CN107964400A - A kind of preparation method of novel magnetic fluorescence nano composite material - Google Patents

A kind of preparation method of novel magnetic fluorescence nano composite material Download PDF

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CN107964400A
CN107964400A CN201711372124.2A CN201711372124A CN107964400A CN 107964400 A CN107964400 A CN 107964400A CN 201711372124 A CN201711372124 A CN 201711372124A CN 107964400 A CN107964400 A CN 107964400A
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CN107964400B (en
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罗爱芹
陈炜杰
张鑫
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Beijing Institute of Technology BIT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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Abstract

The present invention relates to a kind of method for preparing novel magnetic fluorescence nano composite material, belong to materials chemistry and Inorganic synthese field.Magnetic-particle is combined by the present invention with quantum dot, is prepared for the nanocomposite with strong magnetic induction effect and high fluorescence property.The magnetic fluorescence nano composite material of synthesis, while can accomplish the quick separating under magnetic field and the high intensity fluorescent emission under light excitation.In the presence of a magnetic field, which can be quickly by magnetic suck, and after removing magnetic field, which can disperse rapidly again.This method preparation method has the advantages that convieniently synthesized, yield is high, nano particle is uniform, particle diameter is smaller and is widely used, and has very big potential application in medicine detection, bio-sensing, food analysis and environmental protection.

Description

A kind of preparation method of novel magnetic fluorescence nano composite material
Technical field
The present invention relates to a kind of method for preparing magnetic fluorescence nano composite material, and specifically, the magnetic fluorescence is received Nano composite material is a kind of new function material, belongs to Inorganic synthese technical field.
Background technology
Magnetic fluorescence nano composite material, as a kind of new functional material, while has the super of magnetic Nano material concurrently The optical property of paramagnetism and quanta point material.
In recent years, novel nano-material, including quantum dot, mesoporous material, carbon nanotubes and magnetic nanoparticle etc. are in life Using more and more extensive in thing, chemistry, medicine and environmental area.Wherein, since its unique physicochemical properties, magnetism are received Rice material becomes the research hotspot in many fields.Magnetic nanoparticle, is a kind of soft magnetism with cube inverse spinel structure Nano-function thin films, cell parameter a=0.839nm, 32 O in structure cell2-Along the close ordered arrangement in [111] direction, part Fe3+Occupy tetrahedral site, remaining Fe2+And Fe3+Octahedral site is occupied, electronics can turn rapidly between two kinds of iron ions Move.Meanwhile magnetic nano-particle is at a certain temperature, particle warm-up movement can cause particle moment orientation to change, and add outer Boundary magnetic field, particle are magnetized；External magnetic field is cancelled, beads magnetic rapidly disappears, and shows superparamagnetism.It prepares pattern can Control, size is controllable, the easy functionalization in surface.For the separation materials such as conventional silica gel particle and resin particle, magnetism is received Rice grain can realize accurate microoperation under the action of externally-applied magnetic field, show more efficient quick adsorption separation efficiency.
Magnetic composite is formed after magnetic Nano material surface modification, combines pair of magnetic material and nonmagnetic substance Principal characteristic matter, has important application value in physics, chemistry, biology and medical domain.Fe3O4Magnetic composite has following excellent Point：First, improve Fe3O4Stability, dispersiveness and biocompatibility；Second, assign Fe3O4New active function groups, such as Hydroxyl, carboxyl, amino, sulfydryl etc., and by electrostatic interaction or covalent bond form combination inorganic particulate, such as gold, silver, Copper, platinum, silica or organic molecule (Methylaminopterin, adriamycin, protein, enzyme, antibody and nucleic acid)；3rd, in extraneous magnetic Fe is utilized under field action3O4High magnetic responsiveness, can accurately control the direction of motion of magnetic composite.Therefore, Fe3O4It is magnetic Compound is gathered around in fields such as catalytic reaction, waste water water purification, bio-molecular separation, targeted drug treatments to have broad application prospects. However, the above-mentioned various methods to magnetic nanoparticle surface modification, generally require magnetic nanoparticle surface into Capable complicated and interminable multistep reaction.Often magnetic saturation is low for the magnetic nanoparticle that these methods are modified, saturation magnetic strength It is low, and need complicated synthesis step, it is necessary to high-temperature operation and to cause nanometer to be reunited serious, seriously affect magnetic nanoparticle Practical application.Thus, Rapid Modification and particularly important to improve its performance with high magnetic magnetic nanoparticle is developed, In order to overcome problem above, present invention selection one-step synthesis surface carries the magnetic-particle of carboxyl modified.
