CN106833650A - A kind of magnetic fluorescent dual-function nano material - Google Patents

A kind of magnetic fluorescent dual-function nano material Download PDF

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CN106833650A
CN106833650A CN201710083648.3A CN201710083648A CN106833650A CN 106833650 A CN106833650 A CN 106833650A CN 201710083648 A CN201710083648 A CN 201710083648A CN 106833650 A CN106833650 A CN 106833650A
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刘福田
丁永玲
孙康宁
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University of Jinan
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Abstract

The invention belongs to field of nano material preparation, specifically related to a kind of magnetic fluorescent dual-function nanoparticle probe and preparation method thereof, the composite particles have been provided simultaneously with the fluorescence property of quantum dot and the magnetic property of magnetic nanoparticle, can be used as targeting positioning and bioluminescence imaging aspect in organism.The invention provides a kind of preparation method of magnetic fluorescent dual-function nano material, with chitosan-modified magnetic nano-particle as core, water-soluble quantum dot is connected by ionic cross-linking to obtain, the fluorescence quantum is distributed in the surface of magnetic nanoparticle, wherein, in 10 200 nm, the particle diameter of quantum dot is in 1.5 10 nm for the particle size of magnetic nanoparticle.Reaction condition of the present invention is gentle, operating method is simple, the composite nanometer particle of preparation has good luminescent properties and magnetic property, biomarker, fluoroimmunoassay, bio-separation, protein D NA enrichments and separate, the field such as the preparation of medicine-carried system and target imaging is widely applied prospect.

Description

A kind of magnetic fluorescent dual-function nano material
This case is divisional application, and original application is entitled：A kind of magnetic fluorescent dual-function nanoparticle probe and preparation method thereof, it is former Number of patent application is：2015100487318, the applying date is：On January 30th, 2015, it is desirable to the Application No. of priority document： 201410311445, priority date is：On 07 02nd, 2014
Technical field
The invention belongs to field of nano material preparation, and in particular to a kind of magnetic fluorescent dual-function nanoparticle probe and its Preparation method, the composite particles have been provided simultaneously with the fluorescence property of quantum dot and the magnetic property of magnetic nanoparticle, can be used as life Targeting positioning and bioluminescence imaging aspect in object.
Background technology
With further going deep into for nanotechnology research, requirement of the people to nano material is from monodispersity, pattern Control be changed into the multi-component composite nanometer particle of structure.Various different materials are combined by methods such as surface epitaxial growths Together, the new focus of nanoscale science and technology research is become.Compared to the nano particle of one-component, multi-functional nanometer material Various excellent performances are provided simultaneously with, preferably solving the unitary function of physical presence is limited the use of some nano materials The problem of system, multi-functional nanometer material is fast-developing with its excellent performance, is increasingly widely applied to different fields.Its In, fluorescent material and magnetic material are received significant attention because it is in biochemical and medical domain extensive use.
Quantum dot is crystallite of the size in 1-100nm, is generally made up of II-VI in the periodic table of elements or iii-v atom, By adjusting particle size, the quantum dot of different fluorescence emission wavelengths can be obtained.Compared with traditional organic fluorescent dye, amount Son is put has adjustable fluorescence emission wavelengths, narrow and symmetrical fluorescence emission spectrum, wide and continuous ultra-violet absorption spectrum, and Preferable photochemical stability.At present, fluorescence quantum has been widely used in biological fluorescent labeling, biomedical imaging and is immunized The fields such as detection and analysis.Preferable magnetic fluorescent microspheres requirement with specific saturation magnetization higher, can produce it is stronger glimmering Light and fluorescent stability is good, Microsphere Size is controllable, particle diameter distribution is narrow, chemical stability is good, abundant function base is contained on surface Group, and preparation process is simple, repeatability it is good, cheap the features such as, it acts not only as mri contrast agent is used for Medical diagnosis on disease, is also used as pharmaceutical carrier for the separation of disease treatment and various albumen, cell etc..If by magnetic and Fluorescent characteristic is dissolved in the composite nanoparticle for integrally preparing magnetic and fluorescent dual function, will be in biomarker, fluorescence immunoassay Analysis, bio-separation, protein D NA enrichments and separate, the field such as the preparation of medicine-carried system and target imaging is with very big application Potentiality.
