CN104844839A - Preparation method of magnetic fluorescent composite nanoparticle - Google Patents
Preparation method of magnetic fluorescent composite nanoparticle Download PDFInfo
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- CN104844839A CN104844839A CN201510124944.4A CN201510124944A CN104844839A CN 104844839 A CN104844839 A CN 104844839A CN 201510124944 A CN201510124944 A CN 201510124944A CN 104844839 A CN104844839 A CN 104844839A
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Abstract
The invention belongs to the preparation field of nano-materials, and in particular relates to a preparation method of a magnetic fluorescent composite nanoparticle. The preparation method comprises the following steps: firstly using a magnetic nanoparticle with negative charges and modified by carboxymethyl chitosan as a core; and then under the action of poly diallyldimethylammonium choloride (PDDA), an ion cross-linking agent and a polyanion type macromolecular organic compound, linking the core with a water-soluble quantum dot by an ion crosslinking method to obtain the magnetic fluorescent composite nanoparticle. The fluorescent quantum dots provided by the present invention are uniformly distributed on the surface of the magnetic nanometer particle, wherein the particle size of the magnetic nanometer particle is 10-200 nm, and the particle size of the quantum dots is 1.5-10 nm. The preparation method according to the present invention has the advantages that the reaction conditions are mild, the operating method is simple, the prepared composite nanoparticle has favorable luminous performance and favorable magnetic performance, and the prepared composite nanoparticle can be used in the aspects of target positioning and bioluminescence imaging in organisms.
Description
Technical field
The present invention relates to a kind of preparation method of multifunctional nano complex microsphere, be specifically related to a kind of preparation method of magnetic fluorescence composite nanometer particle, this composite particles has possessed the fluorescence property of quantum dot and the magnetic property of magnetic nanoparticle simultaneously, can be used as target location and bioluminescence imaging aspect in organism.
Background technology
Quantum dot and magnetics nanoparticle go out obvious advantage in a lot of field especially biomedical fields.But they often only have single function, as the fluorescent mark of quantum dot, the magnetic resolution etc. of magnetic particle, if two kinds of function-separation and mark function to be dissolved in one, novel magnetic fluorescence nano composite material is prepared by certain physical and chemical process, make it as while fluorescent probe, also there is good magnetic response characteristic.Therefore, magnetic fluorescence nano particle has Magneto separate and fluorescent tracing dual-use function, and its performance and application scope, all considerably beyond the nanoparticle of simple function, not only can be carried out detection on bio-molecular level and be separated; Also achieve various modes imaging, i.e. fluorescence imaging, nuclear magnetic resonance (MRI) and Laser scanning confocal microscopy.
Up to the present, the conventional preparation method of magnetic fluorescent composite material comprises LBL self-assembly method, entrapping method and covalent coupling method etc.Entrapping method (encapsulation) is current comparatively simple a kind of ripe method realizing magnetic nano-particle and quantum dot and assemble.Main process is, previously prepared magnetic nano-particle and quantum dot, then will tensio-active agent, polyelectrolyte molecules etc. be utilized they to be embedded in kernel together, thus forms the Nano/micron ball of magnetic fluorescence compound.Utilize polymkeric substance can also retain the characteristic of polymkeric substance while coated two kinds of nanoparticles.Its sheating material requires good biocompatibility and structural stability, also will be easy to further surface-functionalized modification simultaneously, to be connected with specific target molecule, finally realize targeting.
Using biodegradable macromolecular material as coating material, there is the features such as nontoxic, biodegradable, good histocompatibility, have a wide range of applications in medical science and biological field.Cm-chitosan is as a kind of derivative of chitosan, it is the electronegative water-soluble polysaccharide that chitosan obtains through carboxymethylation, it have nontoxic, non-stimulated, without sensitization, without mutagenesis, without haemolysis effect, good biocompatibility, biological degradability and adhesion, overcome the defect that chitosan can only be dissolved in acidic solution simultaneously, show the advantageous property that common chitosan does not have.
Ionic cross-linking refers under ion crosslinking agent effect, is tied between the macromolecular chain in raw material by chemical bond, forms method that is netted or body structure macromolecular material.Ionic cross-linking is also physical crosslinking method usually, its advantage be in preparation process not with an organic solvent, avoid most of chemical cross-linking agent if glutaraldehyde cross-linking agent is to the harm of human body, be in this way widely used.
