CN102343240B - Fluorescent magnetic bifunctional dendrimer microspheres and preparation method thereof - Google Patents
Fluorescent magnetic bifunctional dendrimer microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention discloses fluorescent magnetic bifunctional dendrimer microspheres and a preparation method thereof. The microspheres comprises: magnetic nanoparticles, the spherical surfaces of which are modified into dendrimers with an amino terminal connecting fluorescent quantumdots; quantumdots, with a particle size of 2-10nm and a modified surface with carboxylic groups; and the magnetic nanoparticles and the quantumdots are connected through the amino groups at the end of the dendrimers and the carboxylic groups of the quantumdots. The microspheres of the invention both reserve the excellent fluorescence characteristics of quantumdots, and have the superparamagnetism of magnetic particles. Able to be acquired and separated through a simple external magnetic field, the microspheres provided in the invention can be applied in the fields of immunodetection, fluorescence tracking and magnetic separation, etc.
Description
Technical field
The invention belongs to biomedicine, analytical chemistry, nanometer material science, synthesising chemical technology field, be specifically related to difunctional dendrimer microballoon of a kind of fluorescence magnetic and preparation method thereof.
Background technology
Along with the progress of medical technology, to the raising of the requirement of biomaterial, having the nano magnetic material of separation function and the quantum dot of excellent fluorescence labeling function is two more class materials of research.
Easily characteristics such as functionalization are very noticeable because having good biologically active, superparamagnetism and surface for nano magnetic material, and it can be in conjunction with various functional moleculars such as enzyme, antibody, cell, DNA or RNA etc., gather under the effect in magnetic field and separate.Thereby be widely used in fields such as the separation of the immobilization of targeted drug, enzyme, immunoassays, cell and classification.
Quantum dot (quantumdots, claim semiconductor nanocrystal again), it is by the inorganic nanoparticles that II-VI family and III-V family element are formed, and its yardstick is about 2～10 nanometers, because quantum size effect and dielectric confinement effect make their performances have unique photoluminescence performance.The emission light intensity of quantum dot is 20 times of conventional organic fluorescent dye, and stability is stronger more than 100 times than conventional organic fluorescent dye, and can stand repeatedly to excite, and realizes the polynary emission of an elementary excitation, carries out the multi-color marking of different target targets.These distinct characteristics and unique application function make quantum dot be widely used in immunoassay, genetic analysis, drug screening, fields such as live body and cell fluorescence imaging.
Mark with separate the important process that becomes in the modern biomedical engineering field, if mark can be finished in a step with the work that separates, will greatly promote the development of bioscience technology.The present invention therefore.
Summary of the invention
The object of the invention is to provide a kind of fluorescence magnetic difunctional dendrimer microballoon, by at magnetic nano-particle finishing dendrimer, the amino fluorescent nano material quantum dot that connects after TGA is modified of function by big molecular end obtains the bifunctional dendrimer microballoon that existing excellent fluorescence property can separate by magnetic field again.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
The difunctional dendrimer microballoon of a kind of fluorescence magnetic is characterized in that described microballoon has following composition:
Magnetic nano-particle, the modified formation of its spherical surface have as the dendrimer of the amino that connects fluorescence quantum for end;
Fluorescence quantum, its particle diameter is at 2～10nm, and finishing has carboxylic group;
Described magnetic nano-particle is connected with the carboxyl of fluorescence quantum with the amino of fluorescence quantum by the dendrimer end.
Preferably, the particle diameter of the difunctional dendrimer microballoon of described fluorescence magnetic is in 20～100nm scope.
Preferably, the difunctional dendrimer microballoon of described fluorescence magnetic is rule or irregular sphere, square and oval-shaped particle.
Preferably, described fluorescence quantum is selected from nano level CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot.
Preferably, the particle diameter of described fluorescence quantum is in 2～10nm scope.