The preparation method of magnetic fluorescent nanometer particle mainly include coated with silica, polymer overmold, plant crystals growth with And coupling method.However, in its preparation process generally existing quantum dot fluorescent quenching phenomenon.According to the literature, quantum is caused , mainly there are two aspects the reason for point fluorescent quenching, is on the one hand quantum dot photochemical stability in itself, due to applied environment Complexity, quantum dot stability easily receive surrounding environment influence；On the other hand it is the influence of magnetic nano-particle, including magnetic is strong Absorption and between magnetic-particle and quantum dot FRET effect.
Found through being retrieved to existing technology, Wang Feijun etc.（Publication number：CN103525405A, title：Based on natural polymer Magnetic fluorescent dual-function nano material of son and preparation method thereof）With magnetic particle Fe3O4It is core, shitosan and polyanionic Cellulose is Shell Materials, and the fluorescein isothiocynate with Chitosan-coated is obtained as fluorescent material by LBL self-assembly method Arrive.The fluorescent material that the method is selected is organic fluorescence molecule, and this kind of fluorescent material is measured as most of organic fluorescent dyes Sub- yield is relatively low, strict to detecting system requirement；Narrower excitation wavelength range is harsh to selective exitation light source requirements；Transmitted wave Wider range long and in long wavelength region hangover, and brings the problems such as interfering of spectrum between different sense channels, Carry out very big difficulty to detection band.Chen Kezheng（Publication number：CN102020258A, title：A kind of magnetic fluorescence hydroxyapatite nano The preparation method of composite construction）By controlling the mol ratio of calcium/europium, by the mixed solution of calcium nitrate and europium nitrate, phosphoric acid hydrogen two Ammonium salt solution instills magnetic nano-particle solution simultaneously, is stirred vigorously down and obtains brown color precipitation, and magnetic fluorescence hydroxy-apatite is obtained Stone nano composite structure.The method needs to add expensive rare earth element, simultaneously because the limitation of doping, what is obtained is glimmering Light launch wavelength is limited in scope.
It is of the invention with chitosan-modified magnetic nano-particle as core in order to overcome the deficiencies in the prior art, by ion Cross-linking method connection is dissolved in the water-soluble quantum dot in polyanionic macromolecule organic, finally gives biocompatibility good Magnetic fluorescence composite nano particle.Modification due to shitosan to magnetic particle, effectively prevent letting out for magnetic material Leakage and the fluorescent quenching effect to quantum dot；Simultaneously can be by controlling water-soluble quantum in polyanionic macromolecule organic Concentration, crosslinking number of times of point etc., are obtained the magnetic fluorescence composite nanometer particle of different luminescent properties.
The content of the invention
It is an object of the invention to provide a kind of magnetic fluorescent dual-function nano material and the preparation method of ion probe, the party Composite nano particle prepared by method has that magnetic responsiveness is strong, photostability is high, it is simple to prepare, good dispersion and size uniform etc. are excellent Point, compared with the fluorescent material and magnetic material of simple function, while having the multifunctional nanocomposites of fluorescence and magnetic There are wider biomedical applications in nanometer biotechnology, such as cell separation and identification, the analysis of cell multi-modal imaging, Living imaging, biochemical marker and sensing etc..
The present invention is achieved by the following measures：
A kind of preparation method of magnetic fluorescent dual-function nano material, using following steps：
（a）Chitosan-modified magnetic nanocomposites are prepared using chemical covalent cross-linking method（CMCH-MNPs）：1. to magnetic Nano grain surface carries out amination modification by amination silane coupler, obtains amination magnetic nanoparticle；2. by shell Glycan is dissolved in the weak acid solution that volume fraction is 2%-6%, is made into the chitosan gel rubber solution of 0.001-0.01 g/mL；③ And 2. 1. two solution will mix, add aldehyde crosslinking agent, 10-16 h, magnet will be vibrated in 24-26 DEG C of thermostatic control oscillator vibration Collecting reaction product, product is cleaned with distilled water, obtains chitosan-modified magnetic nanocomposites；
（b）Magnetic fluorescent dual-function nano material is prepared using ionic cross-linking：
The aqueous phase quantum point for taking the concentration of preparation is dissolved in distilled water, and adds polyanionic macromolecule organic, wherein poly- The concentration of anionic macromolecule organic is 0.0006-0.02 g/mL, obtains reaction solution A；Take 0.005-0.05g steps （a）The chitosan-modified magnetic nanocomposites of middle preparation are dissolved in distilled water, ultrasonic 20-60 min, make magnetic Nano micro- Grain is uniformly dispersed and obtains reaction solution B；Solution A is added dropwise in B solution, is shaken in 24-26 DEG C of thermostatic control oscillator vibration 8-16 h are swung, magnet collecting reaction product cleans product, obtains final product magnetic fluorescent dual-function nano material with distilled water.