In the present invention, a step modification carries out magnetic nanoparticle surface with trisodium citrate by hydro-thermal method, is grafted carboxylic Base, eliminates the cumbersome synthesis step of modification, and synthesizes obtained magnetic-particle uniform particle diameter, good dispersion, magnetic intensity Height, have preferable actual application value.
Quantum dot, as a kind of novel fluorescence nano material, is mainly made of inorganic II-IV races or iii-v element Nano material, its particle diameter are about 1-100nm.Quantum dot typically contains 200-10000 atom, but is different from common nano material The mixed and disorderly unordered arrangement microcosmic, quantum dot have the regularly arranged of similar body phase crystal, its particle size controls it to shine Characteristic.In simple terms, the unique nano effect and excellent fluorescence property that quantum dot has by it, such as：(1) strong anti-light drift The anti-chemical degradations of Bai Xingyu；(2) wide excitation spectrum；(3) high quantum production rate and molar extinction coefficient (are higher than organic dyestuff 10-100 Times)；(4) there is larger Stokes shift, fluorescence lifetime is long；(5) quantum dot of multicolor fluorescence can be by single ripple The excitation of long light；(6) bio-compatibility of quantum dot surface is more preferable, is easily formed and is conjugated with other molecules.And its fluorescent emission Fluorescence peak half-peak width, colour gamut it is wide, have unrivaled advantage in fluorescence developing field.Quanta point material can quickly into Row qualitative and quantitative analysis, detection result is obvious, and test limit is relatively low, has high application value.Therefore, in order to further improve The performance of magnetic Nano material, in the present invention, by amidation process, is connected to magnetic-particle surface by quantum dot, makes it Form magnetic fluorescence nano composite material, while superparamagnetism and the rapid fluorescence emission effect of quantum dot with magnetic-particle Fruit.
Being contrasted with existing traditional magnetic Nano material, the characteristics of new material that the present invention synthesizes is that synthesis is fast and convenient, There is the superparamagnetism of magnetic Nano material and the excellent optical property of CdS quantum dots, building-up process letter at the same time Single, of low cost, easy to produce scale amplification, the advanced composite material (ACM) have in fields such as biomedical detection, environmental protections Huge potential using value.
The content of the invention
The object of the present invention is to provide a kind of novel nano composite wood synthesized with superparamagnetism with good fluorescence performance The method of material.
