons.
The preparation of embodiment 11 fluorescence-magnetic dual coding microballoon comprises two-layer magnetic Nano γ-Fe
2O
3, one deck yellow fluorescence emission and the emission of one deck red fluorescence quantum dot.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) get 0.5 mL magnetic Nano γ-Fe2O3 respectively and also be scattered in the n-hexyl alcohol after with precipitation with alcohol, join in the step microballoon dispersion liquid 3., reaction 2 hours on shaking table under the room temperature;
5) the reaction centrifugal n-hexyl alcohol of removing that finishes, n-hexane washing 3 times is scattered in 1.5mL 1 mg/mL PEI solution after washing 3 times respectively with ethanol and ultra-pure water successively again, on shaking table, reacts 2 hours under the room temperature, assembles second layer PEI;
6) repeating step 3.;
7) get 0.5 mL magnetic Nano γ-Fe
2O
3, also be scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 6., on shaking table, reacted 2 hours under the room temperature;
8) repeating step 3. after 5. repeating step assembled the 3rd layer of PEI;
9) get the quantum dot that 0.5 mL yellow fluorescence is launched, also be scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 8., on shaking table, reacted 2 hours under the room temperature;
10) repeating step 3. after 5. repeating step assembled the 4th layer of PEI;
11) get the quantum dot that 0.5 mL red fluorescence is launched, also be scattered in behind the precipitation with alcohol in the n-hexyl alcohol, correspondence joins in the step microballoon dispersion liquid 10., on shaking table, reacts 2 hours under the room temperature;
12) after 5. repeating step assembled layer 5 PEI, the product that obtains of reaction with the ultra-pure water washing repeatedly was scattered in the ultra-pure water of certain volume subsequent use.
The preparation of embodiment 12 fluorescence-magnetic dual coding microballoon comprises three layers of magnetic Nano γ-Fe
2O
3Quantum dot with the emission of one deck red fluorescence.
1) adopt improved agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, dialysis is removed and is taken out 20 mL behind unreacted monomer and the initator and add 5 mL hydrazine hydrates and reacted 8 hours down for 45-55 ℃; Take out 10 mL in small beaker after removing unreacted hydrazine hydrate, the effect of stirring adds 0.2 g succinic anhydride (regulating pH about 4 with NaOH simultaneously) down, adds continued reaction 2 hours; Change in the bag filter; Dialysis is clean, obtains the carboxylated microballoon, and is for use;
2) get the microballoon of 1 mL carboxylated, add 1 mL, 0.2 g/mL polyethyleneimine: amine aqueous solution, add 25mg EDC and 15mg NHS again, reaction is spent the night under the room temperature, at microsphere surface assembling one deck PEI;
3) successively with NaCl solution and ultra-pure water respectively centrifuge washing remove the PEI on the unreacted, slough the water that microsphere surface adheres to the ethanol centrifuge washing again, then it is scattered in the n-hexyl alcohol;
4) get 0.5 mL magnetic Nano γ-Fe
2O
3With also being scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 3., on shaking table, reacted 2 hours under the room temperature;
5) the reaction centrifugal n-hexyl alcohol of removing that finishes, n-hexane washing 3 times is scattered in 1.5mL 1 mg/mL PEI solution after washing 3 times respectively with ethanol and ultra-pure water successively again, on shaking table, reacts 2 hours under the room temperature, assembles second layer PEI;
6) repeating step 3.;
7) get 0.5 mL magnetic Nano γ-Fe
2O
3, also be scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 6., on shaking table, reacted 2 hours under the room temperature;
8) repeating step 3. after 5. repeating step assembled the 3rd layer of PEI;
9) get 0.5 mL magnetic Nano γ-Fe
2O
3, also be scattered in the n-hexyl alcohol behind the precipitation with alcohol, join in the step microballoon dispersion liquid 8., on shaking table, reacted 2 hours under the room temperature;
10) repeating step 3. after 5. repeating step assembled the 4th layer of PEI;
11) get the quantum dot that 0.5 mL red fluorescence is launched, also be scattered in behind the precipitation with alcohol in the n-hexyl alcohol, correspondence joins in the step microballoon dispersion liquid 10., on shaking table, reacts 2 hours under the room temperature;
12) after 5. repeating step assembled layer 5 PEI, the product that obtains of reaction with the ultra-pure water washing repeatedly was scattered in the ultra-pure water of certain volume subsequent use.
Fig. 5 is embodiment 10,11,12 assembling multi-layer quantum point and magnetic Nano γ-Fe prepared the time
2O
3The fluorescence spectrum of microballoon: (a) embodiment 10; (b) embodiment 11; (c) embodiment 12.
Embodiment 13 coding microball silanizations
1) quantum dot and magnetic Nano γ-Fe will have been assembled simultaneously
2O
3Microballoon (prepared) by embodiment 10 with the ethanolic solution that adds 4mL polyvinylpyrrolidone (PVP) after the washing with alcohol 3 times, reaction is spent the night;
2) ethanolic solution (10 vol%) of adding 90 mL ammoniacal liquor (29.3 wt %) and 125 mL tetraethoxy silica alkane (TEOS) in reactant liquor; After reacting 12 hours on the shaking table, drip the ethanolic solution (10 vol%) of 125 mL TEOS under the room temperature once more; Continue reaction adds 125 mL 3-aminopropyl triethoxysilanes (APTES) after 12 hours ethanolic solution (10 vol%), reaction is spent the night;
3) reaction finishes, and washs respectively repeatedly with ethanol and ultra-pure water successively, is scattered in the ultra-pure water of certain volume subsequent use.
