CN106833613B - A kind of preparation of magnetic fluorescent dual-function nano material - Google Patents
A kind of preparation of magnetic fluorescent dual-function nano material Download PDFInfo
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Abstract
The invention belongs to field of nano material preparation, more particularly 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 present invention provides a kind of preparation methods of magnetic fluorescent dual-function nano material, using 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 the particle size of magnetic nanoparticle is in 10-200 nm, and the partial size of quantum dot is in 1.5-10 nm.Reaction condition of the present invention is mild, operating method is simple, the composite nanometer particle of preparation has good luminescent properties and magnetic property, biomarker, fluoroimmunoassay, bio-separation, protein D NA enrichment with separate, the fields broad application prospect such as the preparation of medicine-carried system and target imaging.
Description
This case is divisional application, original application title are as follows: a kind of magnetic fluorescent dual-function nanoparticle probe and its preparation side
Method, former number of patent application are as follows: 2015100487318, the applying date are as follows: on January 30th, 2015, it is desirable that the application number of priority document
Are as follows: 201410311445, priority date are as follows: 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 giving birth to
Targeting positioning and bioluminescence imaging aspect in object.
Background technique
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 building.A variety of different materials are combined by the methods of surface epitaxial growth
Together, become the new hot spot of nanoscale science and technology research.Compared to the nano particle of one-component, multi-functional nanometer material
A variety of excellent performances are provided simultaneously with, preferably solving having a single function for physical presence keeps the use of some nano materials limited
The problem of processed, multi-functional nanometer material is fast-developing with its excellent performance, is more and more widely used different fields.Its
In, fluorescent material and magnetic material are received significant attention because it is in the extensive use of biochemical and medical domain.
Quantum dot is crystallite of the size in 1-100nm, is usually made 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, which is put, has adjustable fluorescence emission wavelengths, narrow and symmetrical fluorescence emission spectrum, wide and continuous ultra-violet absorption spectrum, and
Preferable photochemical stability.Currently, fluorescence quantum has been widely used in biological fluorescent labeling, biomedical imaging and is immunized
The fields such as detection and analysis.Ideal magnetic fluorescent microspheres require higher specific saturation magnetization, can generate it is stronger glimmering
Light and fluorescent stability is good, Microsphere Size is controllable, particle diameter distribution is narrow, chemical stability is good, surface function base rich in
Group, and the features such as preparation process is simple, repeatability is good, cheap, it acts not only as mri contrast agent and is used for
Medical diagnosis on disease is also used as separation of the pharmaceutical carrier for 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 enrichment with separate, the fields such as the preparation of medicine-carried system and target imaging are with very big application
Potentiality.
The preparation method of magnetic fluorescent nanometer particle mainly include coated with silica, polymer overmold, kind 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
The reason of point fluorescent quenching is main, and there are two aspects, are on the one hand the photochemical stabilities of quantum dot itself, due to application environment
Complexity, quantum dot stability is vulnerable to surrounding environment influence；It on the other hand is the influence of magnetic nano-particle, including the strong of magnetic
Absorption and magnetic-particle and quantum dot between fluorescence resonance energy transfer effect.
It is found through being retrieved to existing technology, (publication number: title: CN103525405A is based on natural polymer to Wang Feijun etc.
The magnetic fluorescent dual-function nano material and preparation method thereof of son) with magnetic particle Fe3O4For core, chitosan and polyanionic
Cellulose is Shell Materials, using the fluorescein isothiocynate of Chitosan-coated as fluorescent material, is obtained by LBL self-assembly method
It arrives.The fluorescent material that the method is selected is organic fluorescence molecule, and this kind of fluorescent material is as most of organic fluorescent dyes, amount
Sub- yield is lower, requires detection system stringent；Relatively narrow excitation wavelength range is harsh to selective exitation light source requirements；Transmitted wave
It long wider range and trails in long wavelength region, and brings the problems such as interfering with each other of spectrum between different sense channels,
Very big difficulty is brought to detection.Chen Kezheng (publication number: CN102020258A, a kind of title: magnetic fluorescence hydroxyapatite nano
The preparation method of composite construction) by control calcium/europium molar ratio, by the mixed solution of calcium nitrate and europium nitrate, phosphoric acid hydrogen two
Ammonium salt solution instills magnetic nano-particle solution simultaneously, is vigorously stirred down and obtains brown color precipitating, magnetic fluorescence hydroxy-apatite is made
Stone nano composite structure.The method needs to be added expensive rare earth element, simultaneously because the limitation of doping, what is obtained is glimmering
Light emitting wave-length coverage is limited.
