CN106905696B - A kind of synthetic method of magnetism phosphorescence Microcystin imprinted material - Google Patents
A kind of synthetic method of magnetism phosphorescence Microcystin imprinted material Download PDFInfo
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Abstract
The present invention provides a kind of synthetic methods of magnetic phosphorescence Microcystin imprinted material, it include: that crosslinking agent is added in the aqueous solution of magnetic nanoparticle in (1), mechanical stirring, Mn is added and adulterates ZnS phosphorescence quantum dot, stirring is crosslinked magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot to obtain nanocomposite；Magneto separate；(2) nanocomposite and algae toxin is soluble in water, polyethyleneimine and crosslinking agent is added in ultrasound, stirs, and the magnetic nanoparticle surface in nanocomposite forms first layer algae toxin imprinted material, Magneto separate purification；First layer algae toxin imprinted material is repeated into n times above step (2), forms multilayer algae toxin imprinted material.(3) dry by multilayer algae toxin imprinted material refluxing extraction template molecule algae toxin, obtain algae toxin molecular engram nanocomposite.Material of the present invention has the function of that Magnetic Isolation enrichment function, phosphorescence detection function and catalysis are removed to object algae toxin.
Description
Technical field
The invention belongs to technical field of nanometer material preparation more particularly to a kind of magnetic phosphorescence Microcystin imprinted materials
Synthetic method.
Background technique
Magnetic nano-particle (MNP) is a kind of novel nano magnetic material, and relative to common magnetic-particle material, it has
Have property specific to nano material: its partial size is small, large specific surface area, therefore selective adsorption capacity increases, when adsorption equilibrium
Between greatly shorten；With good magnetic responsiveness and superparamagnetism, it can assemble and position under magnetic field；Physicochemical properties are steady
It is fixed, there is certain mechanical strength and chemical stability, be resistant to the degradation of certain density acid-base solution and microorganism；Pass through
To the modified functional group for having various active in its surface, special molecular can also be coupled.Currently, researcher is opened both at home and abroad
The related work that magnetic nanoparticle surface molecule print is extracted and detected for object is opened up.These magnetic nanoparticle tables
The method of face molecular engram can separate object from complex sample system, but since imprinted material itself does not have inspection
Brake generally requires to evaluate imprinting effect using the characteristic or round-about way of object itself.Magnetic nano-particle
Such as Fe3O4、Fe2O3、BiFeO3Deng, other than having excellent separation function, and Fenton-like catalysis well
Agent can be used for the catalytic degradation of certain contaminant molecules in water.
Quantum dot be partial size be less than or close to exciton Bohr radius semiconductor nano crystal grain.Although quantum dot fluorescence
The application of matter is very extensive, the phosphorescence of quantum dot and its obtained concern of application in analysis detection still compared with
It is few.Based on the room temperature phosphorimetry sensor of Mn doping ZnS quantum point in addition to have transmission spectra analytic approach it is quick, it is easy, sensitive and
Except economic feature, highly selective, hypotoxicity, strong anti-interference ability outstanding advantage be that the room temperature phosphorimetry of quantum dot senses
Wide application prospect is opened up.
Summary of the invention
For the above problem in background technique, the main purpose of the present invention is to provide a kind of magnetic phosphorescence microcystins
Phosphorescence quantum dot is assembled in magnetic nano-particle surface, has obtained having magnetic to algae toxin by the synthetic method of plain imprinted material
Property separation and concentration, phosphorescence detection and remove function molecular engram material.
In order to achieve the above object, the present invention adopts the following technical scheme: a kind of magnetism phosphorescence Microcystin trace material
The synthetic method of material, which comprises
(1) crosslinking agent is added in the aqueous solution of magnetic nanoparticle, then Mn doping is added in mechanical stirring 10-15h
ZnS phosphorescence quantum dot continues to stir 2-24h, and magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot are crosslinked to obtain nanometer and be answered
Condensation material；By Magneto separate, removes the Mn not with magnetic nanoparticle crosslinking and adulterate ZnS phosphorescence quantum dot；
(2) nanocomposite obtained in step (1) and algae toxin is soluble in water, then ultrasonic 2-20min is added
Polyethyleneimine and crosslinking agent continue to stir 2-24h, the extra amino of the phosphorescence quantum dot surface in the nanocomposite
It is crosslinked with the amino of polyethyleneimine, the magnetic nanoparticle surface in the nanocomposite forms first layer algae toxin print
Mark material, product are purified by Magneto separate；The first layer algae toxin imprinted material is repeated into n times above step (2), in magnetism
Nano grain surface forms multilayer algae toxin imprinted material；
(3) dry by the resulting multilayer algae toxin imprinted material refluxing extraction template molecule algae toxin of step (2), it obtains
Algae toxin molecular engram nanocomposite.