Preferably, described magnetic nano-particle is super paramagnetic, paramagnetic or ferromagnetic metal, metal alloy or metal oxide nanoparticles.
Preferably, described magnetic nano-particle is selected from Fe
3O
4, γ-Fe
2O
3, MeFe
2O
3, NiCoFe, FeCo and NiFe magnetic nanoparticle, wherein Me is Co, Mn, Ni.
The present invention also provides the preparation method of the difunctional dendrimer microballoon of a kind of fluorescence magnetic, it is characterized in that said method comprising the steps of:
(1) preparation magnetic nano-particle;
(2) magnetic nano-particle is soaked in tetramethyl aqua ammonia (TMAOH) solution, makes upward hydroxyl of the abundant modification in its surface, and then reacts with 3-aminopropyl triethoxysilane (APTES), and obtaining amino is the zero for magnetic particle of end;
(3) zero formation after esters of acrylic acid, ethylene diamine-modified connection repeatedly successively for magnetic particle is with aminoterminal deriving for magnetic particle;
(4) preparation fluorescence quantum is controlled particle diameter in 2～10nm scope, and modifies with TGA, makes its surface have carboxylic group;
(5) make zero for magnetic particle and/or derive and connect the fluorescence quantum of going up the band carboxyl for magnetic particle, obtain the difunctional dendrimer microballoon of fluorescence magnetic.
Preferably, esters of acrylic acid is selected from methyl acrylate, butyl acrylate in the described method step (3), and the solvent of employing is selected methyl alcohol for use.
Preferably, the fluorescence quantum after the described modification is water miscible, and being connected used system with magnetic nano-particle after the finishing is water.
Derive for magnetic particle can be generation magnetic particle, two generation magnetic particle even more for magnetic particle.In per generation,, the magnetic particle end all was with amino, can be connected to form the difunctional dendrimer microballoon of fluorescence magnetic of the present invention with the fluorescence quantum of band carboxylic group.
As typically, magnetic nano-particle is selected Fe for use
3O
4, be reflected at magnetic nano-particle with tetramethyl aqua ammonia (TMAOH) and form abundant hydroxyl, then with 3-aminopropyl triethoxysilane (APTES) reaction, obtain end and have the zero for magnetic particle of amino; Be dissolved in the methanol solution for magnetic particle zero, add the butyl acrylate reaction, the back adding reacting ethylenediamine of purifying obtains generation magnetic particle; Be dissolved in the methanol solution after will generation magnetic particle purifying again, and add the butyl acrylate reaction again, the back of purifying adds ethylenediamine, continues reaction, obtain two generation magnetic particle.
The present invention with magnetic nano-particle and quantum dot in conjunction with forming magnetic fluorescent microspheres, make the process of once finishing selection, collection and the analysis etc. of biomolecule in the body become possibility, be widely used in fields such as immune detection, targeted therapy, cell separation, represented it in interdisciplinary science field good prospects for application such as biology, chemistry, medical science.