Summary of the invention
A kind of ionic cross-linking is the object of the present invention is to provide to prepare the method for magnetic fluorescence composite nanometer particle; composite nano particle prepared by the method has that magnetic responsiveness is strong, light stability is high, preparation technology is simple, good dispersity and the advantages such as size uniform; simultaneously due to the coating function of macromolecule organic; the composite nanometer particle prepared also has the features such as high specific surface area, good biocompatibility, biological functionality and biodegradability, has apply widely in field of nano biotechnology.
The present invention is achieved by the following measures:
A preparation method for magnetic fluorescence composite nanometer particle, adopts following steps:
A () adopts blended entrapping method to prepare cm-chitosan magnetic nanocomposites (CMCH-MNPs):
1. take 50-500mg magnetic nanoparticle and be dissolved in 30 mL pH=7.4, concentration is in the PBS buffered soln of 0.01mol/L, and logical nitrogen deoxidation, utilizes Ultrasonic Cleaners to be uniformly dispersed by magnetic particle; 2. take 10-800 mg cm-chitosan to be dissolved in the PBS buffered soln of 20 mL pH=7.4, add the group that 0.1-0.5 g 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) activates cm-chitosan surface simultaneously; 3. incite somebody to action 1. and 2. two solution mixing, 25 DEG C of vibration 2-6 h in water bath with thermostatic control vibrator, then use distilled water and PBS (pH=7.4) buffered soln fully to wash successively, namely obtain cm-chitosan magnetic nanocomposites;
B () adopts ionic cross-linking to prepare magnetic fluorescence composite nanometer particle:
The concentrated aqueous phase quantum point getting preparation is dissolved in distilled water, and add polyanionic macromolecule organic and ion crosslinking agent, wherein the mass concentration of polyanionic macromolecule organic and ion crosslinking agent is respectively 0.33-6.67 mg/mL and 0.67-2.67 mg/mL, obtains reaction soln A; The magnetic nanocomposites getting the carboxymethyl chitosan of preparation in 0.005-0.05g step (a) sugar-modified is dissolved in distilled water, and ultrasonic 20-60 min, makes magnetic nanometer particles be uniformly dispersed, and adds diallyl dimethyl ammoniumchloride and obtain reaction soln B; Dropwise joined by reaction soln A in reaction soln B, oscillatory reaction 2-10 h under normal temperature, centrifugation, distilled water wash, namely obtains magnetic fluorescence composite nanometer particle; Wherein diallyl dimethyl ammoniumchloride: polyanionic macromolecule organic: the mass ratio of ion crosslinking agent is 1:0.1-2:0.01-0.5.
The preparation of magnetic fluorescence composite nanometer particle of the present invention, the particle diameter of magnetic fluorescence composite nanometer particle is 10-220 nm; Magnetic nanoparticle (MNPs) has superparamagnetic, paramagnetic or ferromagnetic metal and metal oxide, is selected from Fe
3o
4, Fe
2o
3, MeFe
2o
4(Me=Co, Mn, Ni), compound neodymium iron boron, SmCo etc., metal Fe, Co, Ni and alloy Fe
2co, Ni
2one in the nano particle of the metal oxide of Fe; The preparation method of magnetic nanoparticle comprises coprecipitation method, hydrothermal method; Magnetic nanoparticle surface is containing at least one in hydroxyl, amino, carboxyl.
Quantum dot of the present invention be surface with the water-soluble quantum dot of hydrophilic radical, quantum dot is II-VI group semiconductor material, or is the matrix material of II-VI group semiconductor material formation, and described quantum point grain diameter is 1.5-10 nm; Preferred quantum dot is ZnSe, CdSe, CdTe, CdS, ZnSe/ZnS, CdS/ZnS, CdSe/ZnS, CdTe/ZnS, Zn
xcd
1-Xse, CdSe
1-Xs
x, CdSe
1-Xte
x, CdSe/ZnSe, CdS/ZnSe, CdTe/ZnSe, CdSe/CdS, CdTe/CdS, CdS/Zn
xcd
1-Xs, ZnSe/Zn
xcd
1-Xs, CdSe/Zn
xcd
1-Xs or CdTe/Zn
xcd
1-Xone in S, wherein 0 < X < 1.
Ion crosslinking agent of the present invention comprises one or more in tri-polyphosphate, four poly-phosphate, hexametaphosphate, pyrophosphate salt, molybdate, hyaluronic acid or gamma-polyglutamic acid-; One or more in polyanionic macromolecule organic Xylo-Mucine, Ushercell, Mierocrystalline cellulose carboxylic acid sodium, Carboxylic Acid Fibre element, cm-chitosan, potassium carboxymethylcellulose or Xylo-Mucine potassium; Described cm-chitosan can select O-CMC or CMC; Molecular weight and the mass concentration of diallyl dimethyl ammoniumchloride are respectively 1 × 10
5~ 2 × 10
5with 0.51 ~ 5.1 mg/mL.