As a further preference, in the step (1), when the dosage of magnetic nanoparticle is 1-10mg, crosslinking agent
Dosage is 0.5-5mL, and the dosage of Mn doping ZnS quantum point is 5-50mg.
As a further preference, in the step (2), the mass ratio of the nanocomposite and algae toxin are as follows:
0.4-40, the mass ratio of the nanocomposite and polyethyleneimine are as follows: 2.5-250.
As a further preference, in the step (1) and (2), the crosslinking agent is selected from glutaraldehyde, isocyanates and second
Alkene sulfone.
As a further preference, in the step (3), the solvent of the reflux includes the first solvent and the second solvent
Mixed liquor, first solvent be selected from ethyl alcohol, second solvent be selected from acetonitrile, water and toluene.
As a further preference, in the step (3), the volume ratio of first solvent and the second solvent is 8-10:
1。
As a further preference, in the step (1), the synthetic method of the magnetic nanoparticle includes: by chlorination
Iron is added in ethylene glycol solution, and sodium acetate and polyethyleneimine is then added, and stirring obtains uniform solution, then by institute
It states solution and reacts 2-10h at 100-200 DEG C, through cooling, washing is dried to obtain the magnetic nanoparticle.
As a further preference, the molecular weight of the polyethyleneimine is selected from 1800,6000 and 12000.
As a further preference, in the step (1), the synthesis of the Mn doping ZnS quantum point includes: (a) by Zn
(Ac)2With Mn (Ac)2Ultrasonic dissolution in deionized water, is stirred at room temperature down, after inert gas shielding 10-100 minutes, is completely cutting off
Na is slowly added under conditions of air2S aqueous solution, reactant the reaction was continued 2-10h, obtains Mn doping ZnS quantum point, washs,
It is dried in vacuo spare；(b) the Mn doping ZnS quantum point is dissolved in dehydrated alcohol, cysteamine is added, continue to stir 20-
30h, obtained product are purified with dehydrated alcohol, are centrifuged off excessive half Guang ammonia, product drying.
As a further preference, the Zn (Ac)2With Mn (Ac)2The molar ratio of dosage are as follows: 10:1, the Zn (Ac)2
And Na2The molar ratio of S dosage are as follows: 2-10:1.
The beneficial effects of the present invention are: the present invention hands over magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot particle
Connection obtains nanocomposite, then using nanocomposite and polyethyleneimine as function monomer, using algae toxin as template point
Son, by crosslinking agent, independently molecular engram nanocomposite is prepared in dress layer by layer.Since nanometer molecular imprinting material has
Higher specific surface area, big multiple binding sites are located near or at material surface, and the present invention is expected to really solve conventional molecular trace
The difficulty encountered is the algae toxin trace for preparing high density imprinted sites, highly selective, high-affinity and fast binding kinetics
The synthetic method of nano material.Moreover, the molecular engram material that is formed of the present invention is to object algae toxin while having magnetic point
Function is removed from enrichment function, phosphorescence detection function and catalysis.
Detailed description of the invention
Fig. 1 is the electron microscope of magnetic nanoparticle of the embodiment of the present invention.
Fig. 2 is the phosphorescence map of Mn of embodiment of the present invention doping ZnS quantum point particle.