With respect to scheme of the prior art, advantage of the present invention is:
The invention provides difunctional dendrimer microballoon of a kind of fluorescence magnetic and preparation method thereof, dendrimer in the magnetic nano-particle finishing first, have the dendrimer that enriches function amino by end and be connected with a large amount of fluorescent nano material quantum dot through absorption, bonding, obtained having the bifunctional Nano microsphere of fluorescence magnetic.The difunctional dendrimer microballoon of fluorescence magnetic of the present invention thing had both kept the fluorescent characteristic of quantum dot excellence, had the superparamagnetism of magnetic particle again, can gather and separated by simple externally-applied magnetic field.This difunctional fluorescence magnetic particulate can be applicable to fields such as immune detection, fluorescence tracking, Magnetic Isolation.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described:
Fig. 1 for zero generation of preparation, a generation, two generation magnetic particle composition principle figure;
Fig. 2 is the zero composition principle figure that is connected with quantum dot for magnetic particle;
Fig. 3 is the molecular structure of the difunctional dendrimer microballoon of two generation fluorescence magnetics;
Fig. 4 is the transmission electron microscope photo of quantum dot and the difunctional dendrimer microballoon of three generations's fluorescence magnetic; Wherein a is the CdSe/CdS QDs that TGA is modified; B is that G0F-zero is for the difunctional dendrimer microballoon of fluorescence magnetic; C is the difunctional dendrimer microballoon of G1F-generation fluorescence magnetic; D, e are the difunctional dendrimer microballoon of G2F-two generations fluorescence magnetic;
Fig. 5 is the fluorescence spectrum of quantum dot and the difunctional dendrimer microballoon of three generations's fluorescence magnetic; Wherein a is CdSe/CdS QDs; B is that G0F-zero is for the difunctional dendrimer microballoon of fluorescence magnetic; C is the difunctional dendrimer microballoon of G1F-generation fluorescence magnetic; D is the difunctional dendrimer microballoon of G2F-two generations fluorescence magnetic;
The susceptibility curve of Fig. 6 for being obtained by vibrating specimen magnetometer under the room temperature; Wherein a is Fe
3O
4B is that G0F-zero is for the difunctional dendrimer microballoon of fluorescence magnetic; C is the difunctional dendrimer microballoon of G1F-generation fluorescence magnetic; D is the difunctional dendrimer microballoon of G2F-two generations fluorescence magnetic.
The specific embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Embodiment 1Fe
3O
4The preparation of the difunctional dendrimer microballoon of/CdSe/CdS fluorescence magnetic
As shown in Figure 1, Fe
3O
4The preparation process of the difunctional dendrimer microballoon of/CdSe/CdS fluorescence magnetic is as follows:
1, preparation fluorescence quantum, the control particle diameter is 2～10nm.
Synthetic and the modification of cadmium selenide outer wrapping cadmium sulfide (CdSe/CdS), concrete preparation method is as follows:
By literature method (Diao, X.L.; Xia, Y.S.; Zhang, T.L.; Li, Y.; Zhu, C.Q.J.Anal.Bioanal.Chem.2007,388,1191), adopt the synthetic CdSe quantum dot of oil phase.With the CdO of 20mmol, the atoleine of 9.6mL oleic acid and 40mL adds successively and adds thermal agitation in the three-necked bottle, and the CdO dissolving generates uniform flaxen Cd solution in the time of 150 ℃.1mmol Se powder and 50mL atoleine are added stirring fast in another there-necked flask, be heated to 240 ℃, the solution faint yellow Chinese red that becomes earlier becomes redness then.The Cd solution (containing the 2mmol Cd that has an appointment) of about 5mL is expelled in the Se solution lightly, stirs fast simultaneously and obtain red CdSe.Temperature drops to 210 ℃ after having injected, and maintains 220 ℃ at last.Take by weighing the S powder of 0.0352g simultaneously, 0.1157g NaBH
4The absolute ethyl alcohol of solid and 30mL mixes, and adds thermal agitation.With the H that generates
2S gas feeds in the CdSe solution, namely generates nucleocapsid CdSe/CdS QDs after continuing to add thermal agitation 0.5h.
Get the above-mentioned quantum dot of 1mL in small beaker, add the 30mL n-hexane, place on the magnetic stirring apparatus and stir, all dissolve to CdSe/CdS.Solution is carried out centrifugation with supercentrifuge, leave and take supernatant liquor.Get excessive TGA and add in the clear liquid, continue to stir 30min.Leave standstill and obtain the stable CdSe/CdS precipitation of red TGA, remove supernatant, and wash 2～3 times with n-hexane.To precipitate and be dissolved in ethanolic solution after air-dry, namely obtain the transparent CdSe/CdS solution of water miscible redness.
2, preparation magnetic nano-particle.