Magnetic fluorescence composite nanometer particle preparation of the present invention, in step (a), the thickness of cm-chitosan on magnetic nanoparticle surface is 3-10 nm; In step (b), the mol ratio of cm-chitosan magnetic nanocomposites and quantum dot is 1:1 ~ 1:20.
Quantum dot surface of the present invention contains at least one in sulfydryl, carboxyl, amino; The hydrophilic radical part used in semiconductor-quantum-point synthesis comprises one or more in 3-thiohydracrylic acid, Thiovanic acid, Cys, 2 mercaptopropionic acid, mercaptobutyric acid, mercaptopentanoic acid, mercaptohexanoic acid, dimercaptosuccinic acid, mercaptoethanol, gsh, mercaprol or mercaptoethylamine.
beneficial effect of the present invention:
(1) select water-soluble carboxymethyl chitosan and other polysaccharide derivates to replace common chitosan in the present invention, avoid the use of acidic medium, eliminate the detrimentally affect that acidic medium brings, expand the range of application at biomedical sector;
(2) the present invention utilizes the electrostatic interaction between opposite charges polyelectolyte material to be assembled into magnetic fluorescence composite nanometer particle by ionic cross-linking, and without the need to an organic solvent, reaction conditions is gentle, can protect the activity of biomolecules to greatest extent;
(3) the present invention selects diallyl dimethyl ammoniumchloride (PDDA) as cationic polyelectrolyte, it has safe, nontoxic, the soluble in water and characteristic such as stability to hydrolysis is good, cohesive force is strong, avoids the bio-toxicity using other organic polyelectrolyte to cause;
(4) in the present invention because cm-chitosan is to the modification of magnetic particle, effectively prevent the leakage of magneticsubstance and the fluorescent quenching effect to quantum dot; The size of final product, fluorescence property and magnetic property, can by regulation and control water-soluble quantum dot and the mol ratio of magnetic nanoparticle, the concentration, ionomer agent concentration etc. of polyanionic macromolecule organic, the magnetic fluorescence composite nanometer particle of obtained different performance, can be used for carrying out the transport of organism targeted drug and organism fluorescence imaging; Meanwhile, preparation technology of the present invention is simple, mild condition, plays maximum protection to actives mass-energy.
Accompanying drawing explanation
The XRD figure spectrum of Fig. 1 magnetic fluorescence composite nanometer particle
The fluorescence spectrum of Fig. 2 magnetic fluorescence composite nanometer particle and absorption spectrum
The TEM photo of Fig. 3 magnetic fluorescence composite nanometer particle
The magnetic hysteresis loop of Fig. 4 magnetic fluorescence composite nanometer particle.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described, but technical scheme of the present invention is not limited with specific embodiment.
Embodiment 1:
1.1 aqueous phases prepare CdTe quantum.Under nitrogen protection, by 0.0945g NaBH
4be dissolved in 5 mL distilled water with 0.0063g Te powder, be heated to 40 DEG C, after dissolving completely, obtain NaHTe solution; Get 0.293 g Cd (Ac)
2dissolve in 100 mL distilled water, after it dissolves completely, add 2.0 mmol Thiovanic acids, regulate pH=11 by the NaOH solution of 1mol/L, obtain the precursor solution of Cd; Proceed in there-necked flask by the presoma of Cd, inject NaHTe solution rapidly under nitrogen protection, oil bath 100 DEG C backflow, after magnetic agitation 3h, taking-up is put into refrigerator and is quickly cooled to room temperature, obtains red solution, is the CdTe QDs solution prepared.
1.2 adopt hydrothermal method to prepare Fe
3o
4nano particle.Take 3 g FeCl
3be dissolved in 80 mL ethylene glycol and stir ultrasonic dissolution, add polyoxyethylene glycol 2 g that molecular weight is 2000, sodium-acetate 7 g, stir ultrasonic making it to dissolve, precursor solution is proceeded in hydrothermal reaction kettle, at 200 DEG C of reaction 5 h, after having reacted, gained solution with water and dehydrated alcohol are alternately washed, through vacuum-drying, obtain dry Fe
3o
4magnetic nanoparticle.