For overcome the deficiencies in the prior art, the present invention passes through ion using chitosan-modified magnetic nano-particle as core
Cross-linking method connects the water-soluble quantum dot being dissolved in polyanionic macromolecule organic, and it is good to finally obtain biocompatibility
Magnetic fluorescence composite nano particle.Modification due to chitosan to magnetic particle effectively prevents letting out for magnetic material
It leaks and the fluorescent quenching of quantum dot is acted on；Water-soluble quantum in control polyanionic macromolecule organic can be passed through simultaneously
Concentration, crosslinking number of point etc., are made the magnetic fluorescence composite nanometer particle of different luminescent properties.
Summary of the invention
The object of the present invention is to provide a kind of magnetic fluorescent dual-function nano material and the preparation method of ion probe, the party
The composite nano particle of method preparation has that magnetic responsiveness is strong, photostability is high, it is simple to prepare, good dispersion and of uniform size etc. excellent
Point compared with the fluorescent material of simple function and magnetic material, while having fluorescence and magnetic multifunctional nanocomposites
In nanometer biotechnology have wider biomedical applications, such as cell separate and identify, cell multi-modal imaging analysis,
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 (CMCH-MNPs) is prepared using chemical covalent cross-linking method: 1. right
Magnetic nanoparticle surface carries out amination modification by amination silane coupling agent, obtains amination magnetic nanoparticle；②
It dissolves chitosan in the weak acid solution that volume fraction is 2%-6%, the chitosan gel rubber for being made into 0.001-0.01 g/mL is molten
Liquid；1. and 2. 3. two solution will mix, aldehyde crosslinking agent is added, vibrates 10-16 in 24-26 DEG C of thermostatic control oscillator vibration
H, magnet collecting reaction product, reaction product, obtains chitosan-modified magnetic nanocomposites wash with distilled water；
(b) magnetic fluorescent dual-function nano material is prepared using ionic cross-linking:
It takes the aqueous phase quantum point of the concentration of preparation to be dissolved in distilled water, and polyanionic macromolecule organic is added,
The concentration of middle polyanionic macromolecule organic is 0.0006-0.02 g/mL, obtains reaction solution A；Take 0.005-0.05g
The chitosan-modified magnetic nanocomposites prepared in step (a) are dissolved in distilled water, and ultrasonic 20-60 min makes magnetism receive
Rice particle is uniformly dispersed to obtain reaction solution B；Solution A is added dropwise in B solution, in 24-26 DEG C of thermostatic control oscillator vibration
Middle oscillation 8-16 h, magnet collecting reaction product, reaction product is wash with distilled water to get magnetic fluorescent dual-function nanometer material
Material.
A kind of efficient ion probe preparation process of the present invention is as follows: taking the 100 above-mentioned magnetic fluorescent dual-functions of μ L
Nano material, wherein the concentration of composite nanocrystalline is 2 × 10-4~2×10-3Mol/L, is added 1.8 pH=7.4 mL, and concentration is
In the buffer solution of 0.01 mol/L, while it is 2 × 10 that maximum concentration, which is added,-5~2×10-4Copper, mercury, silver or the lead of mol/L
The fluorescence probe for detecting trace metal ion is made in metal ion.
The preparation of magnetic fluorescent dual-function nano material of the present invention, magnetic nanoparticle (MNPs) are with super suitable
Magnetic, paramagnetic or ferromagnetic metal and metal oxide are selected from Fe3O4、Fe2O3、Fe3O4、MeFe2O4(Me=Co, Mn, Ni), change
Close object 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, particle size are 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 the water-soluble quantum dot that surface has hydrophilic radical, quantum dot II-VI, III-
V race semiconductor material, or be the composite material of II-VI and 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, amination silane coupling agent packet in step (a)
Include trimethoxy amine propyl silane (APS), 3- aminopropyl triethoxysilane (APTES), triethoxy amine propyl silane, ammonia third
Base trimethoxy silane, 2- aminoethyl-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, amination modified magnetic nanometer in step (a)
Particle process is: magnetic nanoparticle being dissolved in dehydrated alcohol, amination silane coupling agent is added, shakes in thermostatic control oscillator vibration
5-12 h is swung, magnet collecting reaction product modifies magnetic with distilled water and dehydrated alcohol alternating washing reaction product to get amination
Property nano particle, wherein the volume ratio of dehydrated alcohol and amination silane coupling agent is 200:1-50:1.