Prepare Fe with chemical coprecipitation
3O
4Nano particle, concrete grammar is as follows:
By literature method (Hong, R.-Y.; Wang, J.; Li, J.-H.; Li, H.-Z.Chin.J.Process Eng.2004,4,472).Compound concentration is the FeCl of 0.5mol/L respectively
3And FeSO
4Solution is pressed Fe
3+With Fe
2+The amount of substance ratio is about 1.75: 1 and evenly pours two kinds of salt solution mix into there-necked flask, lead to nitrogen while stirring, the while dropping sodium aqueous solution (1mol/L), regulating the pH value is 11, produce to the black colloid substance, continue to stop behind the reaction 30min. product is left standstill a week, behind 80 ℃ of slaking 30min, alternately wash to neutral with absolute ethyl alcohol and deionized water, namely obtain Fe
3O
4Nano particle.
3, magnetic nanoparticle is modified and is gone up dendrimer
As shown in Figure 1, with Fe
3O
4Nano particle sinks in TMAOH (7%) aqueous solution and left standstill two hours, washes 2 ethanol then and washes 2 times.It is dissolved in 150mL ethanol/water (volume ratio 1: 1) solution, adds a certain amount of APTES, ultrasonic 20min is uniformly dispersed particle.With solution room temperature stirring reaction 7h, make the magnetic Nano surface be with functional amino.Utilize magnetic that it is separated at last.Wash 2 times, ethanol is washed 3 times, and is air-dry.Namely obtain zero for magnetic particle (G0).
(StepA) be dissolved in the 100mL methanol solution for magnetic particle (G0) zero, add the methyl acrylate (or butyl acrylate) of 1mL, sealing is at room temperature reacted 48h behind the ultrasonic dispersion 30min down; (StepB) separate the back of purifying in the magnetic field and add 100mL methyl alcohol and 2mL ethylenediamine, sealing is at room temperature reacted 48h behind the ultrasonic dispersion 30min down, and separating in the magnetic field purifies obtains generation magnetic particle (G1).
Repeat above-mentioned steps, with butyl acrylate and the anhydrous ethylenediamine of double amount, obtain two generation magnetic particles (G2).Standby in the ethanol during G0, G1, G2 disperseed respectively.
4, three generations's fluorescence magnetic dendrimer microballoon (G0F, G1F and G2F) is synthetic
As shown in Figure 2, getting the G0 magnetic particle of 15 μ L and put into bottle, is solvent with ethanol, disperses 30min in ultrasonic, adds the CdSe/CdS quantum dot that excessive TGA is modified then.Mixed solution is put into constant temperature shaking table reaction 20h, and purification is separated in magnetic field, obtains the zero dendrimer microballoon (G0F) for fluorescence magnetic.Synthetic and the G0F's of G1F and G2F is synthetic similar.
Embodiment 2Fe
3O
4The preparation of the difunctional dendrimer microballoon of/CdTe fluorescence magnetic
Concrete steps are similar embodiment 1 roughly, and used quantum dot is the CdTe after TGA is modified.Concrete preparation method's step is as follows:
1, the preparation of Te precursor
Get 80mg Te powder, 50mg NaBH respectively
4Join in the bottle, seal a bottle, inject 1mL distilled water with syringe.Seal bottleneck with unsintered tape, insert the H that a syringe needle produces reaction at bottle stopper then
2Discharge.Bottle at 0 ℃ of reaction 8h, can be observed black Te powder and disappeared, and the upper strata is colourless NaHTe solution, and lower floor is Na
2B
4O
7White precipitate.
2, the preparation of Cd precursor
Get 0.2854g (1.25 * 10
-3Mo1) CdCl
22.5H
2O is dissolved in 100mL distilled water and adds in the there-necked flask, stirs fast to add 219 μ L TGAs (TGA) down.Mix the back and regulate the regulator solution pH value to 8-11 with 1mol/LNaOH.Use N
2With solution deoxidation 30min in enclosed system.