1.3 adopt blended entrapping method to prepare cm-chitosan magnetic nanocomposites (Fe
3o
4-CMCH).Take 0.08 g Fe
3o
4magnetic nanoparticle is dissolved in 30 mL pH=7.4, and concentration is in the PBS buffered soln of 0.01mol/L, and logical nitrogen deoxidation, utilizes Ultrasonic Cleaners to be uniformly dispersed by magnetic particle, obtain finely dispersed Fe
3o
4nanoparticles solution; Take 0.2 g cm-chitosan to be dissolved in the PBS buffered soln of 20 mL pH=7.4, add the group that 0.1 g 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) activates cm-chitosan surface simultaneously; Afterwards carboxymethyl chitosan solution is added Fe
3o
4nanoparticles solution, 25 DEG C of vibration 2 h in water bath with thermostatic control vibrator, reaction terminates rear magnet and collects product, then uses distilled water and PBS (pH=7.4) buffered soln fully to wash successively, namely obtains cm-chitosan magnetic nanocomposites.
1.4 adopt ionic cross-linking to prepare magnetic fluorescence composite nanometer particle.Get the concentrated aqueous phase CdTe quantum of 1.1 preparations, be dissolved in 5mL distilled water after Virahol separating-purifying, and add sodium polyphosphate and cm-chitosan, wherein the concentration of sodium polyphosphate and cm-chitosan is respectively 1 mg/mL and 1.5 mg/mL, CdTe quantum concentration is 0.04mol/L, obtains reaction soln A; The magnetic nanocomposites getting in 0.01g step 1.3 carboxymethyl chitosan of preparation sugar-modified is dissolved in 10 mL distilled water, ultrasonic 30 min, magnetic nanometer particles is uniformly dispersed, and to add mass concentration be 1 mg/mL diallyl dimethyl ammoniumchloride, obtain reaction soln B; Solution A dropwise added in B solution, vibrate 4h in the water bath with thermostatic control vibrator of 25 DEG C, and magnet collecting reaction product, with distilled water cleaning reaction product, obtains magnetic fluorescent dual-function nano material.The XRD figure spectrum of Fig. 1 magnetic fluorescence composite nanometer particle.
Embodiment 2:
2.1 adopt Aqueous phase to prepare CdTe/ZnS quantum dot. and first adopt chemical coprecipitation to prepare CdTe quantum, preparation method is as described in above-described embodiment 1, and difference is the reaction times is 4h.Getting the CdTe quantum prepared is dissolved in 30 mL distilled water, and wherein the concentration of CdTe quantum is 1.67 × 10
-3mol/L, adds 0.0329 g Zn (Ac)
2, 0.0921 g reductive glutathione, be 1 mol/L NaOH solution adjust ph by the concentration configured be 8, under magnetic stirring, oil bath 100 DEG C backflow, magnetic agitation is put into refrigerator after reacting 2 h and is quickly cooled to room temperature, obtains the CdTe/ZnS quantum dot of water-soluble high-luminous-efficiency.
2.2 adopt hydrothermal method to prepare Fe
3o
4magnetic nanoparticle.Get 2.78 g FeSO
47H
2o, 4.32 g FeCl
36H
2o is dissolved in 30 mL distilled water; after magnetic agitation is dissolved; add 30 mL ethylene glycol again; after stirring under nitrogen protection; add in there-necked flask, regulate pH to 9-11 by the NaOH solution that the concentration configured is 2 mol/L, add tensio-active agent polyvinylpyrrolidone 0.15 g; 30min is reacted, obtained Fe after abundant stirring
3o
4the presoma of magnetic nanoparticle.By Fe
3o
4the presoma of magnetic nanoparticle proceeds in hydrothermal reaction kettle, at 160 DEG C, react 6h.After having reacted, gained solution with water and dehydrated alcohol are alternately washed, through vacuum-drying, obtain dry Fe
3o
4magnetic nanoparticle.
2.3 adopt blended entrapping method to prepare cm-chitosan magnetic nanocomposites (Fe
3o
4-CMCH).Take 0.2 g Fe
3o
4magnetic nanoparticle is dissolved in 30 mL pH=7.4, and concentration is in the PBS buffered soln of 0.01mol/L, and logical nitrogen deoxidation, utilizes Ultrasonic Cleaners to be uniformly dispersed by magnetic particle, obtain finely dispersed Fe
3o
4nanoparticles solution; Take 0.5 g cm-chitosan to be dissolved in the PBS buffered soln of 20 mL pH=7.4, add the group that 0.3 g 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) activates cm-chitosan surface simultaneously; Afterwards carboxymethyl chitosan solution is added Fe
3o
4nanoparticles solution, 25 DEG C of vibration 4 h in water bath with thermostatic control vibrator, reaction terminates rear magnet and collects product, then uses distilled water and PBS (pH=7.4) buffered soln fully to wash successively, namely obtains cm-chitosan magnetic nanocomposites.