The purpose of the present invention is mainly realized by following technological means：
The synthesis of the present invention comprises the following steps that：
1) a certain amount of iron chloride, trisodium citrate, sodium acetate are weighed, its quality is iron chloride than scope：Citric acid three Sodium：Sodium acetate=2:1:2~5:1:5；Iron chloride and trisodium citrate are added in a certain amount of ethylene glycol solution first, surpassed Sound dissolves；Secondly, it is slowly added to anhydrous sodium acetate and is stirred continuously；Again, above-mentioned product is put into reaction kettle, is taken the photograph in 200 When family name's degree baking oven heating 12 is small, it is cooled to room temperature；Finally, by products therefrom, it is put into refrigerator freezing after twenty minutes, product is placed in When centrifuge tube vacuum freeze drying 4~5 is small, preserved under 4 degrees Celsius of environment；
2) a certain amount of Zinc vitriol (ZnSO is weighed4·7H2O), four hydration manganous chloride (MnCl2·4H2O), four Hydrated sodium sulfide (Na2S·4H2O), its quality is Zinc vitriol than scope：Four hydration manganous chloride：Four hydrated sodium sulfides =12:1:12~25:1:25；
3) first, Zinc vitriol is added in a certain amount of deionized water with four hydration manganous chloride and is dissolved, is mixed Compound is stirred at room temperature 30 minutes under nitrogen protection；Secondly, four hydrated sodium sulfides are slowly added into solution dropwise, at room temperature Continue stirring 2~3 it is small when；Again, product is centrifuged, precipitation is collected, is washed three times with ethanol/water mixed solution；Finally, will Products therefrom, is put into refrigerator freezing after twenty minutes, by product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, at 4 degrees Celsius Preserved under environment；
4) in mass ratio it is mercaptoethylmaine (MEA)：ZnS quantum dots=1:1.25~1:1.5 weigh a certain amount of sulfydryl Ethamine, ZnS quantum dots, are subsequently added to dissolve in a certain amount of ethanol, when room temperature lucifuge stirring reaction 10 is small, by gained Product centrifuges, and collects precipitation, is washed three times with ethanol/water mixed solution；
5) by products therefrom, it is put into refrigerator freezing after twenty minutes, it is small that product is placed in centrifuge tube vacuum freeze drying 4~5 When, preserved under 4 degrees Celsius of environment, obtain amido modified quantum dot；
6) in mass ratio scope be carboxyl modified ferroso-ferric oxide (Fe3O4)：1- (3- dimethylamino-propyls) -3- ethyls Carbodiimide hydrochloride (EDC)：N-hydroxysuccinimide (NHS)=1:80:150~1:120:200, weigh a certain amount of Fe3O4, EDC and NHS, be added in citrate buffer solution, when stir-activating 1~2 is small；
7) added into the EDC/NHS reaction systems after activation it is a certain amount of it is amido modified after ZnS quantum dot, wherein ZnS quantum dot：Fe3O4Magnetic-particle quality is 8 than scope:1~15:1, after ultrasonic dissolution, stirring reaction 20 is small under 30 degrees Celsius When；
8) reaction product obtained is washed three times with ethanol/water mixed solution, and Magneto separate collects precipitation；Products therefrom puts ice Case freeze after twenty minutes, obtain yellowish-brown product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, afterwards in 4 degrees Celsius of environment Lower preservation.
The magnetic flourescent nano material for magnetic measure application that the present invention synthesizes is as follows：
The magnetic fluorescence nano composite material that synthesis obtains is disperseed in aqueous, can be detected with stronger glimmering Light, while adsorbed by magnet, can in 10 minutes complete adsorption and sedimentation so that supernatant clear, and supernatant The substantially all disappearance of fluorescence of liquid.
Brief description of the drawings
The magnetic nanoparticle TEM electron microscopes of synthesis
Attached drawing 1
The actual effect figure of magnetic suck
Attached drawing 2
Fluorescence intensity change during magnetic suck
Attached drawing 3
The magnetic intensity VSM figures of the magnetic fluorescence nano composite material of synthesis
Attached drawing 4
The magnetic fluorescence nano composite material TEM electron microscopes of synthesis
Attached drawing 5
Embodiment
Embodiment 1
The conjunction of carboxyl modified magnetic Nano material and the magnetic fluorescence nano composite material of amido modified ZnS quantum dot Into：
1) 1.95g FeCl are taken3, 0.6g trisodium citrates, 60mL ethylene glycol, add beaker in；Ultrasonic dissolution, and start Stirring, in whipping process, is slowly added to 3.6g anhydrous sodium acetates；Above-mentioned product is put into reaction kettle, in 200 degrees Celsius of bakings After when case heating 12 is small, it is cooled to room temperature；By products therefrom, refrigerator freezing is put after twenty minutes, product is placed in centrifuge tube vacuum When freeze-drying 4~5 is small, be placed under 4 degrees Celsius of environment and preserve；
2) ZnSO of 1.797g is taken4·7H2The MnCl of O and 98.955mg2·4H2O, and 20mL deionized water successively It is added in the three-necked flask of 50mL, mixture is stirred at room temperature 30 minutes under nitrogen protection；