3, the preparation of CdTe quantum dot
Under suitable mixing speed, in solution, add freshly prepd anaerobic NaHTe solution, reactant liquor is heated to 96 ℃, condensing reflux.The mol ratio of each reactant is Cd
2+: NaHTe: TGA=1: 2.4: 0.5.Stop heating behind the reaction 120min.With the cooling of the product that obtains, add absolute ethyl alcohol then and make quantum dot flocculate out, filter, namely obtain pure CdTe QDs with solid is water-soluble.
Embodiment 3Fe
3O
4The preparation of the difunctional dendrimer microballoon of/ZnO fluorescence magnetic
Concrete other steps are similar embodiment 1 roughly, and different is that the used quantum dot of present embodiment is the ZnO quantum dot after TGA is modified.
The concrete preparation method's step of ZnO quantum dot is as follows:
(1) preparation of ZnO quantum dot
Get 22g (10mmo1) ZnAc
22H
2O places the 100mL absolute ethyl alcohol, and (condenser pipe top is connected to CaCl at 80 ℃ of backflow 3h
2Drying tube prevents that steam from entering in the reaction system).Solution after the backflow is colourless transparent liquid.Measure this solution 10mL with pipette and place the 100mL beaker, then add surfactant PVP (polyvinylpyrrolidone), make the mass concentration of system reach 4g/L, the ZnO precursor solution is made in dissolving; Take by weighing 0.118g LiOH simultaneously and join in the 10mL ethanolic solution, sonic oscillation 10min makes it accelerate dissolution.Above-mentioned LiOH solution dropwise is added in the precursor solution of vigorous stirring, makes ZnO quantum dot (reaction temperature is 50 ℃).
(2) purifying and drying
About 20mL n-hexane is added in the ZnO colloidal sol, leaves standstill 1h.Centrifugal 10min (5000r/min) pipettes supernatant liquor, adds 20mL anhydrous alcohol solution precipitation.2 times repeatedly.With sediment vacuum drying under room temperature, be kept in the drier under the lucifuge.
(3) TGA is to the finishing of ZnO quantum dot
Pipette a certain amount of ZnO quantum dot solution, under vigorous stirring, add the TGA of capacity, react 10min down at 20 ℃.
Embodiment 4 present embodiments adopt improved coprecipitation to prepare Fe
3O
4Magnetic nano-particle obtains the difunctional dendrimer microballoon of fluorescence magnetic.
Its preparation process is: ferrous sulfate amine, ammoniacal liquor and hydrazine hydrate are joined in the reactor according to a certain percentage, and after evenly disperseing, 80 ℃ were reacted 2 hours, and sediment gets Fe through deionized water and absolute ethyl alcohol cyclic washing after the vacuum drying
3O
4Nanoparticle.
Course of reaction is as follows:
In the course of reaction, hydrazine hydrate is energy and oxygen reaction on the one hand, and the oxygen in the consumption system plays the effect of protection ferrous ion; Another reverse side, hydrazine hydrate also can directly be settled out Fe
3O
4Nanoparticle.The Fe that this method prepares
3O
4Nanoparticle good dispersion, magnetic are strong.
Other steps are similar embodiment 1 roughly, and that different is the used Fe of present embodiment
3O
4Be prepared as and improve the coprecipitation preparation.
Embodiment 5 adopts the magnetic nanoparticle of distinct methods preparation to obtain the difunctional dendrimer microballoon of fluorescence magnetic
Concrete preparation method's step is as follows:
10mmol ferric acetyl acetonade Fe (acac) is equipped with in the 2-Pyrrolidone adding of drying
3Three-necked bottle in; remove air; stir at argon gas (Ar) protection lower magnetic force; 245 ℃ of control reaction temperatures; the boiling reflux certain hour. stop heating, continue logical argon gas and be cooled to room temperature. add a large amount of methyl alcohol, obtain pitch-black glossy magnetic fluid; with acetone washing 3 times, obtain product in 60 ℃ of vacuum drying.