A kind of efficient ion probe preparation process of the present invention is as follows：Take the 100 above-mentioned magnetic fluorescent dual-functions of μ L The concentration of nano material, wherein composite nanocrystalline is 2 × 10-4~2×10-3Mol/L, adds 1.8 mL pH=7.4, and concentration is In the cushioning liquid of 0.01 mol/L, while it is 2 × 10 to add maximum concentration-5~2×10-4The copper of mol/L, mercury, silver or lead Metal ion, is obtained the fluorescence probe for detecting trace metal ion.
The preparation of magnetic fluorescent dual-function nano material of the present invention, magnetic nanoparticle（MNPs）It is with super suitable Magnetic, paramagnetic or ferromagnetic metal and metal oxide, selected from Fe3O4、Fe2O3、Fe3O4、MeFe2O4(Me=Co, Mn, Ni), change Compound neodymium iron boron, SmCo etc., metal Fe, Co, Ni and alloy Fe2Co、Ni2The nano particle of the metal oxide of Fe.
Magnetic fluorescent dual-function nano material of the present invention, its particle size is 10-220 nm.
The preparation method of magnetic nanoparticle of the present invention includes coprecipitation, hydro-thermal method.
Quantum dot of the present invention is water-soluble quantum dot of the surface with hydrophilic radical, and quantum dot is II-VI, III- V races semi-conducting material, or be II-VI and the composite of III-V group semi-conductor material formation, the 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、ZnXCd1-XSe、CdSe1-XSX、CdSe1-XTeX、CdSe/ZnSe、CdS/ZnSe、CdTe/ZnSe、CdSe/CdS、CdTe/ CdS、CdS/ZnXCd1-XS、ZnSe/ZnXCd1-XS、CdSe/ZnXCd1-XS、CdTe/ZnXCd1-XS, wherein 0 ＜ X ＜ 1.
The preparation of magnetic fluorescent dual-function nano material of the present invention, step（a）Middle amination silane coupler bag Include trimethoxy amine propyl silane（APS）, 3- aminopropyl triethoxysilanes（APTES）, triethoxy amine propyl silane, ammonia third Base trimethoxy silane, 2- aminoethyls-aminopropyl trimethoxysilane, divinyl triammonium base propyl trimethoxy silicane, ammonia second Base aminopropyltriethoxy dimethoxysilane.
The preparation of magnetic fluorescent dual-function nano material of the present invention, step（a）Middle amination modified magnetic nanometer Particle process is：Magnetic nanoparticle is dissolved in absolute ethyl alcohol, amination silane coupler is added, shaken in thermostatic control oscillator vibration 5-12 h are swung, magnet collecting reaction product replaces washing reaction product with distilled water and absolute ethyl alcohol, obtains final product amination modification magnetic Property nano particle, the wherein volume ratio of absolute ethyl alcohol and amination silane coupler is 200:1-50:1.
The preparation of magnetic fluorescent dual-function nano material of the present invention, step（a）Described weak acid solution includes ant Acid, glacial acetic acid, tartaric acid, citric acid.
The preparation of magnetic fluorescent dual-function nano material of the present invention, step（a）The aldehyde crosslinking agent includes first Aldehyde, glyoxal, glutaraldehyde, concentration are 4%-15%.
The preparation of magnetic fluorescent dual-function nano material of the present invention, step（b）Middle polyanionic macromolecule has Machine thing includes sodium polyphosphate, sodium carboxymethylcellulose, cellulose sodium sulfate, cellulose carboxylic acid sodium, Carboxylic Acid Fibre element, carboxymethyl One kind in cellulose potassium, sodium carboxymethylcellulose potassium, nano-cellulose.
Magnetic fluorescence composite nano-microsphere of the present invention, step（b）In chitosan-modified magnetic nanocomposites It is 1 with the mol ratio of quantum dot:1-1:30.
Fluorescence probe buffer solution system of the present invention includes potassium dihydrogen phosphate-disodium hydrogen phosphate（PBS）, boric acid- Borax, Glycine-NaOH, Tri(Hydroxymethyl) Amino Methane Hydrochloride（Tris-HCl）Or Acetic acid-sodium acetate.