The preparation of magnetic fluorescent dual-function nano material of the present invention, weak acid solution described in step (a) 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) aldehyde crosslinking agent includes first
Aldehyde, glyoxal, glutaraldehyde, concentration 4%-15%.
The preparation of magnetic fluorescent dual-function nano material of the present invention, polyanionic macromolecule has in step (b)
Machine object includes sodium polyphosphate, sodium carboxymethylcellulose, cellulose sodium sulfate, cellulose carboxylic acid sodium, Carboxylic Acid Fibre element, carboxymethyl
One of cellulose potassium, sodium carboxymethylcellulose potassium, nano-cellulose.
Magnetic fluorescence composite nano-microsphere of the present invention, chitosan-modified magnetic nanocomposites in step (b)
Molar ratio with quantum dot is 1:1-1:30.
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 of hydroxyl, amino, carboxyl in magnetic nanoparticle surface of the present invention.
Quantum dot surface of the present invention contains at least one of sulfydryl, carboxyl, amino;Semiconductor-quantum-point closes
Hydrophilic radical ligand used in includes 3- mercaptopropionic acid, thioacetic acid, L-cysteine, 2 mercaptopropionic acid, sulfydryl fourth
Acid, mercaptopentanoic acid, mercaptohexanoic acid, dimercaptosuccinic acid, mercaptoethanol, mercaprol, mercaptoethylmaine.
Beneficial effects of the present invention:
(1) chitosan-modified magnetic nano-particle is connect by the present invention by ionic cross-linking with water-soluble quantum dot
Get up, used preparation method process is simple, easy to operate, it may be convenient to which the magnetic fluorescence applied to other types is compound
The preparation of nanosphere.
(2) modification due to chitosan to magnetic particle in the present invention, effectively prevent magnetic material leakage and
Fluorescent quenching effect to quantum dot；The fluorescence property of final product can pass through water in regulation polyanionic macromolecule organic
The concentration of dissolubility quantum dot, crosslinking number etc., are made the magnetic fluorescence composite nanometer particle of different luminescent properties, can be used into
The transport of row organism targeted drug and organism fluorescence imaging.
Detailed description of the invention
The TEM photo of Fig. 1 magnetic fluorescence composite nano-microsphere
The fluorescence spectrum and absorption spectrum of Fig. 2 magnetic fluorescence composite nano-microsphere
The fluorescence spectrum of the magnetic fluorescence composite nano-microsphere of Fig. 3 different mol ratio preparation
Fig. 4 CdTe@ZnS-Fe2O3The fluorescence spectrum of magnetic fluorescence composite nano-microsphere
The digital photograph of Fig. 5 magnetic fluorescence composite nano-microsphere
The hysteresis loop of Fig. 6 magnetic fluorescence composite nano-microsphere.
Specific embodiment
Illustrate technical solution of the present invention below by specific embodiment, but technical solution of the present invention is not with specific real
Example is applied to be limited.
Embodiment 1:
1.1 prepare ZnSe quantum dot using Aqueous phase.Under nitrogen protection, by 0.01g NaBH4With 0.0061g 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 0.0439 g Zn (Ac)2Dissolve in 20
In mL distilled water, reduced glutathione 0.0737g is added after it is completely dissolved, with the NaOH solution of 1mol/L adjust pH=
11.5, obtain the precursor solution of Zn；The presoma of Zn is transferred in there-necked flask, injection NaHSe is molten rapidly under nitrogen protection
Liquid, 100 DEG C of oil bath are flowed back, and taking-up, which is put into refrigerator, after magnetic agitation 1h is rapidly cooled to room temperature, and obtain colourless transparent solution, i.e.,
For the ZnSe QDs solution prepared.
1.2 prepare Fe using hydro-thermal method3O4Nano particle.Weigh 3 g FeCl3It is dissolved in 80 mL ethylene glycol and stirs ultrasound
Dissolution, is added 2 g of polyethylene glycol, 7 g of sodium acetate that molecular weight is 2000, and stirring ultrasound is allowed to dissolve, precursor solution is turned
Enter in hydrothermal reaction kettle, in 200 DEG C of 5 h of reaction, acquired solution water is replaced into washing with dehydrated alcohol after the reaction was completed, through true
Sky is dry, obtains dry Fe3O4Magnetic nanometer particles.