Other steps are similar embodiment 1 roughly, and that different is the used Fe of present embodiment
3O
4Magnetic nano-particle for the oil phase preparation.
Embodiment 6Fe
3O
4The performance study of the difunctional dendrimer microballoon of/CdSe/CdS fluorescence magnetic
The Fe that present embodiment obtains with embodiment 1
3O
4The difunctional dendrimer microballoon of/CdSe/CdS fluorescence magnetic is some performances of the dendrimer microballoon of example research acquisition.
Through transmission electron microscope, spectrofluorimetry, fluorescence quantum yield calculate, magnetic property is measured the luminescent properties of having studied the difunctional microballoon of three generations's fluorescence magnetic and magnetic property etc.
Be illustrated in figure 4 as the transmission electron microscope photo of quantum dot and the difunctional dendrimer microballoon of three generations's fluorescence magnetic, wherein a is the CdSe/CdS QDs that TGA is modified; B is G0F (zero for the difunctional dendrimer microballoon of fluorescence magnetic); C is G1F (the difunctional dendrimer microballoon of generation fluorescence magnetic); D, e are G2F (the difunctional dendrimer microballoon of two generation fluorescence magnetics).Apparent pattern and the granular size of the difunctional dendrimer microballoon of fluorescence magnetic after compound with the CdSe/CdS QDs of TEM and three generations are analyzed.By Fig. 4 a as seen, CdSe/CdS QDs in water dispersed better, shape approximation is that sphere and average-size are about 3nm.Figure b, c and d, e are respectively the TEM image of the fluorescence magnetic difunctional dendrimer microballoon of three generations after compound, can observe the Fe after dendrimer is modified
3O
4The surface has connected one deck CdSe/CdS QDs uniformly, and its average grain diameter is followed successively by 15nm, 34nm and 49nm.
Fig. 5 is the fluorescence spectrum of CdSe/CdS QDs and the difunctional dendrimer microballoon of three generations's fluorescence magnetic.The fluorescence emission spectrum of quantum dot and the compound front and back of magnetic particle all be symmetrically distributed and half-peak breadth narrower, when excitation wavelength is 400nm, the emission peak of CdSe/Cd SQDs solution is at the 569nm place, and with after three generations's magnetic particle is connected, about 10nm red shift has all taken place the emission peak of its solution.
The fluorescence quantum yield of sample is measured and is adopted rhodamine B (QY=95% in the ethanol) as reference material, the fluorescence quantum productive rate that calculates CdSe/CdS QDs is 30.2%, and be respectively 10.1% (G0F) in conjunction with the fluorescence quantum yield of the three generations's dendrimer microballoon behind the magnetic nano-particle, 24.1% (G1F), 19.7% (G2F).This shows, be not that the more quantum yield is higher for the amount of the quantum dot that connects on the magnetic microsphere, after the amount of quantum dot reached certain value, the fluorescence quantum yield of the difunctional dendrimer microballoon of fluorescence magnetic reduced on the contrary, and this is main relevant with the concentration quenching effect of luminescent quantum dot.
Measured the magnetic property of three generation products with vibrating specimen magnetometer (VSM).Fe under the room temperature
3O
4The magnetization curve of the difunctional dendrimer microballoon of the fluorescence magnetic after compound with the three generations as shown in Figure 6.By curve as can be seen, sample does not have remanent magnetism and coercivity, has shown typical superparamagnetism.Fe
3O
4The saturation magnetization of nano particle is 56.54emu/g, and the saturation magnetization of the difunctional dendrimer microballoon of three generations's fluorescence magnetic is respectively 15.96emu/g, 8.72emu/g and 1.24emu/g.Its magnetic property weakens gradually, and this is because along with Fe
3O
4The growth of surface dendrimer and in conjunction with the increase of quantum dot relative populations, the magnetic screening action of its formation also will increase, and hinder the detection of magnetometer to sample.Simultaneously, these non-magnetic functional groups itself also have certain influence to the magnetic of sample.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All spirit essence is done according to the present invention equivalent transformation or modification all should be encompassed within protection scope of the present invention.