Specific embodiment
The present invention solves conventional molecular by providing a kind of synthetic method of magnetic phosphorescence Microcystin imprinted material
The difficulty that trace encounters, obtained molecular engram material is to object algae toxin while having Magnetic Isolation enrichment function, phosphorescence
Function is removed in detection function and catalysis.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is:
The synthetic method of magnetism phosphorescence Microcystin imprinted material of the embodiment of the present invention, which comprises
(1) crosslinking agent is added in the aqueous solution of magnetic nanoparticle, then Mn doping is added in mechanical stirring 10-15h
ZnS quantum dot continues to stir 2-24h, magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot is crosslinked to obtain nano combined
Material；By Magneto separate, removes the Mn not with magnetic nanoparticle crosslinking and adulterate ZnS phosphorescence quantum dot；
(2) nanocomposite obtained in step (1) and algae toxin is soluble in water, then ultrasonic 2-20min is added
Polyethyleneimine and crosslinking agent continue to stir 2-24h, the extra amino of the phosphorescence quantum dot surface in the nanocomposite
It is crosslinked with the amino of polyethyleneimine, the magnetic nanoparticle surface in the nanocomposite forms first layer algae toxin print
Mark material, product are purified by Magneto separate；The first layer algae toxin imprinted material is repeated into n times above step (2), in magnetism
Nano grain surface forms multilayer algae toxin imprinted material.
(3) dry by the resulting multilayer algae toxin imprinted material refluxing extraction template molecule algae toxin of step (2), it obtains
Algae toxin molecular engram nanocomposite.
The magnetic nanoparticle and Mn doping ZnS quantum point can be prepared by conventional method, it also may be preferable for use this hair
Bright hydro-thermal method synthesizes the magnetic nanoparticle, and selects the synthesis of amido modified Mn doping ZnS quantum point.
In the step (1) and (2), the crosslinking agent can be selected from glutaraldehyde, isocyanates and vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan).
In the step (3), the molecular weight of the polyethyleneimine can be selected from 1800,6000 and 12000.
In the step (3), the solvent of the reflux may include the mixed liquor of the first solvent and the second solvent, described
One solvent is selected from ethyl alcohol, and second solvent is selected from acetonitrile, water and toluene.
The embodiment of the present invention is investigated the parameters such as usage ratio and reaction time, temperature, purification between each substance, makes every effort to
Reach optimal synthetic effect.
In order to which above and other purpose, feature and the advantage of the present invention can be clearer and more comprehensible, several implementations are cited below particularly
Example, to illustrate the synthetic method of magnetism phosphorescence Microcystin imprinted material of the present invention.
Embodiment 1
The synthetic method of the magnetic phosphorescence Microcystin imprinted material of the embodiment of the present invention 1, includes the following steps: (1) water
Thermal method synthesizing magnetic nano particle: 0.15g iron chloride is added in 50mL ethylene glycol solution, then be added 1g sodium acetate and
Solution magneton is stirred 1h, obtains uniform solution, be then transferred to solution instead by the polyethyleneimine that 0.25g molecular weight is 1800
It answers in kettle, 200 DEG C of reaction 8h.It after reaction, through cooling, washes 3 times, ethyl alcohol is washed 1 time, and vacuum drying obtains magnetic nano-particle
Dried powder.Fig. 1 is the electron microscope of magnetic nanoparticle of the embodiment of the present invention.
(2) synthesis of amido modified Mn doping ZnS quantum point: (a) in the three-necked flask of 100mL, by 50mmol Zn
(Ac)2With 5mmol Mn (Ac)2Ultrasonic dissolution is in 40ml deionized water.Under room temperature magnetic agitation, after nitrogen protection 30 minutes,
The 50mmol Na of 10mL is added under conditions of isolation air with syringe2S aqueous solution, reactant the reaction was continued 5h, obtained Mn
Doping ZnS quantum point is respectively washed 3 times with second alcohol and water, is dried in vacuo spare.(b) 0.1g Mn doping ZnS quantum point is dissolved in 50ml
Then 2.5mmol cysteamine is added in dehydrated alcohol, continue stirring for 24 hours.Product is purified with dehydrated alcohol, is centrifuged off excessive
Half Guang ammonia, product vacuum drying are spare.Fig. 2 is the phosphorescence map of Mn of embodiment of the present invention doping ZnS quantum point particle.
(3) glutaraldehyde cross-linking magnetic nanoparticle and Mn adulterate ZnS phosphorescence quantum dot: in the magnetic Nano of 100mg/L
50% glutaraldehyde of 2mL is added in the 50mL aqueous solution of grain, then the Mn doping ZnS quantum point of 20mg is added in mechanical stirring 12h,
Continue to stir 12h, by magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinking.By Magneto separate, removing is not received with magnetism
The Mn of rice grain crosslinking adulterates ZnS phosphorescence quantum dot.