1.3 prepare chitosan-modified magnetic nanocomposites (CMCH-MNPs) using chemical covalent cross-linking method.1. claiming
Take the Fe that in 0.5g step 1.2 prepared by hydro-thermal method3O4Magnetic nanoparticle is dissolved in 100 mL dehydrated alcohols, and 0.5 mL tri- is added
Methoxyamine propyl silane (APS) carries out amination modification, obtains amination magnetic nanoparticle；2. dissolving chitosan in
In the acetum that volume fraction is 3%, it is made into the chitosan gel rubber solution of 0.002 g/mL；3. will 1. and 2. two solution mix
It closes, the 100 μ L of glutaraldehyde that concentration is 10% is added, 10 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet collects reaction
Product alternately cleans reaction product with distilled water and dehydrated alcohol, obtains chitosan-modified magnetic nanocomposites；
1.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase of the concentration of 1.1 preparations
ZnSe quantum dot is dissolved in 5mL distilled water after isopropanol separating-purifying, and sodium polyphosphate is added, wherein sodium polyphosphate
Concentration is 0.001g/mL, and ZnSe quantum dot concentration is that 0.1 mol/L obtains reaction solution A；It takes and prepares in 0.01g step 1.3
Chitosan-modified magnetic nanocomposites are dissolved in 15 mL distilled water, and 30 min of ultrasound make magnetic nanometer particles be uniformly dispersed
Obtain reaction solution B；Solution A is added dropwise in B solution, 10 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet is received
Collect reaction product, reaction product is wash with distilled water to get magnetic fluorescent dual-function nano material.Fig. 1 is that the magnetism of preparation is glimmering
The TEM photo of photoreactivation nanosphere.
The 1.5 magnetic fluorescent dual-function nano particles for taking 100 μ L to prepare, wherein the concentration of composite nanometer particle is 2 × 10-4
Mol/L, be added 1.8 pH=7.4 mL, concentration be 0.01 mol/L PBS buffer solution in, while be added 100 μ L concentration be
0~2×10-5The Cu of mol/L2+The fluorescence probe for detecting trace copper ion is made in metal ion.
Embodiment 2:
The preparation of 2.1 ZnSe@ZnS quantum dot solution.ZnSe quantum dot, preparation are prepared using chemical coprecipitation first
Method is described as in example 1 above.Take 15 mL of ZnSe quantum dot prepared, wherein the concentration of ZnSe quantum dot be 2.7 ×
10-30.0138 g Zn (Ac) is added in mol/L2, 0.0277 g reductive glutathione and 0.01 g thiocarbamide, use it is configured
Concentration is that 1 mol/L NaOH solution adjusting pH value is 10.5, under magnetic stirring, 100 DEG C of oil bath reflux, magnetic agitation reaction 2
It is put into refrigerator after h to be rapidly cooled to room temperature, obtains the ZnSe@ZnS quantum dot of faint yellow high water solubility 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 dissolution, adds 30 mL ethylene glycol and add after mixing evenly under nitrogen protection
Enter in there-necked flask, adjusts pH to 9-11 with the NaOH solution that configured concentration is 2 mol/L, surfactant polyethylene is added
0.15 g of pyrrolidones, reacts 30min after being sufficiently stirred, and Fe is made3O4The presoma of magnetic nanometer particles.By Fe3O4Magnetism is received
The presoma of rice particle is transferred in hydrothermal reaction kettle, reacts 6h at 160 DEG C.After the reaction was completed by acquired solution water with it is anhydrous
Ethyl alcohol alternately washs, vacuum dried, obtains dry Fe3O4Magnetic nanometer particles.