3) by the Na of 1.801g2S·4H2O (being dissolved in the water of 5mL) is slowly added into there-necked flask dropwise, is continued at room temperature When stirring 2~3 is small；Products therefrom is centrifuged, precipitation is collected, is washed three times with ethanol/water mixed solution；Finally, by institute Product, be put into refrigerator freezing after twenty minutes, by product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, in 4 degrees Celsius of rings Preserved under border；
4) ZnS quantum dot is modified with mercaptoethylmaine：The mercaptoethylmaine (MEA) of 150mg is taken, 5mL ethanol, is added to 200mg In ZnS quantum dot, when room temperature lucifuge stirring reaction 10 is small；Products therefrom is centrifuged, precipitation is collected, is mixed with ethanol/water Solution washs three times；Finally, by products therefrom, it is put into refrigerator freezing after twenty minutes, product is placed in centrifuge tube vacuum refrigeration does It is dry 4~5 it is small when, preserved under 4 degrees Celsius of environment, obtain amido modified ZnS quantum dot；
5) magnetic particle of 20mg carboxyl modifieds is taken, adds the buffer solution (citric acid-trisodium citrate buffer body of 20mL System, pH=6.4) the carboxyl magnetic fluid of 1mg/mL is configured to, it is spare；2mL carboxyl magnetic fluids are taken, add 50mL activating reagents, its Middle activating reagent EDC/NHS (4:4.8mg/mL), when stirring 1~2 is small；
6) added into the carboxyl magnetic fluid after activation 20mg it is amido modified after ZnS quantum dot, after ultrasonic dissolution, measure Fluorescence intensity, when reaction 20 is small in the stirring that temperature is 30 degrees Celsius；Products therefrom is centrifuged, precipitation is collected, uses second Alcohol/water mixed solution washing is three times；Finally, by products therefrom, it is put into refrigerator freezing after twenty minutes, it is true that product is placed in centrifuge tube When vacuum freecing-dry 4~5 is small, is preserved under 4 degrees Celsius of environment, obtain magnetic fluorescence nano composite material.
Embodiment 2
The conjunction of carboxyl modified magnetic Nano material and the magnetic fluorescence nano composite material of amido modified ZnS quantum dot Into：
1) 1g FeCl are taken3, 0.2g trisodium citrates, 60mL ethylene glycol, add beaker in；The above-mentioned mixing of ultrasonic dissolution is molten Liquid, and start to stir, in whipping process, it is slowly added to 2g anhydrous sodium acetates；Above-mentioned product is put into reaction kettle, in 200 After when degree Celsius baking oven heating 12 is small, it is cooled to room temperature；By products therefrom, put refrigerator freezing after twenty minutes, by product be placed in from When heart pipe vacuum freeze drying 4~5 is small, be placed under 4 degrees Celsius of environment and preserve；
2) ZnSO of 1.152g is taken4·7H2The MnCl of O and 39.42mg2·4H2O, and the deionized water of 20mL add successively Enter into the three-necked flask of 50mL, mixture is stirred at room temperature 30 minutes under nitrogen protection；
3) by the Na of 1.2g2S·4H2O (being dissolved in the water of 5mL) is slowly added into there-necked flask dropwise, continues to stir at room temperature Mix 2~3 it is small when；Products therefrom is centrifuged, precipitation is collected, is washed three times with ethanol/water mixed solution；Finally, by gained Product, is put into refrigerator freezing after twenty minutes, by product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, in 4 degrees Celsius of environment Lower preservation；
4) ZnS quantum dot is modified with mercaptoethylmaine：The mercaptoethylmaine (MEA) of 100mg is taken, 5mL ethanol, is added to 150mg In ZnS quantum dot, when room temperature lucifuge stirring reaction 10 is small；Products therefrom is centrifuged, precipitation is collected, is mixed with ethanol/water Solution washs three times；Finally, by products therefrom, it is put into refrigerator freezing after twenty minutes, product is placed in centrifuge tube vacuum refrigeration does It is dry 4~5 it is small when, preserved under 4 degrees Celsius of environment, obtain amido modified ZnS quantum dot；
5) magnetic particle of 20mg carboxyl modifieds is taken, adds the buffer solution (citric acid-trisodium citrate buffer body of 20mL System, pH=6.4) the carboxyl magnetic fluid of 1mg/mL is configured to, it is spare；2mL carboxyl magnetic fluids are taken, add 50mL activating reagents, its Middle activating reagent EDC/NHS (2:2.4mg/mL), when stirring 1~2 is small；
6) added into the carboxyl magnetic fluid after activation 15mg it is amido modified after ZnS quantum dot, after ultrasonic dissolution, measure Fluorescence intensity, when reaction 20 is small in the stirring that temperature is 30 degrees Celsius；Products therefrom is centrifuged, precipitation is collected, uses second Alcohol/water mixed solution washing is three times；Finally, by products therefrom, it is put into refrigerator freezing after twenty minutes, it is true that product is placed in centrifuge tube When vacuum freecing-dry 4~5 is small, is preserved under 4 degrees Celsius of environment, obtain magnetic fluorescence nano composite material.
