CN106905696A - A kind of synthetic method of magnetic phosphorescence Microcystin imprinted material - Google Patents
A kind of synthetic method of magnetic phosphorescence Microcystin imprinted material Download PDFInfo
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Abstract
The invention provides a kind of synthetic method of magnetic phosphorescence Microcystin imprinted material, including：(1) crosslinking agent is added in the aqueous solution of magnetic nanoparticle, mechanical agitation adds Mn doping ZnS phosphorescence quantum dots, and magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinkings are obtained nano composite material by stirring；Magneto separate；(2) nano composite material and Algae toxins is soluble in water, ultrasound adds polyethyleneimine and crosslinking agent, stirring, and the magnetic nanoparticle surface in nano composite material forms ground floor Algae toxins imprinted material, Magneto separate purification；Ground floor Algae toxins imprinted material is repeated into n times above step (2), multilayer Algae toxins imprinted material is formed.(3) by multilayer Algae toxins imprinted material refluxing extraction template molecule Algae toxins, dry, obtain Algae toxins molecular engram nano composite material.There is material of the present invention Magnetic Isolation enrichment function, phosphorescence detection function and catalysis to remove function to object Algae toxins.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, more particularly to a kind of magnetic phosphorescence Microcystin imprinted material
Synthetic method.
Background technology
Magnetic nano-particle (MNP) is a kind of new nano magnetic material, and relative to common magnetic-particle material, it has
There is property specific to nano material：Its particle diameter is small, specific surface area big, therefore selective adsorption capacity increases, during adsorption equilibrium
Between greatly shorten；With good magnetic responsiveness and superparamagnetism, can assemble and position under magnetic field；Physicochemical properties are steady
It is fixed, with certain mechanical strength and chemical stability, it is resistant to the degraded of certain density acid-base solution and microorganism；Pass through
Be modified the functional group with various active to its surface, it is also possible to is coupled special molecular.At present, domestic and international researcher is opened
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 because imprinted material does not possess inspection in itself
Brake, generally requires to evaluate imprinting effect using object characteristic in itself or round-about way.Magnetic nano-particle
Such as Fe3O4、Fe2O3、BiFeO3Deng being also good Fenton-like catalysis in addition to possessing excellent separation function
Agent, can be used for the catalytic degradation of some contaminant molecules in water.
Quantum dot is that particle diameter is less than or close to the semiconductor nano crystal grain of exciton Bohr radius.Although quantum dot fluorescence
The application of matter is quite varied, the phosphorescence of quantum dot and its concern that obtains of application in detection is analyzed still compared with
It is few.Room temperature phosphorimetry sensor based on Mn doping ZnS quantum points except possess transmission spectra analytic approach it is quick, easy, sensitive and
Outside economic the characteristics of, its high selectivity, hypotoxicity, the outstanding advantage of strong anti-interference ability are the room temperature phosphorimetry sensing of quantum dot
Wide application prospect is opened up.
The content of the invention
For the above mentioned problem in background technology, it is a primary object of the present invention to provide a kind of magnetic phosphorescence microcystin
The synthetic method of plain imprinted material, magnetic nano-particle surface is assembled in by phosphorescence quantum dot, has obtained possessing magnetic to Algae toxins
Property separation and concentration, phosphorescence detection and remove function molecular engram material.
In order to achieve the above object, the present invention is adopted the following technical scheme that：A kind of magnetic phosphorescence Microcystin trace material
The synthetic method of material, methods described includes：
(1) crosslinking agent, mechanical agitation 10-15h is added to be subsequently adding Mn doping in the aqueous solution of magnetic nanoparticle
ZnS phosphorescence quantum dots, continue to stir 2-24h, and magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinkings are obtained nanometer and answered
Condensation material；By Magneto separate, the Mn doping ZnS phosphorescence quantum dots not being crosslinked with magnetic nanoparticle are removed；
(2) nano composite material and Algae toxins that will be obtained in step (1) are soluble in water, and ultrasonic 2-20min is subsequently adding
Polyethyleneimine and crosslinking agent, continue to stir 2-24h, the unnecessary amino of the phosphorescence quantum dot surface in the nano composite material
Amino with polyethyleneimine is crosslinked, and the magnetic nanoparticle surface in the nano composite material forms ground floor Algae toxins print
Mark material, product is purified by Magneto separate；The ground floor Algae toxins imprinted material is repeated into n times above step (2), in magnetic
Nano grain surface forms multilayer Algae toxins imprinted material；
(3) by the multilayer Algae toxins imprinted material refluxing extraction template molecule Algae toxins obtained by step (2), dry, obtain
Algae toxins molecular engram nano composite material.