2.3 prepare chitosan-modified magnetic nanocomposites (CMCH-MNPs) using chemical covalent cross-linking method.1. claiming
Take the Fe that in 0.5g step 2.2 prepared by hydro-thermal method3O4Magnetic nanoparticle is dissolved in 100 mL dehydrated alcohols, and 1 mL 3- ammonia is added
Propyl-triethoxysilicane (APTES) carries out amination modification, obtains amination magnetic nanoparticle；2. chitosan is dissolved
In the acetum that volume fraction is 3%, it is made into the chitosan gel rubber solution of 0.005 g/mL；3. will 1. and 2. two solution mix
It closes, the 100 μ L of glyoxal that concentration is 8% is added, 10 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet is collected reaction and produced
Object alternately cleans reaction product with distilled water and dehydrated alcohol, obtains chitosan-modified magnetic nanocomposites；
2.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase of the concentration of 2.1 preparations
ZnSe@ZnS quantum dot is dissolved in 5mL distilled water after isopropanol separating-purifying, and sodium carboxymethylcellulose is added, wherein carboxylic first
The concentration of base sodium cellulosate is 0.003g/mL, and ZnSe quantum dot concentration is that 0.3 mol/L obtains reaction solution A；0.015g is taken to walk
The chitosan-modified magnetic nanocomposites prepared in rapid 2.3 are dissolved in 15 mL distilled water, and 30 min of ultrasound make magnetism receive
Rice particle is uniformly dispersed to obtain reaction solution B；Solution A is added dropwise in B solution, is shaken in 25 DEG C of thermostatic control oscillator vibration
12 h are swung, magnet collecting reaction product, reaction product is wash with distilled water to get magnetic fluorescent dual-function nano material.Fig. 2
For the fluorescence spectrum and absorption spectrum of the magnetic fluorescence composite nano-microsphere of preparation.
2.5 take 100 μ L prepare magnetic fluorescent dual-function nano particles, wherein the concentration of composite nanometer particle be 5 ×
10-4Mol/L, is added 1.8 pH=7.4 mL, and concentration is to be added simultaneously in boric acid-borax buffer solution of 0.01 mol/L
100 μ L concentration are 0 ~ 5 × 10-5The Hg of mol/L2+The fluorescence probe for detecting trace amount mercury ion is made in metal ion.
Embodiment 3:
3.1 water phases prepare CdTe quantum.Under nitrogen protection, by 0.0945g NaBH45 are dissolved in 0.0063g Te powder
In mL 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 distillation
In water, 2.0 mmol are added after it is completely dissolved, adjust pH=11 with the NaOH solution of 1mol/L, the presoma for obtaining Cd is molten
Liquid；The presoma of Cd is transferred in there-necked flask, injects NaHTe solution, 100 DEG C of oil bath reflux, magnetic force rapidly under nitrogen protection
It takes out to be put into refrigerator after stirring 4h and be rapidly cooled to room temperature, obtain colourless transparent solution, the CdTe QDs as prepared is molten
Liquid.
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 (CMCH-MNPs) using chemical covalent cross-linking method.1. claiming
Take the Fe prepared in 0.8 g step 3.23O4/ CoO core-shell structure magnetic nano particle is dissolved in 100 mL dehydrated alcohols, is added
1.5 mL triethoxy amine propyl silanes carry out amination modification, obtain amination magnetic nanoparticle；2. chitosan is dissolved
In the formic solutions that volume fraction is 4%, it is made into the chitosan gel rubber solution of 0.007 g/mL；3. will 1. and 2. two solution mix
It closes, the 100 μ L of glyoxal that concentration is 8% is added, 14 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet is collected reaction and produced
Object alternately cleans reaction product with distilled water and dehydrated alcohol, obtains chitosan-modified magnetic nanocomposites；
3.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase of the concentration of 3.1 preparations
CdTe quantum is dissolved in 5mL distilled water after isopropanol separating-purifying, and sodium carboxymethylcellulose is added, and wherein carboxymethyl is fine
The concentration for tieing up plain sodium is 0.006 g/mL, and CdTe quantum concentration is that 0.6 mol/L obtains reaction solution A；Take 0.02 g step
The chitosan-modified magnetic nanocomposites prepared in 3.3 are dissolved in 15 mL distilled water, and 30 min of ultrasound make magnetic Nano
Particle is uniformly dispersed to obtain reaction solution B；Solution A is added dropwise in B solution, is vibrated in 25 DEG C of thermostatic control oscillator vibration
16 h, magnet collecting reaction product, reaction product is wash with distilled water to get magnetic fluorescent dual-function nano material.Fig. 3 is not
With the fluorescence spectrum of the magnetic fluorescence composite nano-microsphere of molar ratio preparation.
The 3.5 magnetic fluorescence composite nanocrystallines for taking 100 μ L to prepare, wherein the concentration of composite nanocrystalline is 8 × 10-4 mol/L
It is added 1.8 pH=7.4 mL, concentration is in the Glycine-NaOH buffer solution of 0.01 mol/L, while 100 μ L are added
Concentration is 0 ~ 1 × 10-4The Ag of mol/L+The fluorescence probe for detecting trace silver ion is made in metal ion.