(4) autonomous dress prepares the synthesis of Microcystin molecular engram nanocomposite layer by layer: with receiving in step (3)
The polyethyleneimine that nano composite material and molecular weight are 1800 passes through penta 2 using algae toxin as template molecule as function monomer
Independently dress prepares molecular engram nanocomposite to aldehyde layer by layer.By the nanocomposite synthesized in 10mg step (3) and 2mg algae
Toxin is dissolved in 20mL pure water, ultrasonic 10min, and 0.1g polyethyleneimine and 50% glutaraldehyde of 2mL is then added, continues to stir
Mix 12h, the amino of the extra amino of phosphorescence quantum dot surface and polyethyleneimine passes through glutaraldehyde cross-linking, magnetic nanoparticle table
Face forms first layer algae toxin imprinted material.Then, product is purified by Magneto separate.(b) it is repeated 4 times above step, magnetism is received
Rice grain surface forms the 4th layer of algae toxin imprinted material.
(5) elution is handled: polymerization reaction is sufficiently completed, and obtains algae toxin molecular engram nanocomposite with Magneto separate,
Resulting trace nanocomposite flows back repeatedly in the ethanol/acetonitrile mixed liquor that volume ratio is 9:1 to extract template molecule algae
Toxin until extracting solution at 245nm without UV absorption, dry under product vacuum room temperature to constant weight, algae toxin molecule can be obtained
Trace nanocomposite.
Embodiment 2
The synthetic method of the magnetic phosphorescence Microcystin imprinted material of the embodiment of the present invention 2, includes the following steps:
(1) hydro-thermal method synthesizing magnetic nano particle: 0.4g iron chloride is added in 50mL ethylene glycol solution, is then added
Solution magneton is stirred 1h, obtains uniform solution by the polyethyleneimine that 3g sodium acetate and 0.8g molecular weight are 6000, then will be molten
Liquid is transferred in reaction kettle, 150 DEG C of reaction 7h.It after reaction, through cooling, washes 3 times, ethyl alcohol is washed 1 time, and vacuum drying obtains magnetism
The dried powder of nanoparticle.
(2) synthesis of amido modified Mn doping ZnS quantum point: (a) in the three-necked flask of 100mL, by 30mmol Zn
(Ac)2With 3mmol Mn (Ac)2Ultrasonic dissolution is in 30ml deionized water.Under room temperature magnetic agitation, after nitrogen protection 50 minutes,
The 50mmol Na of 10mL is added under conditions of isolation air with syringe2S aqueous solution, reactant the reaction was continued 4h, obtained Mn
Doping ZnS quantum point is respectively washed 3 times with second alcohol and water, is dried in vacuo spare.(b) 0.4g Mn doping ZnS quantum point is dissolved in 35ml
Then 6mmol cysteamine is added in dehydrated alcohol, continue stirring for 24 hours.Product is purified with dehydrated alcohol, is centrifuged off excessive half
Guang ammonia, product vacuum drying are spare.
(3) isocyanate-crosslinked magnetic nanoparticle and Mn adulterate ZnS phosphorescence quantum dot: in the magnetic Nano of 100mg/L
1mL isocyanates is added in the 30mL aqueous solution of particle, then the Mn doping ZnS quantum point of 10mg is added in mechanical stirring 12h,
Continue to stir 14h, by magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinking.By Magneto separate, removing is not received with magnetism
The Mn of rice grain crosslinking adulterates ZnS phosphorescence quantum dot.
(4) autonomous dress prepares the synthesis of Microcystin molecular engram nanocomposite layer by layer: with receiving in step (3)
The polyethyleneimine that nano composite material and molecular weight are 6000 is as function monomer, using algae toxin as template molecule, by being crosslinked
Independently dress prepares molecular engram nanocomposite to oxidant layer layer.By the nanocomposite synthesized in 7mg step (3) and 2mg algae
Toxin is dissolved in 50mL pure water, ultrasonic 14min, and 0.2g polyethyleneimine and 1.5mL isocyanates is then added, continues to stir
For the amino of 10h, the extra amino of phosphorescence quantum dot surface and polyethyleneimine by being crosslinked, magnetic nanoparticle surface forms the
One layer of algae toxin imprinted material.Then, product is purified by Magneto separate.(b) above step, magnetic nanoparticle table are repeated 4 times
Face forms the 4th layer of algae toxin imprinted material.