As it is further preferably, 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 points is 5-50mg.
As further preferably, in the step (2), the mass ratio of the nano composite material and Algae toxins is：
The mass ratio of 0.4-40, the nano composite material and polyethyleneimine is：2.5-250.
As further preferably, in the step (1) and (2), the crosslinking agent is selected from glutaraldehyde, isocyanates and second
Alkene sulfone.
As further preferably, in the step (3), the solvent of the backflow includes the first solvent and the second solvent
Mixed liquor, first solvent be selected from ethanol, second solvent be selected from acetonitrile, water and toluene.
As further preferably, in the step (3), the volume ratio of first solvent and the second solvent is 8-10：
1。
As further preferably, in the step (1), the synthetic method of the magnetic nanoparticle includes：By chlorination
Iron is added in ethylene glycol solution, is subsequently adding sodium acetate and polyethyleneimine, stirring, homogeneous solution is obtained, then by institute
State solution and react 2-10h at 100-200 DEG C, through cooling, washing is dried to obtain the magnetic nanoparticle.
As further preferably, the molecular weight of the polyethyleneimine is selected from 1800,6000 and 12000.
As further preferably, in the step (1), the synthesis of the Mn doping ZnS quantum points includes：A () is by Zn
(Ac)2With Mn (Ac)2Ultrasonic dissolution in deionized water, is stirred at room temperature down, after inert gas shielding 10-100 minutes, in isolation
Na is slowly added under conditions of air2The S aqueous solution, reactant continues to react 2-10h, obtains Mn doping ZnS quantum points, washs,
Vacuum drying is standby；B be dissolved in the Mn doping ZnS quantum points in absolute ethyl alcohol by (), add cysteamine, continues to stir 20-
30h, the product for obtaining is purified with absolute ethyl alcohol, is centrifuged off half excessive Guang ammonia, product drying.
As further preferred, the Zn (Ac)2With Mn (Ac)2The molar ratio of consumption is：10:1, the Zn (Ac)2
And Na2The molar ratio of S consumptions is：2-10:1.
The beneficial effects of the invention are as follows：The present invention hands over magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dots particles
Connection obtains nano composite material, then is template point with Algae toxins using nano composite material and polyethyleneimine as function monomer
Son, by crosslinking agent, independently dress prepares molecular engram nano composite material layer by layer.Because nanometer molecular imprinting material has
Specific surface area higher, big multiple binding sites is located near or at material surface, and the present invention is expected to really solve conventional molecular trace
The difficulty for running into, is the Algae toxins trace for preparing high density imprinted sites, high selectivity, high-affinity and fast binding kinetics
The synthetic method of nano material.And, the molecular engram material that the present invention is formed has magnetic point simultaneously to object Algae toxins
Function is removed from enrichment function, phosphorescence detection function and catalysis.
Brief description of the drawings
Fig. 1 is the electron microscope of embodiment of the present invention magnetic nanoparticle.
Fig. 2 is the phosphorescence collection of illustrative plates of embodiment of the present invention Mn doping ZnS quantum point particles.