Embodiment 4:
4.1 use chemical coprecipitation to prepare CdTe quantum first using Aqueous phase preparation CdTe@ZnS quantum dot,
Preparation method as described in above-described embodiment 3, difference be the reaction time be 2h.The CdTe quantum prepared is taken to be dissolved in 30
In mL distilled water, wherein the concentration of CdTe quantum is 1.67 × 10-30.0352 g Zn (Ac) is added in mol/L2、0.0984
It is 8 that g reductive glutathione, which is 1 mol/L NaOH solution adjusting pH value with configured concentration, under magnetic stirring, oil bath
100 DEG C are flowed back, and are put into refrigerator after 2 h of magnetic agitation reaction and are rapidly cooled to room temperature, obtain the CdTe@of high water solubility luminous efficiency
ZnS quantum dot.
The preparation of 4.2 magnetic nanoparticles.Patent publication No. is used to prepare α-Fe for the method for 101928043 A of CN2O3
Magnetic nanoparticle.
4.3 prepare chitosan-modified magnetic nanocomposites (CMCH-MNPs) using chemical covalent cross-linking method.1. claiming
Take the α-Fe prepared in 0.8 g step 4.22O3Magnetic nanoparticle is dissolved in 100 mL dehydrated alcohols, and 2 mL aminopropyls three are added
Methoxy silane carries out amination modification, obtains amination magnetic nanoparticle；2. dissolving chitosan in volume fraction is 4%
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, concentration is added
For 8% 100 μ L of glyoxal, 16 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet collecting reaction product uses distilled water
Reaction product is alternately cleaned with dehydrated alcohol, obtains chitosan-modified magnetic nanocomposites；
4.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase of the concentration of 4.1 preparations
CdTe@ZnS quantum dot is dissolved in 5mL distilled water after isopropanol separating-purifying, and sodium carboxymethylcellulose is added, wherein carboxylic first
The concentration of base sodium cellulosate is 0.01 g/mL, and CdTe quantum concentration is that 1.0 mol/L obtain reaction solution A；Take 0.025 g
The chitosan-modified magnetic nanocomposites prepared in step 4.3 are dissolved in 15 mL distilled water, and 30 min of ultrasound make magnetism
Nanoparticle is uniformly dispersed to obtain reaction solution B；Solution A is added dropwise in B solution, in 25 DEG C of thermostatic control oscillator vibration
14 h are vibrated, magnet collecting reaction product, reaction product is wash with distilled water to get magnetic fluorescent dual-function nano material.Fig. 4
For the CdTe@ZnS-Fe of preparation2O3The fluorescence spectrum of magnetic fluorescence composite nano-microsphere；Fig. 5 magnetic fluorescence composite nano-microsphere
Digital photograph.
The 4.5 magnetic fluorescence composite nanocrystallines for taking 100 μ L to prepare, wherein the concentration of composite nanocrystalline is 1 × 10-3mol/ L,
1.8 pH=7.4 mL are added, concentration is Tri(Hydroxymethyl) Amino Methane Hydrochloride (Tris-HCl) buffer solution of 0.01 mol/L
In, while it is 0 ~ 2 × 10 that 100 μ L concentration, which are added,-4The Pb of mol/L2+Metal ion is made 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 is dissolved in 2 mL distilled water, is heated to 40 DEG C, and NaHSe solution is obtained after being completely dissolved；Take 0.0533 g Cd (Ac)2It is molten
Enter in 20 mL distilled water, 1.0 mmol are added after it is completely dissolved, adjusts pH=11.5 with the NaOH solution of 1mol/L, obtain
The precursor solution of Cd；The presoma of Cd is transferred in there-necked flask, injects NaHSe solution, oil bath 100 rapidly under nitrogen protection
DEG C reflux, takes out to be put into refrigerator after magnetic agitation 1h and is rapidly cooled to room temperature, and obtains colourless transparent solution, as prepares
CdSe 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 dissolution, under nitrogen protection, it is added in there-necked flask, heating water bath is to 80 DEG C, mechanical stirring
Under, 0.1 g of surfactant polyvinylpyrrolidone is added, adjusts pH to 9- with the ammonia spirit that configured concentration is 15%
11,60min is reacted after being sufficiently stirred, Fe is made3O4Magnetic nanometer particles.After the reaction was completed by acquired solution water and anhydrous second
Alcohol alternately washs, vacuum dried, obtains dry Fe3O4Magnetic nanometer particles.