2.4 adopt ionic cross-linking to prepare magnetic fluorescence composite nanometer particle.Get the concentrated aqueous phase CdTe/ZnS quantum dot of 2.1 preparations, be dissolved in 5mL distilled water after Virahol separating-purifying, and add sodium tetrapolyphosphate and Xylo-Mucine, wherein the concentration of sodium tetrapolyphosphate and Xylo-Mucine is respectively 1.5 mg/mL and 3 mg/mL, CdTe/ZnS quantum dot concentration is 0.05mol/L, obtains reaction soln A; The magnetic nanocomposites getting in 0.02 g step 2.3 carboxymethyl chitosan of preparation sugar-modified is dissolved in 10 mL distilled water, ultrasonic 30 min, magnetic nanoparticle is uniformly dispersed, and to add mass concentration be 2 mg/mL diallyl dimethyl ammoniumchloride, obtain reaction soln B; Solution A dropwise added in B solution, vibrate 6h in the water bath with thermostatic control vibrator of 25 DEG C, and magnet collecting reaction product, with distilled water cleaning reaction product, obtains magnetic fluorescent dual-function nano material.Fig. 2 is fluorescence spectrum and the absorption spectrum of the magnetic fluorescence composite nanometer particle of preparation.
Embodiment 3:
The preparation of 3.1 ZnSe/ZnS quantum dot solutions.First chemical coprecipitation is adopted to prepare ZnSe quantum dot, under nitrogen protection, by 0.01g NaBH
4be dissolved in 2 mL distilled water with 0.0061g Se powder, be heated to 40 DEG C, after dissolving completely, obtain NaHSe solution; Get 0.0439 g Zn (Ac)
2dissolve in 20 mL distilled water, after it dissolves completely, add reduced glutathion 0.0737g, regulate pH=11.5 by the NaOH solution of 1mol/L, obtain the precursor solution of Zn; Proceed in there-necked flask by the presoma of Zn, inject NaHSe solution rapidly under nitrogen protection, oil bath 100 DEG C backflow, after magnetic agitation 1h, taking-up is put into refrigerator and is quickly cooled to room temperature, obtains colourless transparent solution, is the ZnSe QDs solution prepared.Get ZnSe quantum dot 15 mL prepared, wherein the concentration of ZnSe quantum dot is 2.7 × 10
-3mol/L, adds 0.0138 g Zn (Ac)
2, 0.0277 g reductive glutathione and 0.01 g thiocarbamide, be 1 mol/L NaOH solution adjust ph by the concentration configured be 10.5, under magnetic stirring, oil bath 100 DEG C backflow, magnetic agitation is put into refrigerator after reacting 2 h and is quickly cooled to room temperature, obtains the ZnSe/ZnS quantum dot of faint yellow water-soluble high-luminous-efficiency.
The preparation of 3.2 magnetic nanoparticles.Employing patent publication No. is that the method for CN101597495A prepares Fe
3o
4/ CoO core-shell structure magnetic nano particle.
3.3 adopt blended entrapping method to prepare cm-chitosan magnetic nanocomposites.Take 0.35 g Fe
3o
4/ CoO magnetic nanoparticle is dissolved in 30 mL pH=7.4, and concentration is in the PBS buffered soln of 0.01mol/L, and logical nitrogen deoxidation, utilizes Ultrasonic Cleaners to be uniformly dispersed by magnetic particle, obtain finely dispersed Fe
3o
4/ CoO nanoparticles solution; Take 0.65 g cm-chitosan to be dissolved in the PBS buffered soln of 20 mL pH=7.4, add the group that 0.3 g 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) activates cm-chitosan surface simultaneously; Afterwards carboxymethyl chitosan solution is added Fe
3o
4/ CoO nanoparticles solution, 25 DEG C of vibration 5 h in water bath with thermostatic control vibrator, reaction terminates rear magnet and collects product, then uses distilled water and PBS (pH=7.4) buffered soln fully to wash successively, namely obtains cm-chitosan magnetic nanocomposites.