(5) elution is handled: polymerization reaction is sufficiently completed, and obtains algae toxin molecular engram nanocomposite with Magneto separate,
Resulting trace nanocomposite repeatedly volume ratio be 8:1 ethanol/water reflux with extract template molecule algae toxin until
Extracting solution without UV absorption, is dried to constant weight under product vacuum room temperature at 245nm, algae toxin molecular engram nanometer can be obtained
Composite material.
Embodiment 3
The synthetic method of the magnetic phosphorescence Microcystin imprinted material of the embodiment of the present invention 3, includes the following steps:
(1) hydro-thermal method synthesizing magnetic nano particle: 0.8g iron chloride is added in 50mL ethylene glycol solution, is then added
Solution magneton is stirred 1h, obtains uniform solution, then by the polyethyleneimine that 0.4g sodium acetate and 0.54 molecular weight are 12000
Solution is transferred in reaction kettle, 120 DEG C of reaction 4h.After reaction, through cooling, wash 3 times, ethyl alcohol is washed 1 time, and vacuum drying obtains
The dried powder of magnetic nano-particle.
(2) synthesis of amido modified Mn doping ZnS quantum point: (a) in the three-necked flask of 100mL, by 47mmol Zn
(Ac)2With 6.2mmol Mn (Ac)2Ultrasonic dissolution is in 43ml deionized water.Under room temperature magnetic agitation, after nitrogen protection 30 minutes,
The 50mmol Na of 7mL is added with syringe in the absence of air conditions2S aqueous solution, reactant the reaction was continued 7.6h, obtains
Mn doping ZnS quantum point respectively washed 3 times with second alcohol and water, be dried in vacuo it is spare.(b) 0.25g Mn doping ZnS quantum point is molten
In 35ml dehydrated alcohol, 4.8mmol cysteamine is then added, continues stirring for 24 hours.Product is purified with dehydrated alcohol, is centrifuged off
Excessive half Guang ammonia, product vacuum drying are spare.
(3) vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) crosslinking magnetic nanoparticle and Mn adulterate ZnS phosphorescence quantum dot: in the magnetic Nano of 100mg/L
3.5mL vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) is added in the 34mL aqueous solution of grain, then the Mn doping ZnS quantum point of 35mg is added in mechanical stirring 12h, after
Continuous stirring 10h, by magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinking.By Magneto separate, do not remove not and magnetic Nano
The Mn of particle crosslinking adulterates ZnS phosphorescence quantum dot.
(4) autonomous dress prepares the synthesis of Microcystin molecular engram nanocomposite layer by layer: with receiving in step (3)
The polyethyleneimine that nano composite material and molecular weight are 12000 is as function monomer, using algae toxin as template molecule, by being crosslinked
Independently dress prepares molecular engram nanocomposite to oxidant layer layer.The nanocomposite and 2.8mg that will be synthesized in 12mg step (3)
Algae toxin is dissolved in 76mL pure water, ultrasonic 12min, and 0.25g polyethyleneimine and 3.2mL vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) is then added, continues to stir
Mix 15h, by being crosslinked, magnetic nanoparticle surface is formed the amino of the extra amino of phosphorescence quantum dot surface and polyethyleneimine
First layer algae toxin imprinted material.Then, product is purified by Magneto separate.(b) above step, magnetic nanoparticle are repeated 5 times
Surface forms layer 5 algae toxin imprinted material.
(5) elution is handled: polymerization reaction is sufficiently completed, and obtains algae toxin molecular engram nanocomposite with Magneto separate,
Resulting trace nanocomposite is repeatedly straight to extract template molecule algae toxin in the ethanol/toluene reflux that volume ratio is 10:1
To extracting solution without UV absorption at 245nm, dries under product vacuum room temperature to constant weight, algae toxin molecular engram can be obtained and receive
Nano composite material.