5.3 prepare chitosan-modified magnetic nanocomposites (CMCH-MNPs) using chemical covalent cross-linking method.1. claiming
Take the Fe prepared in 0.8 g step 5.23O4Magnetic nanoparticle is dissolved in 100 mL dehydrated alcohols, and 1.8 mL 2- ammonia second are added
Base-aminopropyl trimethoxysilane carries out amination modification, obtains amination magnetic nanoparticle；2. dissolving chitosan in
In the glacial acetic acid solution that volume fraction is 4%, it is made into the chitosan gel rubber solution of 0.01 g/mL；3. will 1. and 2. two solution mix
It closes, the 100 μ L of glutaraldehyde that concentration is 10% is added, 14 h are vibrated in 25 DEG C of thermostatic control oscillator vibration, magnet collects reaction
Product alternately cleans reaction product with distilled water and dehydrated alcohol, obtains chitosan-modified magnetic nanocomposites；
5.4 prepare magnetic fluorescent dual-function nano material using ionic cross-linking.Take the water phase of the concentration of 5.1 preparations
CdSe quantum dot is dissolved in 5mL distilled water after isopropanol separating-purifying, and Carboxylic Acid Fibre element is added, wherein Carboxylic Acid Fibre element
Concentration is 0.015 g/mL, and CdSe quantum dot concentration is that 2.0 mol/L obtain reaction solution A；It takes in 0.03 g step 5.3 and prepares
Chitosan-modified magnetic nanocomposites be dissolved in 15 mL distilled water, 30 min of ultrasound keep magnetic nanometer particles dispersion equal
It is even to obtain reaction solution B；Solution A is added dropwise in B solution, 16 h, magnet are vibrated in 25 DEG C of thermostatic control oscillator vibration
Collecting reaction product, reaction product is wash with distilled water to get magnetic fluorescent dual-function nano material.Fig. 6 is multiple for magnetic fluorescence
Close the hysteresis loop of nanosphere.
The 5.5 magnetic fluorescence composite nanocrystallines for taking 100 μ L to prepare, wherein the concentration of composite nanocrystalline is 2 × 10-3 mol/
L, is added 1.8 pH=7.4 mL, and Tri(Hydroxymethyl) Amino Methane Hydrochloride (Tris-HCl) buffering that concentration is 0.01 mol/L is molten
In liquid, while it is 0 ~ 2 × 10 that 100 μ L concentration, which are added,-4The Pb of mol/L2+Metal ion is made for detecting trace lead ion
Fluorescence probe.
Claims (5)
1. a kind of preparation of magnetic fluorescent dual-function nano material, it is characterised in that: with chitosan-modified magnetic nanoparticle
For core, water-soluble quantum dot being connected by ionic cross-linking and is obtained, the quantum dot is distributed in the surface of magnetic nanoparticle,
The particle size of middle magnetic nanoparticle is in 10-200nm, and the partial size of quantum dot is in 1.5-10nm；The preparation method includes
Following steps:
(a) chitosan-modified magnetic nanocomposites (CMCH-MNPs) is prepared using chemical covalent cross-linking method: 1. magnetism is received
Rice grain surface carries out amination modification by amination silane coupling agent, obtains amination magnetic nanoparticle；2. shell is gathered
Sugar is dissolved in the weak acid solution that volume fraction is 2%-6%, is made into the chitosan gel rubber solution of 0.001-0.01g/mL；3. will
2. aldehyde crosslinking agent is added 1. two solution mix, 10-16h is vibrated in 24-26 DEG C of thermostatic control oscillator vibration, magnet is received
Collect reaction product, reaction product, obtains chitosan-modified magnetic nanocomposites wash with distilled water；
(b) magnetic fluorescent dual-function nano material is prepared using ionic cross-linking:
It takes the aqueous phase quantum point of the concentration of preparation to be dissolved in distilled water, and polyanionic macromolecule organic is added, wherein gathering
The concentration of anionic macromolecule organic is 0.0006-0.02g/mL, obtains reaction solution A；Take 0.005-0.05g step
(a) the chitosan-modified magnetic nanocomposites prepared in are dissolved in distilled water, and ultrasonic 20-60min makes magnetic nanometer particles
It is uniformly dispersed to obtain reaction solution B；Solution A is added dropwise in B solution, is vibrated in 24-26 DEG C of thermostatic control oscillator vibration
8-16h, magnet collecting reaction product, reaction product is wash with distilled water to get magnetic fluorescent dual-function nano material；It is described poly-
Anionic macromolecule organic is sodium polyphosphate, sodium carboxymethylcellulose or Carboxylic Acid Fibre element.