3.4 adopt ionic cross-linking to prepare magnetic fluorescence composite nanometer particle.Get the concentrated aqueous phase ZnSe/ZnS quantum dot of 3.1 preparations, be dissolved in 5mL distilled water after Virahol separating-purifying, and add trisodium phosphate and Ushercell, wherein the concentration of trisodium phosphate and Ushercell is respectively 2 mg/mL and 4 mg/mL, ZnSe/ZnS quantum dot concentration is 0.1 mol/L, obtains reaction soln A; The magnetic nanocomposites getting in 0.035 g step 3.3 carboxymethyl chitosan of preparation sugar-modified is dissolved in 10 mL distilled water, ultrasonic 30 min, magnetic nanometer particles is uniformly dispersed, and to add mass concentration be 2 mg/mL diallyl dimethyl ammoniumchloride, obtain reaction soln B; Solution A dropwise added in B solution, vibrate 6h in the water bath with thermostatic control vibrator of 25 DEG C, and magnet collecting reaction product, with distilled water cleaning reaction product, obtains magnetic fluorescent dual-function nano material.Fig. 3 is the TEM photo of the magnetic fluorescence composite nanometer particle of preparation.
Embodiment 4:
4.1 adopt Aqueous phase to prepare CdSe quantum dot. under nitrogen protection, by 0.0106 g NaBH
4be dissolved in 2 mL distilled water with 0.0063 g Se powder, be heated to 40 DEG C, after dissolving completely, obtain NaHSe solution; Get 0.0533 g Cd (Ac)
2dissolve in 20 mL distilled water, after it dissolves completely, add 1.0 mmol thiohydracrylic acids, regulate pH=11.5 by the NaOH solution of 1mol/L, obtain the precursor solution of Cd; Proceed in there-necked flask by the presoma of Cd, inject NaHSe solution rapidly under nitrogen protection, oil bath 100 DEG C backflow, after magnetic agitation 1h, taking-up is put into refrigerator and is quickly cooled to room temperature, obtains colourless transparent solution, is the CdSe QDs solution prepared.
The preparation of 4.2 magnetic nanoparticles.Employing patent publication No. is that the method for CN 101928043 A prepares α-Fe
2o
3magnetic nanoparticle.
4.3 adopt blended entrapping method to prepare cm-chitosan magnetic nanocomposites (CMCH-MNPs).Take 0.5 g α-Fe
2o
3magnetic nanoparticle is dissolved in 30 mL pH=7.4, and concentration is in the PBS buffered soln of 0.01mol/L, and logical nitrogen deoxidation, utilizes Ultrasonic Cleaners to be uniformly dispersed by magnetic particle, obtain finely dispersed α-Fe
2o
3nanoparticles solution; Take 0.8 g cm-chitosan to be dissolved in the PBS buffered soln of 20 mL pH=7.4, add the group that 0.5 g 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) activates cm-chitosan surface simultaneously; Afterwards carboxymethyl chitosan solution is added α-Fe
2o
3nanoparticles solution, 25 DEG C of vibration 6 h in water bath with thermostatic control vibrator, reaction terminates rear magnet and collects product, then uses distilled water and PBS (pH=7.4) buffered soln fully to wash successively, namely obtains cm-chitosan magnetic nanocomposites.
4.4 adopt ionic cross-linking to prepare magnetic fluorescence composite nanometer particle.Get the concentrated aqueous phase CdSe quantum dot of 4.1 preparations, be dissolved in 5 mL distilled water after Virahol separating-purifying, and add Sodium orthomolybdate and Carboxylic Acid Fibre element, wherein the concentration of Sodium orthomolybdate and Carboxylic Acid Fibre element is respectively 2.5 mg/mL and 6 mg/mL, CdSe quantum dot concentration is 0.25 mol/L, obtains reaction soln A; The magnetic nanocomposites getting in 0.05 g step 4.3 carboxymethyl chitosan of preparation sugar-modified is dissolved in 10 mL distilled water, ultrasonic 30 min, magnetic nanometer particles is uniformly dispersed, and to add mass concentration be 5 mg/mL diallyl dimethyl ammoniumchloride, obtain reaction soln B; Solution A dropwise added in B solution, vibrate 10 h in the water bath with thermostatic control vibrator of 25 DEG C, and magnet collecting reaction product, with distilled water cleaning reaction product, obtains magnetic fluorescent dual-function nano material.Fig. 4 is the magnetic hysteresis loop of the magnetic fluorescence composite nanometer particle of preparation.