Technical solution in above-mentioned the embodiment of the present application, at least have the following technical effects or advantages:
The present invention is crosslinked magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot particle to obtain nanocomposite,
Again using nanocomposite and polyethyleneimine as function monomer, using algae toxin as template molecule, by crosslinking agent layer by layer from
Molecular engram nanocomposite is prepared in main dress.Due to nanometer molecular imprinting material specific surface area with higher, mostly
Binding site is located near or at material surface, and the present invention is expected to really solve the difficulty that conventional molecular trace encounters, and has obtained height
The algae toxin trace nano material of density imprinted sites, highly selective, high-affinity and fast binding kinetics.Moreover, this hair
The molecular engram material of bright formation has Magnetic Isolation enrichment function, phosphorescence detection function simultaneously to object algae toxin and urges
Change and removes function.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to encompass these modification and variations and exists
It is interior.
Claims (10)
1. a kind of synthetic method of magnetism phosphorescence Microcystin imprinted material, it is characterised in that: the described method includes:
(1) crosslinking agent is added in the aqueous solution of magnetic nanoparticle, then mechanical stirring 10-15h is added Mn and adulterates ZnS phosphorus
Light quanta point continues to stir 2-24h, magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot is crosslinked to obtain nano combined
Material；By Magneto separate, removes the Mn not with magnetic nanoparticle crosslinking and adulterate ZnS phosphorescence quantum dot；
(2) nanocomposite obtained in step (1) and algae toxin is soluble in water, then poly- second is added in ultrasonic 2-20min
Alkene imines and crosslinking agent continue to stir 2-24h, the extra amino of the phosphorescence quantum dot surface in the nanocomposite and poly-
The amino of aziridine is crosslinked, and the magnetic nanoparticle surface in the nanocomposite forms first layer algae toxin trace material
Material, product are purified by Magneto separate；The first layer algae toxin imprinted material is repeated into n times above step (2), in magnetic Nano
Particle surface forms multilayer algae toxin imprinted material；
(3) dry by the resulting multilayer algae toxin imprinted material refluxing extraction template molecule algae toxin of step (2), obtain magnetism
Phosphorescence Microcystin imprinted material.
2. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that: described
In step (1), when the dosage of magnetic nanoparticle is 1-10mg, crosslinking agent additive amount is 0.5-5mL, and Mn adulterates ZnS phosphorescence
The dosage of quantum dot is 5-50mg.
3. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that: described
In step (2), the mass ratio of the nanocomposite and algae toxin are as follows: 0.4-40, the nanocomposite and polyethylene
The mass ratio of imines are as follows: 2.5-250.
4. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that: described
In step (1) and (2), the crosslinking agent is selected from glutaraldehyde, isocyanates and vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan).
5. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that: described
In step (3), the solvent of the reflux includes the mixed liquor of the first solvent and the second solvent, and first solvent is selected from second
Alcohol, second solvent are selected from acetonitrile, water and toluene.
6. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 5, it is characterised in that: described
In step (3), the volume ratio of first solvent and the second solvent is 8-10:1.
7. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that: described
In step (1), the synthetic method of the magnetic nanoparticle includes: that iron chloride is added in ethylene glycol solution, is then added
Sodium acetate and polyethyleneimine, stirring, obtain uniform solution, the solution are then reacted 2-10h at 100-200 DEG C,
Through cooling, washing is dried to obtain the magnetic nanoparticle.
8. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 1 or claim 7, it is characterised in that:
The molecular weight of the polyethyleneimine is selected from 1800,6000 and 12000.
9. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that: described
In step (1), the synthesis of Mn doping ZnS phosphorescence quantum dot includes: (a) by Zn (Ac)2With Mn (Ac)2Ultrasonic dissolution is being gone
It in ionized water, is stirred at room temperature down, after inert gas shielding 10-100 minutes, is slowly added to Na in the absence of air conditions2S water
Solution, reactant the reaction was continued 2-10h, obtains Mn doping ZnS quantum point, washs, and is dried in vacuo spare；(b) Mn is mixed
Miscellaneous ZnS quantum dot is dissolved in dehydrated alcohol, and cysteamine is added, and continues to stir 20-30h, and obtained product is purified with dehydrated alcohol,
It is centrifuged off excessive half Guang ammonia, product drying.
10. the synthetic method of magnetism phosphorescence Microcystin imprinted material according to claim 9, it is characterised in that: institute
State Zn (Ac)2With Mn (Ac)2The molar ratio of dosage are as follows: 10:1, the Zn (Ac)2And Na2The molar ratio of S dosage are as follows: 2-
10:1。
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