Contain at least one in hydroxyl, amino, carboxyl in magnetic nanoparticle surface of the present invention.
Quantum dot surface of the present invention contains at least one in sulfydryl, carboxyl, amino;Semiconductor-quantum-point is closed Hydrophilic radical part used in includes 3- mercaptopropionic acids, TGA, Cys, 2 mercaptopropionic acid, sulfydryl fourth Acid, mercaptopentanoic acid, mercaptohexanoic acid, dimercaptosuccinic acid, mercaptoethanol, mercaprol, mercaptoethylmaine.
Beneficial effects of the present invention：
（1）The present invention is coupled together chitosan-modified magnetic nano-particle and water-soluble quantum dot by ionic cross-linking, The preparation method process for being used is simple, easily operation, in that context it may be convenient to be applied to the magnetic fluorescence composite Nano of other species The preparation of ball.
（2）Modification in the present invention due to shitosan to magnetic particle, effectively prevent magnetic material leakage and Fluorescent quenching effect to quantum dot；The fluorescence property of end-product can be by regulating and controlling polyanionic macromolecule organic reclaimed water The concentration of dissolubility quantum dot, crosslinking number of times etc., are obtained the magnetic fluorescence composite nanometer particle of different luminescent properties, can be used into Row organism targeted drug is transported and organism fluorescence imaging.
Brief description of the drawings
The TEM photos of Fig. 1 magnetic fluorescence composite nano-microspheres
The fluorescence spectrum and absorption spectrum of Fig. 2 magnetic fluorescence composite nano-microspheres
The fluorescence spectrum of magnetic fluorescence composite nano-microsphere prepared by Fig. 3 different mol ratios
Fig. 4 CdTe@ZnS-Fe2O3The fluorescence spectrum of magnetic fluorescence composite nano-microsphere
The digital photograph of Fig. 5 magnetic fluorescence composite nano-microspheres
The hysteresis curve of Fig. 6 magnetic fluorescence composite nano-microspheres.
Specific embodiment
Illustrate technical scheme, but technical scheme not with specific real below by specific embodiment Example is applied to be limited.
Embodiment 1：
1.1 prepare ZnSe quantum dots using Aqueous phase.Under nitrogen protection, by 0.01g NaBH42 are dissolved in 0.0061g Se powder In mL distilled water, 40 DEG C are heated to, NaHSe solution is obtained after being completely dissolved；Take 0.0439 g Zn (Ac)2Dissolve in 20 mL distillations In water, reduced glutathione 0.0737g is added after it is completely dissolved, pH=11.5 is adjusted with the NaOH solution of 1mol/L, obtained To the precursor solution of Zn；The presoma of Zn is transferred in there-necked flask, under nitrogen protection rapid injection NaHSe solution, oil bath 100 DEG C of backflows, taking-up is quickly cooled to room temperature in being put into refrigerator after magnetic agitation 1h, obtains colourless transparent solution, as prepares Good ZnSe QDs solution.
1.2 prepare Fe using hydro-thermal method3O4Nano particle.Weigh 3 g FeCl3It is dissolved in stirring ultrasound in 80 mL ethylene glycol Dissolving, adds the g of polyethylene glycol 2, the g of sodium acetate 7 that molecular weight is 2000, and stirring ultrasound is allowed to dissolve, precursor solution is turned Enter in hydrothermal reaction kettle, 5 h are reacted at 200 DEG C, resulting solution water is replaced into washing with absolute ethyl alcohol after the completion of reaction, through true Sky is dried, and obtains dry Fe3O4Magnetic nanometer particles.
1.3 prepare chitosan-modified magnetic nanocomposites using chemical covalent cross-linking method（CMCH-MNPs）.1. claim Take the Fe of hydro-thermal method preparation in 0.5g steps 1.23O4Magnetic nanoparticle is dissolved in 100 mL absolute ethyl alcohols, adds 0.5 mL tri- Methoxyamine propyl silane（APS）Amination modification is carried out, amination magnetic nanoparticle is obtained；2. dissolve chitosan in During volume fraction is 3% acetum, the chitosan gel rubber solution of 0.002 g/mL is made into；3. will 1. and 2. two solution are mixed Close, the μ L of glutaraldehyde 100 for adding concentration to be 10%, 10 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet collects reaction Product, product is alternately cleaned with distilled water and absolute ethyl alcohol, obtains chitosan-modified magnetic nanocomposites；
1.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase ZnSe amounts of the concentration of 1.1 preparations It is sub-, it is dissolved in after isopropanol separating-purifying in 5mL distilled water, and sodium polyphosphate is added, the concentration of wherein sodium polyphosphate is 0.001g/mL, ZnSe quantum dot concentration obtain reaction solution A for 0.1 mol/L；Take the shitosan prepared in 0.01g steps 1.3 The magnetic nanocomposites of modification are dissolved in 15 mL distilled water, ultrasonic 30 min, magnetic nanometer particles is uniformly dispersed and are obtained anti- Answer solution B；Solution A is added dropwise in B solution, 10 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet collects reaction Product, product is cleaned with distilled water, obtains final product magnetic fluorescent dual-function nano material.Fig. 1 is that the magnetic fluorescence for preparing is combined The TEM photos of Nano microsphere.