Claims (7)
1. the preparation of a magnetic fluorescence composite nanometer particle, it is characterized in that: be connected water-soluble quantum dot with polyanionic macromolecule organic by ionic cross-linking obtain with the sugar-modified magnetic nano-particle of electronegative carboxymethyl chitosan, diallyl dimethyl ammoniumchloride (PDDA), ion crosslinking agent, described fluorescence quantum is evenly distributed on the surface of magnetic nanoparticle with single dispersing form, wherein the size of magnetic nanoparticle is at 10-200 nm, and the particle diameter of quantum dot is at 1.5-10 nm.
2. the preparation of a kind of magnetic fluorescence composite nanometer particle according to claim 1, it is characterized in that, described preparation method comprises the following steps:
A () adopts blended entrapping method to prepare cm-chitosan magnetic nanocomposites (Fe
3o
4-CMCH): 1. take 50-500mg magnetic nanoparticle and be dissolved in 30 mL pH=7.4, concentration is in the PBS buffered soln of 0.01mol/L, and logical nitrogen deoxidation, utilizes Ultrasonic Cleaners to be uniformly dispersed by magnetic particle; 2. take 10-800 mg cm-chitosan to be dissolved in the PBS buffered soln of 20 mL pH=7.4, add the group that 0.1-0.5 g 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) activates cm-chitosan surface simultaneously; 3. incite somebody to action 1. and 2. two solution mixing, 25 DEG C of vibration 2-6 h in water bath with thermostatic control vibrator, then use distilled water and PBS (pH=7.4) buffered soln fully to wash successively, namely obtain cm-chitosan magnetic nanocomposites;
B () adopts ionic cross-linking to prepare magnetic fluorescence composite nanometer particle:
The concentrated aqueous phase quantum point getting preparation is dissolved in distilled water, add polyanionic macromolecule organic and ion crosslinking agent, wherein the mass concentration of polyanionic macromolecule organic and ion crosslinking agent is respectively 0.33-6.67 mg/mL and 0.67-2.67 mg/mL, obtains reaction soln A; The magnetic nanocomposites getting the carboxymethyl chitosan of preparation in 0.005-0.05g step (a) sugar-modified is dissolved in distilled water, and ultrasonic 20-60 min, makes magnetic nanometer particles be uniformly dispersed, and adds diallyl dimethyl ammoniumchloride and obtain reaction soln B; Dropwise joined by reaction soln A in reaction soln B, oscillatory reaction 2-10 h under normal temperature, centrifugation, distilled water wash, namely obtains magnetic fluorescence composite nanometer particle; Wherein diallyl dimethyl ammoniumchloride: polyanionic macromolecule organic: the mass ratio of ion crosslinking agent is 1:0.1-2:0.01-0.5.
3. the preparation of a kind of magnetic fluorescence composite nanometer particle according to claim 1 and 2, is characterized in that, the particle diameter of described magnetic fluorescence composite nanometer particle is 10-220 nm; Described magnetic nanoparticle (MNPs) is superparamagnetic, paramagnetic or ferromagnetic metal and metal oxide, is selected from Fe
3o
4, Fe
2o
3, MeFe
2o
4(Me=Co, Mn, Ni), compound neodymium iron boron, SmCo etc., metal Fe, Co, Ni and alloy Fe
2co, Ni
2one in the nano particle of the metal oxide of Fe; The preparation method of magnetic nanoparticle comprises coprecipitation method, hydrothermal method; Magnetic nanoparticle surface is containing at least one in hydroxyl, amino, carboxyl.
4. a kind of magnetic fluorescence composite nanometer particle according to claim 1 and 2, it is characterized in that, described quantum dot is the water-soluble quantum dot of surface with hydrophilic radical, quantum dot is II-VI group semiconductor material, or be the matrix material that II-VI group semiconductor material is formed, described quantum point grain diameter is 1.5-10 nm; Preferred quantum dot is ZnSe, CdSe, CdTe, CdS, ZnSe/ZnS, CdS/ZnS, CdSe/ZnS, CdTe/ZnS, Zn
xcd
1-Xse, CdSe
1-Xs
x, CdSe
1-Xte
x, CdSe/ZnSe, CdS/ZnSe, CdTe/ZnSe, CdSe/CdS, CdTe/CdS, CdS/Zn
xcd
1-Xs, ZnSe/Zn
xcd
1-Xs, CdSe/Zn
xcd
1-Xs or CdTe/Zn
xcd
1-Xone in S, wherein 0 < X < 1.