Embodiment 3
The conjunction of carboxyl modified magnetic Nano material and the magnetic fluorescence nano composite material of amido modified ZnS quantum dot Into：
1) 3g FeCl are taken3, 1.5g trisodium citrates, 60mL ethylene glycol, add beaker in；The above-mentioned mixing of ultrasonic dissolution is molten Liquid, and start to stir, in whipping process, it is slowly added to 5g anhydrous sodium acetates；Above-mentioned product is put into reaction kettle, in 200 When degree Celsius baking oven heating 12 is small, it is cooled to room temperature；By products therefrom, refrigerator freezing is put after twenty minutes, product is placed in centrifugation When pipe vacuum freeze drying 4~5 is small, be placed under 4 degrees Celsius of environment and preserve；
2) ZnSO of 2.304g is taken4·7H2The MnCl of O and 197.1mg2·4H2O, and the deionized water of 20mL add successively Enter into the three-necked flask of 50mL, mixture is stirred at room temperature 30 minutes under nitrogen protection；
3) by the Na of 2.4g2S·4H2O (being dissolved in the water of 5mL) is slowly added into there-necked flask dropwise, continues to stir at room temperature Mix 2~3 it is small when；Products therefrom is centrifuged, precipitation is collected, is washed three times with ethanol/water mixed solution；Finally, by gained Product, is put into refrigerator freezing after twenty minutes, by product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, in 4 degrees Celsius of environment Lower preservation；
4) ZnS quantum dot is modified with mercaptoethylmaine：Mercaptoethylmaine (MEA), the 5mL ethanol of 200mg is taken, is added to 250mg In ZnS quantum dot, when room temperature lucifuge stirring reaction 10 is small；Products therefrom is centrifuged, precipitation is collected, is mixed with ethanol/water Solution washs three times；Finally, by products therefrom, it is put into refrigerator freezing after twenty minutes, product is placed in centrifuge tube vacuum refrigeration does It is dry 4~5 it is small when, preserved under 4 degrees Celsius of environment, obtain amido modified ZnS quantum dot；
5) magnetic particle of 20mg carboxyl modifieds is taken, adds the buffer solution (citric acid-trisodium citrate buffer body of 20mL System, pH=6.4) the carboxyl magnetic fluid of 1mg/mL is configured to, it is spare；2mL carboxyl magnetic fluids are taken successively, add 50mL activation examinations Agent, wherein activating reagent EDC/NHS (6:7.2mg/mL), when stirring 1~2 is small；
6) added into the carboxyl magnetic fluid after activation 30mg it is amido modified after ZnS quantum dot, after ultrasonic dissolution, measure Fluorescence intensity, when reaction 20 is small in the stirring that temperature is 30 degrees Celsius；Products therefrom is centrifuged, precipitation is collected, uses second Alcohol/water mixed solution washing is three times；Finally, by products therefrom, it is put into refrigerator freezing after twenty minutes, it is true that product is placed in centrifuge tube When vacuum freecing-dry 4~5 is small, is preserved under 4 degrees Celsius of environment, obtain magnetic fluorescence nano composite material.