The 1.5 magnetic fluorescent dual-function nano particles for taking 100 μ L preparations, the wherein concentration of composite nanometer particle are 2 × 10-4 Mol/L, in adding 1.8 mL pH=7.4, concentration to be the PBS cushioning liquid of 0.01 mol/L, while adding the 100 μ L concentration to be 0~2×10-5The Cu of mol/L2+Metal ion, is obtained the fluorescence probe for detecting trace copper ion.
Embodiment 2：
The preparation of 2.1 ZnSe@ZnS quantum dot solution.ZnSe quantum dots, preparation method are prepared using chemical coprecipitation first As described in above-mentioned embodiment 1.The mL of ZnSe quantum dots 15 for preparing is taken, the wherein concentration of ZnSe quantum dots is 2.7 × 10-3 Mol/L, adds 0.0138 g Zn (Ac)2, 0.0277 g reductive glutathiones and 0.01 g thiocarbamides, with the concentration for having configured For 1 mol/L NaOH solutions regulation pH value is 10.5, under magnetic stirring, 100 DEG C of backflows of oil bath, after magnetic agitation reacts 2 h It is put into refrigerator and is quickly cooled to room temperature, obtains the ZnSe@ZnS quantum dots of faint yellow water-soluble high-luminous-efficiency.
2.2 prepare Fe using hydro-thermal method3O4Nano particle.Take 2.78 g FeSO4·7H2O、4.32 g FeCl3·6H2O It is dissolved in 30 mL distilled water, after magnetic agitation dissolving, adds 30 mL ethylene glycol, after stirring under nitrogen protection, plus Enter in there-necked flask, pH to 9-11 is adjusted with the NaOH solution that the concentration for having configured is 2 mol/L, add surfactant polyethylene The g of pyrrolidones 0.15,30min is reacted after being sufficiently stirred for, and Fe is obtained3O4The presoma of magnetic nanometer particles.By Fe3O4Magnetic is received The presoma of rice particulate is transferred in hydrothermal reaction kettle, and 6h is reacted at 160 DEG C.After the completion of reaction by resulting solution water with it is anhydrous Ethanol is alternately washed, vacuum dried, obtains dry Fe3O4Magnetic nanometer particles.
2.3 prepare chitosan-modified magnetic nanocomposites using chemical covalent cross-linking method（CMCH-MNPs）.1. claim Take the Fe of hydro-thermal method preparation in 0.5g steps 2.23O4Magnetic nanoparticle is dissolved in 100 mL absolute ethyl alcohols, adds 1 mL 3- ammonia Propyl-triethoxysilicane（APTES）Amination modification is carried out, amination magnetic nanoparticle is obtained；2. shitosan is dissolved In the acetum that volume fraction is 3%, the chitosan gel rubber solution of 0.005 g/mL is made into；3. will 1. and 2. two solution are mixed Close, the μ L of glyoxal 100 for adding concentration to be 8%, 10 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet is collected reaction and produced Thing, product is alternately cleaned with distilled water and absolute ethyl alcohol, obtains chitosan-modified magnetic nanocomposites；
2.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase ZnSe@of the concentration of 2.1 preparations ZnS quantum dot, is dissolved in 5mL distilled water after isopropanol separating-purifying, and adds sodium carboxymethylcellulose, wherein carboxymethyl cellulose The concentration of plain sodium is 0.003g/mL, and ZnSe quantum dots concentration obtains reaction solution A for 0.3 mol/L；Take 0.015g steps 2.3 The chitosan-modified magnetic nanocomposites of middle preparation are dissolved in 15 mL distilled water, ultrasonic 30 min, make magnetic nanometer particles It is uniformly dispersed and obtains reaction solution B；Solution A is added dropwise in B solution, 12 are vibrated in 25 DEG C of thermostatic control oscillator vibration H, magnet collecting reaction product, product is cleaned with distilled water, obtains final product magnetic fluorescent dual-function nano material.Fig. 2 is preparation Magnetic fluorescence composite nano-microsphere fluorescence spectrum and absorption spectrum.