5. a kind of magnetic fluorescence composite nanometer particle according to claim 1 and 2, it is characterized in that, described ion crosslinking agent comprises one or more in tri-polyphosphate, four poly-phosphate, hexametaphosphate, pyrophosphate salt, molybdate, hyaluronic acid or gamma-polyglutamic acid-; One or more in polyanionic macromolecule organic Xylo-Mucine, Ushercell, Mierocrystalline cellulose carboxylic acid sodium, Carboxylic Acid Fibre element, cm-chitosan, potassium carboxymethylcellulose or Xylo-Mucine potassium; Described cm-chitosan can select O-CMC or CMC; Molecular weight and the mass concentration of diallyl dimethyl ammoniumchloride are respectively 1 × 10
5-2 × 10
5with 0.51-5.1 mg/mL.
6. a kind of magnetic fluorescence composite nanometer particle according to claim 2, is characterized in that, in step (a), the thickness of cm-chitosan on magnetic nanoparticle surface is 3-10 nm; In step (b), the mol ratio of cm-chitosan magnetic nanocomposites and quantum dot is 1:1-1:20.
7. the preparation of water-soluble quantum dot according to claim 4, is characterized in that: described quantum dot surface contains at least one in sulfydryl, carboxyl, amino; The hydrophilic radical part used in semiconductor-quantum-point synthesis comprises one or more in 3-thiohydracrylic acid, Thiovanic acid, Cys, 2 mercaptopropionic acid, mercaptobutyric acid, mercaptopentanoic acid, mercaptohexanoic acid, dimercaptosuccinic acid, mercaptoethanol, gsh, mercaprol or mercaptoethylamine.
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| CN105400517A (en) * | 2015-10-30 | 2016-03-16 | 玉林师范学院 | Method for preparing dual-functional magnetic fluorescent probe for detecting cadmium ions and application thereof |
| CN106467294A (en) * | 2016-10-17 | 2017-03-01 | 浙江和谱生物科技有限公司 | The aqueous phase preparation method of suppression tumor cell nanometer cadmium telluride |
| CN107858144A (en) * | 2017-11-10 | 2018-03-30 | 四川大学 | A kind of magnetic material for efficient detection circulating tumor cell and preparation method thereof |
| CN111423878A (en) * | 2020-04-30 | 2020-07-17 | 山东交通学院 | Fluorescent magnetic composite nano-particles, preparation method thereof and biological probe prepared from fluorescent magnetic composite nano-particles |
| CN114507299A (en) * | 2022-03-21 | 2022-05-17 | 昆明理工大学 | Method for extracting hemicellulose by adopting ammonium group modified neodymium iron boron magnetic particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105400517A (en) * | 2015-10-30 | 2016-03-16 | 玉林师范学院 | Method for preparing dual-functional magnetic fluorescent probe for detecting cadmium ions and application thereof |
| CN105400517B (en) * | 2015-10-30 | 2018-03-13 | 玉林师范学院 | Detect difunctional magnetic fluorescence probe preparation method and its application of cadmium ion |
| CN106467294A (en) * | 2016-10-17 | 2017-03-01 | 浙江和谱生物科技有限公司 | The aqueous phase preparation method of suppression tumor cell nanometer cadmium telluride |
| CN106467294B (en) * | 2016-10-17 | 2018-08-24 | 浙江和谱生物科技有限公司 | Inhibit the aqueous phase preparation method of tumour cell nanometer cadmium telluride |
| CN107858144A (en) * | 2017-11-10 | 2018-03-30 | 四川大学 | A kind of magnetic material for efficient detection circulating tumor cell and preparation method thereof |
| CN107858144B (en) * | 2017-11-10 | 2019-10-11 | 四川大学 | A kind of magnetic material and preparation method thereof for efficient detection circulating tumor cell |
| CN111423878A (en) * | 2020-04-30 | 2020-07-17 | 山东交通学院 | Fluorescent magnetic composite nano-particles, preparation method thereof and biological probe prepared from fluorescent magnetic composite nano-particles |
| CN111423878B (en) * | 2020-04-30 | 2022-11-08 | 山东交通学院 | Fluorescent magnetic composite nano-particles, preparation method thereof and biological probe prepared from fluorescent magnetic composite nano-particles |
| CN114507299A (en) * | 2022-03-21 | 2022-05-17 | 昆明理工大学 | Method for extracting hemicellulose by adopting ammonium group modified neodymium iron boron magnetic particles |
| CN114507299B (en) * | 2022-03-21 | 2023-02-03 | 昆明理工大学 | Method for extracting hemicellulose by adopting ammonium group modified neodymium iron boron magnetic particles |
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