Embodiment 4：
The conjunction of the magnetic fluorescence nano composite material of hydroxyl modified magnetic Nano material and the ZnS quantum dot of carboxyl modified Into：
1) magnetic particle of 20mg hydroxyl modifieds is taken, adds the buffer solution (citric acid-trisodium citrate buffer body of 20mL System, pH=6.4) magnetic fluid of 1mg/mL is configured to, it is spare；
2) 2mL magnetic fluids are taken, add 50mL activating reagents, wherein activating reagent EDC/NHS (4:4.8mg/mL), 1 is stirred ~2 it is small when；
3) ZnS quantum dot after 20mg carboxyl modifieds, after ultrasonic dissolution, measure are added into the hydroxyl magnetic fluid after activation Fluorescence intensity, when reaction 20 is small in the stirring that temperature is 30 degrees Celsius；
4) products therefrom is centrifuged, collects precipitation, washed three times with ethanol/water mixed solution；Finally, gained is produced Thing, is put into refrigerator freezing after twenty minutes, by product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, under 4 degrees Celsius of environment Preserve, obtain magnetic fluorescence nano composite material.
Embodiment 5：
The conjunction of the magnetic fluorescence nano composite material of amido modified magnetic Nano material and the ZnS quantum dot of carboxyl modified Into：
1) the amido modified magnetic particles of 20mg are taken, add the buffer solution (citric acid-trisodium citrate buffer body of 20mL System, pH=6.4) magnetic fluid of 1mg/mL is configured to, it is spare；
2) 2mL magnetic fluids are taken, add 50mL activating reagents, wherein activating reagent EDC/NHS (4:4.8mg/mL), 1 is stirred ~2 it is small when；
3) ZnS quantum dot after 20mg carboxyl modifieds, after ultrasonic dissolution, measure are added into the hydroxyl magnetic fluid after activation Fluorescence intensity, when reaction 20 is small in the stirring that temperature is 30 degrees Celsius；
4) products therefrom is centrifuged, collects precipitation, washed three times with ethanol/water mixed solution；Finally, gained is produced Thing, is put into refrigerator freezing after twenty minutes, by product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, under 4 degrees Celsius of environment Preserve, obtain magnetic fluorescence nano composite material.
Embodiment 6：
The conjunction of carboxyl modified magnetic Nano material and the magnetic fluorescence nano composite material of amido modified CdTe quantum Into：
1) magnetic particle of 20mg carboxyl modifieds is taken, adds the buffer solution (citric acid-trisodium citrate buffer body of 20mL System, pH=6.4) magnetic fluid of 1mg/mL is configured to, it is spare；
2) 2mL magnetic fluids are taken, add 50mL activating reagents, wherein activating reagent EDC/NHS (4:4.8mg/mL), 1 is stirred ~2 it is small when；
3) added into the hydroxyl magnetic fluid after activation 20mg it is amido modified after CdTe quantum, after ultrasonic dissolution, survey Fluorescence intensity is determined, when reaction 20 is small in the stirring that temperature is 30 DEG C；
4) products therefrom is centrifuged, collects precipitation, washed three times with ethanol/water mixed solution；Finally, gained is produced Thing, is put into refrigerator freezing after twenty minutes, by product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, under 4 degrees Celsius of environment Preserve, obtain magnetic fluorescence nano composite material.
Embodiment 7：
The conjunction of the magnetic fluorescence nano composite material of the ZnS quantum dot of carboxyl modified magnetic Nano material and hydroxyl modified Into：
1) magnetic particle of 20mg carboxyl modifieds is taken, adds the buffer solution (citric acid-trisodium citrate buffer body of 20mL System, pH=6.4) magnetic fluid of 1mg/mL is configured to, it is spare；
2) 2mL magnetic fluids are taken, add 50mL activating reagents, wherein activating reagent EDC/NHS (4:4.8mg/mL), 1 is stirred ~2 it is small when；
3) ZnS quantum dot after 20mg hydroxyl modifieds, after ultrasonic dissolution, measure are added into the hydroxyl magnetic fluid after activation Fluorescence intensity, when reaction 20 is small in the stirring that temperature is 30 degrees Celsius；
4) products therefrom is centrifuged, collects precipitation, washed three times with ethanol/water mixed solution；Finally, gained is produced Thing, is put into refrigerator freezing after twenty minutes, by product be placed in centrifuge tube vacuum freeze drying 4~5 it is small when, under 4 degrees Celsius of environment Preserve, obtain magnetic fluorescence nano composite material.