2.5 take 100 μ L preparation magnetic fluorescent dual-function nano particles, wherein the concentration of composite nanometer particle be 5 × 10-4Mol/L, in adding 1.8 mL pH=7.4, concentration to be the boric acid-borax buffer solution of 0.01 mol/L, while adding 100 μ L concentration are 0 ~ 5 × 10-5The Hg of mol/L2+Metal ion, is obtained the fluorescence probe for detecting trace amount mercury ion.
Embodiment 3：
3.1 water mutually prepare CdTe quantum.Under nitrogen protection, by 0.0945g NaBH45 mL are dissolved in 0.0063g Te powder In distilled water, 40 DEG C are heated to, NaHTe solution is obtained after being completely dissolved；Take 0.293 g Cd (Ac)2Dissolve in 100 mL distilled water In, 2.0 mmol are added after it is completely dissolved, pH=11 is adjusted with the NaOH solution of 1mol/L, obtain the precursor solution of Cd； The presoma of Cd is transferred in there-necked flask, under nitrogen protection rapid injection NaHTe solution, 100 DEG C of backflows of oil bath, magnetic agitation Taking-up is quickly cooled to room temperature in being put into refrigerator after 4h, obtains colourless transparent solution, the CdTe QDs solution for as preparing.
The preparation of 3.2 magnetic nanoparticles.Patent publication No. is used to prepare Fe for the method for CN101597495A3O4/CoO Core-shell structure magnetic nano particle.
3.3 prepare chitosan-modified magnetic nanocomposites using chemical covalent cross-linking method（CMCH-MNPs）.1. claim Take the Fe prepared in 0.8 g steps 3.23O4/ CoO core-shell structure magnetic nano particles are dissolved in 100 mL absolute ethyl alcohols, are added 1.5 mL triethoxy amine propyl silanes carry out amination modification, obtain amination magnetic nanoparticle；2. shitosan is dissolved In the formic solutions that volume fraction is 4%, the chitosan gel rubber solution of 0.007 g/mL is made into；3. will 1. and 2. two solution are mixed Close, the μ L of glyoxal 100 for adding concentration to be 8%, 14 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet is collected reaction and produced Thing, product is alternately cleaned with distilled water and absolute ethyl alcohol, obtains chitosan-modified magnetic nanocomposites；
3.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase CdTe amounts of the concentration of 3.1 preparations It is sub-, it is dissolved in after isopropanol separating-purifying in 5mL distilled water, and add sodium carboxymethylcellulose, wherein sodium carboxymethylcellulose Concentration be 0.006 g/mL, CdTe quantum concentration obtains reaction solution A for 0.6 mol/L；Take system in 0.02 g steps 3.3 Standby chitosan-modified magnetic nanocomposites are dissolved in 15 mL distilled water, ultrasonic 30 min, disperse magnetic nanometer particles Uniformly obtain reaction solution B；Solution A is added dropwise in B solution, 16 h, magnetic are vibrated in 25 DEG C of thermostatic control oscillator vibration Iron collecting reaction product, product is cleaned with distilled water, obtains final product magnetic fluorescent dual-function nano material.Fig. 3 is different moles The fluorescence spectrum of the magnetic fluorescence composite nano-microsphere than preparing.
The 3.5 magnetic fluorescence composite nanocrystallines for taking 100 μ L preparations, the wherein concentration of composite nanocrystalline are 8 × 10-4 mol/L 1.8 mL pH=7.4 are added, during concentration is the Glycine-NaOH cushioning liquid of 0.01 mol/L, while adding 100 μ L Concentration is 0 ~ 1 × 10-4The Ag of mol/L+Metal ion, is obtained the fluorescence probe for detecting trace silver ion.