2. a kind of preparation of magnetic fluorescent dual-function nano material according to claim 1, which is characterized in that the magnetic
Property nano particle MNPs be superparamagnetic, paramagnetic or ferromagnetic metal and metal oxide, be selected from Fe3O4、Fe2O3、MeFe2O4、
Compound neodymium iron boron or SmCo；Wherein Me is Co, Mn or Ni；The partial size of the magnetic fluorescent dual-function nano material is 10-
220nm；
The preparation method of the magnetic nanoparticle includes coprecipitation, hydro-thermal method；Contain on the magnetic nanoparticle surface
At least one of hydroxyl, amino, carboxyl.
3. a kind of preparation of magnetic fluorescent dual-function nano material according to claim 1, which is characterized in that step (a)
Middle amination silane coupling agent includes trimethoxy amine propyl silane APS, 3- aminopropyl triethoxysilane APTES, three ethoxies
Base amine propyl silane, aminopropyl trimethoxysilane, 2- aminoethyl-aminopropyl trimethoxysilane, divinyl triammonium base propyl
Trimethoxy silane, aminoethylaminopropyl methyl dimethoxysilane.
4. a kind of preparation of magnetic fluorescent dual-function nano material according to claim 1, which is characterized in that step (a)
The preparation process of amination magnetic nanoparticle is: magnetic nanoparticle being dissolved in dehydrated alcohol, it is silane coupled that amination is added
Agent, 5-12h is vibrated in thermostatic control oscillator vibration, and magnet collecting reaction product replaces washing reaction with distilled water and dehydrated alcohol
Product is to get amination magnetic nanoparticle, and wherein the volume ratio of dehydrated alcohol and amination silane coupling agent is 200:1-50:
1；
Weak acid solution described in step (a) includes formic acid, glacial acetic acid, tartaric acid, citric acid；Step (a) aldehyde crosslinking agent
Including formaldehyde, glyoxal, glutaraldehyde, concentration 4%-15%.
5. a kind of preparation of magnetic fluorescent dual-function nano material according to claim 1, which is characterized in that step (b)
In the molar ratios of chitosan-modified magnetic nanocomposites and quantum dot be 1:1-1:30.
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| US12102973B2 (en) | 2015-12-18 | 2024-10-01 | Safeguard Biosystems Holdings Ltd. | Three-dimensional polymer networks with channels situated therein |
| CN105903978B (en) * | 2016-04-20 | 2017-12-15 | 中国科学院新疆理化技术研究所 | The preparation method and purposes of a kind of stable fluorescence copper clusters of silane |
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| CN109100339B (en) * | 2018-07-30 | 2020-03-10 | 四川大学 | Kit for selectively detecting concentration of Pb ions and Ag ions and detection method |
| RU2685669C1 (en) * | 2018-08-01 | 2019-04-22 | федеральное государственное бюджетное образовательное учреждение высшего образования "Алтайский государственный университет" | Method of producing colloidal quantum points of zinc selenide in cells of chitosan |
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| CN110376105B (en) * | 2019-07-10 | 2022-06-03 | 赛莱克斯(深圳)科技有限公司 | Method and device for determining characteristics and concentration of small particles in clinical sample |
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| CN110887962A (en) * | 2019-12-05 | 2020-03-17 | 中国人民解放军军事科学院军事医学研究院 | Preparation and immunochromatography application of magnetic composite nanomaterial with double-layer quantum dot shell structure |
| TR201920231A2 (en) * | 2019-12-13 | 2020-06-22 | Cukurova Teknoloji Gelistirme Boelgesi Yoenetici A S | VERSATILE NANO BIOMATERIAL WITH DRUG TARGETING, ENZYME AND DRUG LINKING FEATURES IN HEALTH AND MANUFACTURING INDUSTRY |
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| CN113984726B (en) * | 2021-10-20 | 2024-02-02 | 上海大学 | Method for detecting mercury ions by amino phenylboronic acid functionalized magnetic beads/glyoxal modified DNA |
| CN116023932B (en) * | 2022-12-09 | 2024-03-12 | 山西大学 | Fluorescent probe for glutathione detection and preparation thereof |
| WO2024187253A1 (en) * | 2023-03-10 | 2024-09-19 | Cnpem - Centro Nacional De Pesquisa Em Energia E Materiais | Porous nanocomposites of oxidised nanofibrillated cellulose and natural rubber latex comprising antimicrobial metal oxides, production processes and uses |
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