Synthesizing magnetic fluorescent nano material has optimal performance in embodiment 1, its concrete application is as follows：
The magnetic flourescent nano material for magnetic of synthesis is taken, is configured to the solution of 0.5mg/mL, carries out fluorescent strength determining, Ke Yiguan Measure strong absworption peak.Magnetic absorption is carried out after ten minutes to sample, the fluorescence intensity of supernatant is measured, it is strong to can observe fluorescence Degree is basic to disappear.Meanwhile as control, stand after ten minutes, measure solution fluorescence has no significant change, provable, this method Magnetic-particle is successfully combined with quantum dot, a kind of new magnetic fluorescence nano composite material has been prepared.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention.

Claims (8)

  1. A kind of 1. preparation method of the magnetic Nano material of carboxyl modified, it is characterised in that：
    1) a certain amount of iron chloride (FeCl is weighed3), trisodium citrate (C6H5O7Na3), sodium acetate (CH3COONa), its mass ratio Scope is iron chloride：Trisodium citrate：Sodium acetate=2:1:2~5:1:5；
    2) iron chloride and trisodium citrate are added in a certain amount of ethylene glycol solution, ultrasonic dissolution；
    3) it is slowly added to sodium acetate and is stirred continuously, above-mentioned product is put into reaction kettle, reaction kettle inserts 200 degrees Celsius of baking ovens Heat 12 it is small when after, be cooled to room temperature；
    4) products therefrom puts refrigerator freezing after twenty minutes, and it is small that the black product of acquisition is placed in centrifuge tube vacuum freeze drying 4~5 When, preserved afterwards under 4 degrees Celsius of environment.
  2. A kind of 2. preparation method of amido modified zinc sulphide fluorescence quantum nano material, it is characterised in that：
    1) a certain amount of Zinc vitriol (ZnSO is weighed4·7H2O), four hydration manganous chloride (MnCl2·4H2O), four hydration Vulcanized sodium (Na2S·4H2O), its quality is Zinc vitriol than scope：Four hydration manganous chloride：Four hydrated sodium sulfide=12: 1:12~25:1:25；
    2) Zinc vitriol is added in a certain amount of deionized water with four hydration manganous chloride and dissolved, mixture is in nitrogen It is stirred at room temperature under protection 30 minutes；
    3) four hydrated sodium sulfides are slowly added into solution dropwise, continue at room temperature stirring 2~3 it is small when；
    4) above-mentioned reaction product is centrifuged, collects precipitation, precipitation washs three times (1 with ethanol/water mixed solution:1)；
    5) in mass ratio it is mercaptoethylmaine (MEA)：ZnS quantum dots=1:1.25~1:1.5 weigh a certain amount of sulfydryl second Amine, ZnS quantum dots, are subsequently added to dissolve in a certain amount of ethanol, when room temperature lucifuge stirring reaction 10 is small, up to amino The quantum dot of modification.
  3. A kind of 3. preparation method of magnetic fluorescence nano composite material, it is characterised in that：
    1) in mass ratio scope be carboxyl modified ferroso-ferric oxide (Fe3O4)：1- (3- dimethylamino-propyls) -3- ethyls carbon two Inferior amine salt hydrochlorate (EDC)：N-hydroxysuccinimide (NHS)=1:80:150~1:120:200, weigh a certain amount of Fe3O4、 EDC and NHS, is added in citrate buffer solution, when stir-activating 1~2 is small；
    2) added into the EDC/NHS reaction systems after activation it is a certain amount of it is amido modified after ZnS quantum dot, wherein ZnS amounts Sub- point：Fe3O4Magnetic-particle quality is 8 than scope:1~15:1, after ultrasonic dissolution, when stirring reaction 20 is small under 30 degrees Celsius；
    3) reaction product obtained is washed three times with ethanol/water mixed solution, and Magneto separate collects precipitation；
    4) products therefrom puts refrigerator freezing after twenty minutes, and it is small that acquisition yellowish-brown product is placed in centrifuge tube vacuum freeze drying 4~5 When, preserved afterwards under 4 degrees Celsius of environment.