Embodiment 4：
4.1 prepare CdTe@ZnS quantum dots using Aqueous phase prepares CdTe quantum using chemical coprecipitation first, prepares As described in above-mentioned embodiment 3, it is 2h in the reaction time that difference is to method.Take the CdTe quantum for preparing and be dissolved in 30 mL steamings In distilled water, wherein the concentration of CdTe quantum is 1.67 × 10-3Mol/L, adds 0.0352 g Zn (Ac)2, 0.0984 g also Originality glutathione, is that 1 mol/L NaOH solutions regulation pH value is 8, under magnetic stirring, oil bath 100 with the concentration for having configured DEG C backflow, magnetic agitation is put into refrigerator and is quickly cooled to room temperature after reacting 2 h, obtains the CdTe@ZnS of water-soluble high-luminous-efficiency Quantum dot.
The preparation of 4.2 magnetic nanoparticles.Patent publication No. is used to prepare α-Fe for the method for the A of CN 1019280432O3 Magnetic nanoparticle.
4.3 prepare chitosan-modified magnetic nanocomposites using chemical covalent cross-linking method（CMCH-MNPs）.1. claim Take the α-Fe prepared in 0.8 g steps 4.22O3Magnetic nanoparticle is dissolved in 100 mL absolute ethyl alcohols, adds 2 mL aminopropyls three Methoxy silane carries out amination modification, obtains amination magnetic nanoparticle；2. it is 4% to dissolve chitosan in volume fraction Glacial acetic acid solution in, be made into the chitosan gel rubber solution of 0.009 g/mL；1. and 2. 3. two solution will mix, add concentration It is the 8% μ L of glyoxal 100,16 h is vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet collecting reaction product uses distilled water Product is alternately cleaned with absolute ethyl alcohol, chitosan-modified magnetic nanocomposites are obtained；
4.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase CdTe@of the concentration of 4.1 preparations ZnS quantum dot, is dissolved in 5mL distilled water after isopropanol separating-purifying, and adds sodium carboxymethylcellulose, wherein carboxymethyl cellulose The concentration of plain sodium is 0.01 g/mL, and CdTe quantum concentration obtains reaction solution A for 1.0 mol/L；Take 0.025 g steps 4.3 The chitosan-modified magnetic nanocomposites of middle preparation are dissolved in 15 mL distilled water, ultrasonic 30 min, make magnetic nanometer particles It is uniformly dispersed and obtains reaction solution B；Solution A is added dropwise in B solution, 14 are vibrated in 25 DEG C of thermostatic control oscillator vibration H, magnet collecting reaction product, product is cleaned with distilled water, obtains final product magnetic fluorescent dual-function nano material.Fig. 4 is preparation CdTe@ZnS-Fe2O3The fluorescence spectrum of magnetic fluorescence composite nano-microsphere；The digital photograph of Fig. 5 magnetic fluorescence composite nano-microspheres Piece.
The 4.5 magnetic fluorescence composite nanocrystallines for taking 100 μ L preparations, the wherein concentration of composite nanocrystalline are 1 × 10-3mol/ L, 1.8 mL pH=7.4 are added, concentration is the Tri(Hydroxymethyl) Amino Methane Hydrochloride of 0.01 mol/L（Tris-HCl）Cushioning liquid In, while it is 0 ~ 2 × 10 to add 100 μ L concentration-4The Pb of mol/L2+Metal ion, is obtained for detecting the glimmering of trace lead ion Light probe.
Embodiment 5：
5.1 prepare CdSe quantum dot under nitrogen protection using Aqueous phase, by 0.0106 g NaBH4With 0.0063 g Se powder It is dissolved in 2 mL distilled water, is heated to 40 DEG C, NaHSe solution is obtained after being completely dissolved；Take 0.0533 g Cd (Ac)2Dissolve in 20 In mL distilled water, 1.0 mmol are added after it is completely dissolved, pH=11.5 is adjusted with the NaOH solution of 1mol/L, obtain Cd's Precursor solution；The presoma of Cd is transferred in there-necked flask, under nitrogen protection rapid injection NaHSe solution, 100 DEG C of oil bath is returned Stream, taking-up is quickly cooled to room temperature in being put into refrigerator after magnetic agitation 1h, obtains colourless transparent solution, the CdSe for as preparing QDs solution.
The preparation of 5.2 magnetic nanoparticles.Take 1.39 g FeSO4·7H2O、2.16 g FeCl3·6H2O is dissolved in 50 In mL distilled water, after magnetic agitation dissolving, under nitrogen protection, and in addition there-necked flask, heating water bath to 80 DEG C, mechanical agitation Under, the g of surfactant polyvinylpyrrolidone 0.1 is added, adjust pH to 9- with the ammonia spirit that the concentration for having configured is 15% 11,60min is reacted after being sufficiently stirred for, Fe is obtained3O4Magnetic nanometer particles.By resulting solution water and anhydrous second after the completion of reaction Alcohol is alternately washed, vacuum dried, obtains dry Fe3O4Magnetic nanometer particles.