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 runs into, the molecular engram material for obtaining is to object Algae toxins 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 embodiment of the present invention magnetic phosphorescence Microcystin imprinted material, methods described includes：
(1) crosslinking agent, mechanical agitation 10-15h is added to be subsequently adding Mn doping in the aqueous solution of magnetic nanoparticle
ZnS quantum dot, continues to stir 2-24h, and magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinkings are obtained into nano combined
Material；By Magneto separate, the Mn doping ZnS phosphorescence quantum dots not being crosslinked with magnetic nanoparticle are removed；
(2) nano composite material and Algae toxins that will be obtained in step (1) are soluble in water, and ultrasonic 2-20min is subsequently adding
Polyethyleneimine and crosslinking agent, continue to stir 2-24h, the unnecessary amino of the phosphorescence quantum dot surface in the nano composite material
Amino with polyethyleneimine is crosslinked, and the magnetic nanoparticle surface in the nano composite material forms ground floor Algae toxins print
Mark material, product is purified by Magneto separate；The ground floor Algae toxins imprinted material is repeated into n times above step (2), in magnetic
Nano grain surface forms multilayer Algae toxins imprinted material.
(3) by the multilayer Algae toxins imprinted material refluxing extraction template molecule Algae toxins obtained by step (2), dry, obtain
Algae toxins molecular engram nano composite material.
The magnetic nanoparticle and Mn doping ZnS quantum points can be prepared by conventional method, it also may be preferable for use this hair
Bright hydro-thermal method synthesizes the magnetic nanoparticle, and from the synthesis of amido modified Mn doping ZnS quantum points.
In the step (1) and (2), the crosslinking agent may be selected from glutaraldehyde, isocyanates and vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan).
In the step (3), the molecular weight of the polyethyleneimine may be selected from 1800,6000 and 12000.
In the step (3), the solvent of the backflow may include the mixed liquor of the first solvent and the second solvent, described
One solvent is selected from ethanol, 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, the purification between each material, makes every effort to
Reach optimal synthetic effect.
In order to above and other purpose, feature and the advantage of the present invention can be become apparent, number cited below particularly is implemented
Example illustrates the synthetic method of magnetic 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, comprises the following steps：(1) water
Hot method synthesizing magnetic nano particle：0.15g iron chloride is added in 50mL ethylene glycol solutions, be subsequently adding 1g sodium acetates and
0.25g molecular weight is 1800 polyethyleneimine, and solution magneton is stirred into 1h, obtains uniform solution, is then transferred to anti-solution
Answer in kettle, 200 DEG C are reacted 8h.After reaction, through cooling, wash 3 times, ethanol is washed 1 time, and vacuum drying obtains magnetic nano-particle
Dried powder.Fig. 1 is the electron microscope of embodiment of the present invention magnetic nanoparticle.
(2) synthesis of amido modified Mn doping ZnS quantum points：(a) in the there-necked flask of 100mL, by 50mmol Zn
(Ac)2With 5mmol Mn (Ac)2Ultrasonic dissolution is in 40ml deionized waters.Under room temperature magnetic agitation, after nitrogen is protected 30 minutes,
The 50mmol Na of 10mL are added under conditions of isolation air with syringe2The S aqueous solution, reactant continues to react 5h, the Mn for obtaining
Doping ZnS quantum point second alcohol and water is respectively washed 3 times, is vacuum dried standby.B 0.1g Mn doping ZnS quantum points are dissolved in 50ml by ()
Absolute ethyl alcohol, is subsequently adding 2.5mmol cysteamines, continues to stir 24h.Product is purified with absolute ethyl alcohol, is centrifuged off excessive
Half Guang ammonia, product vacuum drying is standby.Fig. 2 is the phosphorescence collection of illustrative plates of embodiment of the present invention Mn doping ZnS quantum point particles.
(3) glutaraldehyde cross-linking magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dots：In the magnetic Nano of 100mg/L
The glutaraldehydes of 2mL 50%, mechanical agitation 12h is added to be subsequently adding the Mn doping ZnS quantum points of 20mg in the 50mL aqueous solution of grain,
Continue to stir 12h, by magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinkings.By Magneto separate, removing is not received with magnetic
The Mn doping ZnS phosphorescence quantum dots of rice grain crosslinking.