  4. A kind of 4. method for preparing magnetic fluorescence nano composite material according to claim 1, it is characterised in that：Iron chloride： Trisodium citrate：Sodium acetate quality is 2 than scope:1:2~5:1:5, optimum condition 19.5:6:36.
  5. 5. a kind of method for preparing amido modified zinc sulphide fluorescence quantum nano material according to claim 2, it is special Sign is：Zinc vitriol：Four hydration manganous chloride：Four hydrated sodium sulfide quality are 12 than scope:1:12~25:1:25, Optimum condition is 18:1:18.
  6. 6. a kind of method for preparing amido modified zinc sulphide fluorescence quantum nano material according to claim 2, it is special Sign is：Mercaptoethylmaine：ZnS quantum dots quality is 1 than scope:1.25~1:1.5, optimum condition 1:1.3.
  7. A kind of 7. method for preparing magnetic fluorescence nano composite material according to claim 3, it is characterised in that：Four oxidations three Iron：1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides：N-hydroxysuccinimide quality is 1 than scope:80: 150~1:120:200, optimum condition 1:100:120.
  8. A kind of 8. method for preparing magnetic fluorescence nano composite material according to claim 3, it is characterised in that：Zinc sulphide： Ferroso-ferric oxide quality is 100 than scope:1~150:1, optimum condition 12.5:1.
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CN108659822A (en) * 2018-06-29 2018-10-16 徐州得铸生物科技有限公司 A kind of preparation method of novel magnetic nano-luminescent material
CN108840371A (en) * 2018-06-29 2018-11-20 复旦大学 A kind of preparation method of ferroso-ferric oxide/manganese dioxide complex microsphere
CN112349508A (en) * 2020-12-08 2021-02-09 安徽泰龙锌业有限责任公司 Method for preparing magnetic material by using zinc-containing waste material
CN113203779A (en) * 2021-04-23 2021-08-03 北京理工大学 Magnetic Fe3O4Preparation of molecular imprinting electrochemical sensor and detection method of succinic acid

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CN1831079A (en) * 2006-04-20 2006-09-13 上海交通大学 Fluorescent, magnetic, multi-functional nanometer material and its prepn. method
CN101383212A (en) * 2008-06-30 2009-03-11 上海师范大学 Super paramagnetic/fluorescent nano particle, preparation and application thereof
CN105237677A (en) * 2015-10-27 2016-01-13 江苏大学 Preparation method and application for Mn-doped ZnS quantum-dot surface imprinting fluorescent probe

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CN1831079A (en) * 2006-04-20 2006-09-13 上海交通大学 Fluorescent, magnetic, multi-functional nanometer material and its prepn. method
CN101383212A (en) * 2008-06-30 2009-03-11 上海师范大学 Super paramagnetic/fluorescent nano particle, preparation and application thereof
CN105237677A (en) * 2015-10-27 2016-01-13 江苏大学 Preparation method and application for Mn-doped ZnS quantum-dot surface imprinting fluorescent probe

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108659822A (en) * 2018-06-29 2018-10-16 徐州得铸生物科技有限公司 A kind of preparation method of novel magnetic nano-luminescent material
CN108840371A (en) * 2018-06-29 2018-11-20 复旦大学 A kind of preparation method of ferroso-ferric oxide/manganese dioxide complex microsphere
CN112349508A (en) * 2020-12-08 2021-02-09 安徽泰龙锌业有限责任公司 Method for preparing magnetic material by using zinc-containing waste material
CN113203779A (en) * 2021-04-23 2021-08-03 北京理工大学 Magnetic Fe3O4Preparation of molecular imprinting electrochemical sensor and detection method of succinic acid

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