5.3 prepare chitosan-modified magnetic nanocomposites using chemical covalent cross-linking method（CMCH-MNPs）.1. claim Take the Fe prepared in 0.8 g steps 5.23O4Magnetic nanoparticle is dissolved in 100 mL absolute ethyl alcohols, adds 1.8 mL 2- ammonia second Base-aminopropyl trimethoxysilane carries out amination modification, obtains amination magnetic nanoparticle；2. dissolve chitosan in During volume fraction is 4% glacial acetic acid solution, the chitosan gel rubber solution of 0.01 g/mL is made into；3. will 1. and 2. two solution are mixed Close, the μ L of glutaraldehyde 100 for adding concentration to be 10%, 14 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet collects reaction Product, product is alternately cleaned with distilled water and absolute ethyl alcohol, obtains chitosan-modified magnetic nanocomposites；
5.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase CdSe amounts of the concentration of 5.1 preparations It is sub-, it is dissolved in after isopropanol separating-purifying in 5mL distilled water, and Carboxylic Acid Fibre element is added, the wherein plain concentration of Carboxylic Acid Fibre is 0.015 g/mL, CdSe quantum dot concentration obtains reaction solution A for 2.0 mol/L；The shell prepared in 0.03 g steps 5.3 is taken to gather Sugar-modified magnetic nanocomposites are dissolved in 15 mL distilled water, ultrasonic 30 min, magnetic nanometer particles is uniformly dispersed and are obtained Reaction solution B；Solution A is added dropwise in B solution, 16 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet is collected anti- Product is answered, product is cleaned with distilled water, obtain final product magnetic fluorescent dual-function nano material.Fig. 6 is magnetic fluorescence composite Nano The hysteresis curve of microballoon.
The 5.5 magnetic fluorescence composite nanocrystallines for taking 100 μ L preparations, the wherein concentration of composite nanocrystalline are 2 × 10-3 mol/ L, adds 1.8 mL pH=7.4, and concentration is the Tri(Hydroxymethyl) Amino Methane Hydrochloride of 0.01 mol/L（Tris-HCl）Buffering is molten In liquid, while it is 0 ~ 2 × 10 to add 100 μ L concentration-4The Pb of mol/L2+Metal ion, is obtained for detecting trace lead ion Fluorescence probe.

Claims (3)

1. a kind of magnetic fluorescent dual-function nano material, it is characterised in that with chitosan-modified magnetic nanoparticle as core, leads to Cross ionic cross-linking connection water-soluble quantum dot to obtain, the quantum dot is distributed in the surface of magnetic nanoparticle, wherein magnetic , in 10-200 nm, the particle diameter of quantum dot is in 1.5-10 nm for the particle size of nano particle；Described quantum dot is carried for surface The water-soluble quantum dot of hydrophilic radical, quantum dot is II-VI, III-V group semi-conductor material, or is II-VI and iii-v half The composite that conductor material is formed, the quantum point grain diameter is 1.5-10 nm.
2. a kind of magnetic fluorescent dual-function nano material according to claim 1, it is characterised in that the quantum dot is ZnSe、CdSe、CdTe、CdS、ZnSe/ZnS、CdS/ZnS、CdSe/ZnS、CdTe/ZnS、ZnXCd1-XSe、CdSe1-XSX、 CdSe1-XTeX、CdSe/ZnSe、CdS/ZnSe、CdTe/ZnSe、CdSe/CdS、CdTe/CdS、CdS/ZnXCd1-XS、ZnSe/ ZnXCd1-XS、CdSe/ZnXCd1-XS、CdTe/ZnXCd1-XS, wherein 0 ＜ X ＜ 1.
3. a kind of magnetic fluorescent dual-function nano material according to claim 1 and 2, it is characterized in that：The quantum dot table Contain at least one in sulfydryl, carboxyl, amino in face;Hydrophilic radical part used in semiconductor-quantum-point synthesis includes 3- mercaptopropionic acids, TGA, Cys, 2 mercaptopropionic acid, mercaptobutyric acid, mercaptopentanoic acid, mercaptohexanoic acid, sulfydryl fourth two Acid, mercaptoethanol, mercaprol, mercaptoethylmaine.
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