(4) autonomous dress prepares the synthesis of Microcystin molecular engram nano composite material layer by layer：With receiving in step (3)
Nano composite material and molecular weight be 1800 polyethyleneimine as function monomer, with Algae toxins as template molecule, by penta 2
Independently dress prepares molecular engram nano composite material to aldehyde layer by layer.By the nano composite material of synthesis and 2mg algaes in 10mg steps (3)
Toxin is dissolved in 20mL pure water, ultrasonic 10min, is subsequently adding 0.1g polyethyleneimines and the glutaraldehydes of 2mL 50%, continues to stir
Mix 12h, the amino of the unnecessary amino of phosphorescence quantum dot surface and polyethyleneimine is by glutaraldehyde cross-linking, magnetic nanoparticle table
Face forms ground floor Algae toxins imprinted material.Then, product is purified by Magneto separate.B () is repeated 4 times above step, magnetic is received
Rice grain surface forms the 4th layer of Algae toxins imprinted material.
(5) wash-out treatment：Polymerisation is fully completed, and Algae toxins molecular engram nano composite material is obtained with Magneto separate,
The trace nano composite material of gained is repeatedly 9 in volume ratio:1 ethanol/acetonitrile mixed-liquor return is extracting template molecule algae
Toxin until extract solution at 245nm without UV absorption, dried to constant weight under product vacuum normal temperature, you can obtain Algae toxins molecule
Trace nano composite material.
Embodiment 2
The synthetic method of the magnetic phosphorescence Microcystin imprinted material of the embodiment of the present invention 2, comprises the following steps：
(1) hydro-thermal method synthesizing magnetic nano particle：0.4g iron chloride is added in 50mL ethylene glycol solutions, is subsequently adding
3g sodium acetates and the polyethyleneimine that 0.8g molecular weight is 6000,1h is stirred by solution magneton, obtains uniform solution, then will be molten
Liquid is transferred in reactor, 150 DEG C of reaction 7h.After reaction, through cooling, wash 3 times, ethanol is washed 1 time, and vacuum drying obtains magnetic
The dried powder of nano-particle.
(2) synthesis of amido modified Mn doping ZnS quantum points：(a) in the there-necked flask of 100mL, by 30mmol Zn
(Ac)2With 3mmol Mn (Ac)2Ultrasonic dissolution is in 30ml deionized waters.Under room temperature magnetic agitation, after nitrogen is protected 50 minutes,
The 50mmol Na of 10mL are added under conditions of isolation air with syringe2The S aqueous solution, reactant continues to react 4h, the Mn for obtaining
Doping ZnS quantum point second alcohol and water is respectively washed 3 times, is vacuum dried standby.B 0.4g Mn doping ZnS quantum points are dissolved in 35ml by ()
Absolute ethyl alcohol, is subsequently adding 6mmol cysteamines, continues to stir 24h.Product is purified with absolute ethyl alcohol, is centrifuged off excessive half
Guang ammonia, product vacuum drying is standby.
(3) isocyanate-crosslinked magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dots：In the magnetic Nano of 100mg/L
1mL isocyanates, mechanical agitation 12h is added to be subsequently adding the Mn doping ZnS quantum points of 10mg in the 30mL aqueous solution of particle,
Continue to stir 14h, by magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinkings.By Magneto separate, removing is not received with magnetic
The Mn doping ZnS phosphorescence quantum dots of rice grain crosslinking.
(4) autonomous dress prepares the synthesis of Microcystin molecular engram nano composite material layer by layer：With receiving in step (3)
Nano composite material and molecular weight be 6000 polyethyleneimine as function monomer, with Algae toxins as template molecule, by crosslinking
The autonomous dress of oxidant layer layer prepares molecular engram nano composite material.By the nano composite material of synthesis and 2mg algaes in 7mg steps (3)
Toxin is dissolved in 50mL pure water, ultrasonic 14min, is subsequently adding 0.2g polyethyleneimines and 1.5mL isocyanates, continues to stir
The amino of 10h, the unnecessary amino of phosphorescence quantum dot surface and polyethyleneimine forms the by crosslinking, magnetic nanoparticle surface
One layer of Algae toxins imprinted material.Then, product is purified by Magneto separate.B () is repeated 4 times above step, magnetic nanoparticle table
Face forms the 4th layer of Algae toxins imprinted material.