Fig. 7 for embodiment 13 prepared to having assembled quantum dot and magnetic Nano γ-Fe simultaneously
2O
3The microballoon silanization after the transmission electron microscope photo.
Show through signs such as transmission electron microscope, fluorescence spectrum, hysteresis curves; The Nano microsphere of this method preparation has uniform particle diameter property and higher repeatability preferably, and can obtain the Nano microsphere of different fluorescent emission and magnetic response behavior very easily through simple regulation and control.
Claims (7)
1. the preparation method of fluorescence-magnetic dual coding microballoon is characterized in that with polystyrene-acrylamide compolymer/nano microballoon be template, and the method through self assembly layer by layer is with fluorescence quantum and magnetic Nano γ-Fe
2O
3Be assembled into microsphere surface, encapsulate the kind of quantum dot in the process or the package amount of two kinds of nano particles, obtain the dual coding microballoon of different fluorescent emission and magnetic response ability through regulation and control; In turn include the following steps particularly:
1. adopt agalactosis polymerization to prepare the surface and be rich in amino polystyrene-acrylamide compolymer/nano microballoon, and transform surface amino groups as carboxyl with hydrazine hydrate and succinic anhydride successively;
2. utilize 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide/N-succinimide activation method at carboxylated microsphere surface assembling layer of polyethylene imines;
3. remove unreacted polymine, in n-hexyl alcohol, utilize the coordination of metallic element and nitrogen then, quantum dot or magnetic Nano γ-Fe
2O
3Be assembled into microsphere surface;
4. remove unreacted quantum dot or magnetic Nano γ-Fe
2O
3, then at microsphere surface assembling second layer polymine;
5. repeating step 3.-4.;
6. under the effect of polyvinylpyrrolidone, encapsulate SiO at microsphere surface
2
2. the preparation method of fluorescence as claimed in claim 1-magnetic dual coding microballoon; It is characterized in that the assembling polymine described in the step 2 is specially the microballoon of getting carboxylated; Add 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide and N-succinimide; Add polymine again, reaction is 12 hours under the room temperature.
3. according to claim 1 or claim 2 the preparation method of fluorescence-magnetic dual coding microballoon; It is characterized in that the unreacted polymine of removing described in the step 3 is specially successively and removes the polymine on the unreacted with NaCl solution and ultra-pure water centrifuge washing, sloughs the water that microsphere surface adheres to the ethanol centrifuge washing again.
4. according to claim 1 or claim 2 the preparation method of fluorescence-magnetic dual coding microballoon, it is characterized in that described in the step 3 with quantum dot or magnetic Nano γ-Fe
2O
3Being assembled into microsphere surface is specially and gets quantum dot or magnetic Nano γ-Fe
2O
3Behind precipitation with alcohol, disperse with n-hexyl alcohol, add in the n-hexyl alcohol dispersion liquid of microballoon, on shaking table, reacted 2 hours under the room temperature.
5. according to claim 1 or claim 2 the preparation method of fluorescence-magnetic dual coding microballoon is characterized in that removing unreacted quantum dot or magnetic Nano γ-Fe described in the step 4
2O
3Be specially and react the centrifugal n-hexyl alcohol of removing that finishes, unreacted quantum dot or magnetic Nano γ-Fe are removed in the n-hexane washing
2O
3, more successively with ethanol and ultra-pure water washing.
6. according to claim 1 or claim 2 the preparation method of fluorescence-magnetic dual coding microballoon is characterized in that being specially removing unreacted quantum dot or magnetic Nano γ-Fe at microsphere surface assembling second layer polymine described in the step 4
2O
3Microballoon be scattered in the polyethyleneimine: amine aqueous solution, under the room temperature on shaking table the reaction 2 hours.
7. according to claim 1 or claim 2 the preparation method of fluorescence-magnetic dual coding microballoon is characterized in that encapsulating SiO at microsphere surface described in the step 6
2Process be specially in the microballoon after washing successively the ethanolic solution that adds polyvinylpyrrolidone with ultra-pure water and ethanol, reacted 12-24 hour; The ethanolic solution that in reactant liquor, adds ammoniacal liquor and tetraethoxy silica alkane then; After reacting 12 hours on the shaking table, drip the ethanolic solution of tetraethoxy silica alkane under the room temperature once more; Continue reaction adds the 3-aminopropyl triethoxysilane after 12 hours ethanolic solution, reaction is spent the night.
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| CN111790324B (en) * | 2020-06-18 | 2022-05-03 | 浙江工业大学 | Multi-level controllable assembled fluorescent-magnetic bifunctional microsphere and preparation method and application thereof |
| CN111996000B (en) * | 2020-08-25 | 2021-09-03 | 重庆大学 | Rare earth fluorescent coding microsphere and preparation method and fluorescent coding method thereof |
| CN113578214B (en) * | 2021-08-11 | 2023-08-11 | 天津博蕴纯化装备材料科技有限公司 | Micron-sized porous magnetic microsphere and preparation method and application thereof |
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