Claims (8)
1. difunctional dendrimer microballoon of fluorescence magnetic is characterized in that described microballoon has following composition:
Magnetic nano-particle, the modified formation of its spherical surface have as the dendrimer of the amino that connects fluorescence quantum for end;
Fluorescence quantum, its particle diameter is at 2～10nm, and finishing has carboxylic group; Described fluorescence quantum is selected from nano level CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot;
Described magnetic nano-particle is connected with the carboxyl of fluorescence quantum with the amino of fluorescence quantum by the dendrimer end;
Described microballoon is prepared according to following steps:
(1) preparation magnetic nano-particle;
(2) magnetic nano-particle is soaked in tetramethyl aqua ammonia (TMAOH) solution, makes upward hydroxyl of the abundant modification in its surface, and then reacts with 3-aminopropyl triethoxysilane (APTES), and obtaining amino is the zero for magnetic particle of end;
(3) zero formation after esters of acrylic acid, ethylene diamine-modified connection repeatedly successively for magnetic particle is with aminoterminal deriving for magnetic particle;
(4) preparation fluorescence quantum is controlled particle diameter in 2～10nm scope, and modifies with TGA, makes its surface have carboxylic group;
(5) make zero for magnetic particle and/or derive and connect the fluorescence quantum of going up the band carboxyl for magnetic particle, obtain the difunctional dendrimer microballoon of fluorescence magnetic.
2. the difunctional dendrimer microballoon of fluorescence magnetic according to claim 1 is characterized in that the particle diameter of the difunctional dendrimer microballoon of described fluorescence magnetic is in 20～100nm scope.
3. the difunctional dendrimer microballoon of fluorescence magnetic according to claim 1 and 2 is characterized in that described microballoon is regular or irregular sphere, square and oval-shaped particle.
4. the difunctional dendrimer microballoon of fluorescence magnetic according to claim 1 is characterized in that described magnetic nano-particle is super paramagnetic, paramagnetic or ferromagnetic metal, metal alloy or metal oxide nanoparticles.
5. the difunctional dendrimer microballoon of fluorescence magnetic according to claim 1 is characterized in that described magnetic nano-particle is selected from Fe
3O
4, γ-Fe
2O
3, MeFe
2O
3, NiCoFe, FeCo and NiFe magnetic nanoparticle, wherein Me is Co, Mn, Ni.
6. the preparation method of the difunctional dendrimer microballoon of the described fluorescence magnetic of claim 1 is characterized in that said method comprising the steps of:
(1) preparation magnetic nano-particle;
(2) magnetic nano-particle is soaked in tetramethyl aqua ammonia (TMAOH) solution, makes upward hydroxyl of the abundant modification in its surface, and then reacts with 3-aminopropyl triethoxysilane (APTES), and obtaining amino is the zero for magnetic particle of end;
(3) zero formation after esters of acrylic acid, ethylene diamine-modified connection repeatedly successively for magnetic particle is with aminoterminal deriving for magnetic particle;
(4) preparation fluorescence quantum is controlled particle diameter in 2～10nm scope, and modifies with TGA, makes its surface have carboxylic group;
(5) make zero for magnetic particle and/or derive and connect the fluorescence quantum of going up the band carboxyl for magnetic particle, obtain the difunctional dendrimer microballoon of fluorescence magnetic.
7. according to the method for claim 6, it is characterized in that esters of acrylic acid is selected from methyl acrylate, butyl acrylate described in the described method step (3).
8. according to the method for claim 6, the fluorescence quantum of its feature after being set forth in modification is water miscible, and being connected used system with magnetic nano-particle after the finishing is water.
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| CN106635024B (en) * | 2016-12-30 | 2018-11-13 | 淮安新能源材料技术研究院 | A kind of magnetic fluorescent dual-function nano material and preparation method thereof |
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