(5) wash-out treatment：Polymerisation is fully completed, and Algae toxins molecular engram nano composite material is obtained with Magneto separate,
The trace nano composite material of gained is repeatedly 8 in volume ratio:1 ethanol/water backflow with extract template molecule Algae toxins until
Extract solution, without UV absorption, is dried to constant weight at 245nm under product vacuum normal temperature, you can obtain Algae toxins molecular engram nanometer
Composite.
Embodiment 3
The synthetic method of the magnetic phosphorescence Microcystin imprinted material of the embodiment of the present invention 3, comprises the following steps：
(1) hydro-thermal method synthesizing magnetic nano particle：0.8g iron chloride is added in 50mL ethylene glycol solutions, is subsequently adding
0.4g sodium acetates and the polyethyleneimine that 0.54 molecular weight is 12000,1h is stirred by solution magneton, obtains uniform solution, then
Solution is transferred in reactor, 120 DEG C of reaction 4h.After reaction, through cooling, wash 3 times, ethanol is washed 1 time, and vacuum drying is obtained
The dried powder of magnetic nano-particle.
(2) synthesis of amido modified Mn doping ZnS quantum points：(a) in the there-necked flask of 100mL, by 47mmol Zn
(Ac)2With 6.2mmol Mn (Ac)2Ultrasonic dissolution is in 43ml deionized waters.Under room temperature magnetic agitation, after nitrogen is protected 30 minutes,
The 50mmol Na of 7mL are added with syringe under conditions of air is completely cut off2The S aqueous solution, reactant continues to react 7.6h, obtains
Mn doping ZnS quantum point second alcohol and waters respectively wash 3 times, be vacuum dried it is standby.B () is molten by 0.25g Mn doping ZnS quantum points
In 35ml absolute ethyl alcohols, 4.8mmol cysteamines are subsequently adding, continue to stir 24h.Product is purified with absolute ethyl alcohol, is centrifuged off
Half excessive Guang ammonia, product vacuum drying is standby.
(3) vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) crosslinking magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dots：In the magnetic Nano of 100mg/L
3.5mL vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan)s, mechanical agitation 12h is added to be subsequently adding the Mn doping ZnS quantum points of 35mg in the 34mL aqueous solution of grain, after
Continuous stirring 10h, by magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinkings.By Magneto separate, do not remove not and magnetic Nano
The Mn doping ZnS phosphorescence quantum dots of particle crosslinking.
(4) autonomous dress prepares the synthesis of Microcystin molecular engram nano composite material layer by layer：With receiving in step (3)
Nano composite material and molecular weight be 12000 polyethyleneimine as function monomer, with Algae toxins as template molecule, by crosslinking
The autonomous dress of oxidant layer layer prepares molecular engram nano composite material.By the nano composite material and 2.8mg of synthesis in 12mg steps (3)
Algae toxins are dissolved in 76mL pure water, ultrasonic 12min, are subsequently adding 0.25g polyethyleneimines and 3.2mL vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan)s, continue to stir
Mix 15h, by crosslinking, magnetic nanoparticle surface is formed the amino of the unnecessary amino of phosphorescence quantum dot surface and polyethyleneimine
Ground floor Algae toxins imprinted material.Then, product is purified by Magneto separate.B () is repeated 5 times above step, magnetic nanoparticle
Surface forms layer 5 Algae toxins imprinted material.
(5) wash-out treatment：Polymerisation is fully completed, and Algae toxins molecular engram nano composite material is obtained with Magneto separate,
The trace nano composite material of gained is repeatedly 10 in volume ratio:1 ethanol/toluene backflow is straight to extract template molecule Algae toxins
To extract solution at 245nm without UV absorption, dried to constant weight under product vacuum normal temperature, you can obtain Algae toxins molecular engram and receive
Nano composite material.
Technical scheme in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
Magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dots particle crosslinkings are obtained nano composite material by the present invention,
Again using nano composite material and polyethyleneimine as function monomer, with Algae toxins as template molecule, by crosslinking agent layer by layer from
Main dress prepares molecular engram nano composite material.Because nanometer molecular imprinting material has specific surface area 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 runs into, and has obtained height
The Algae toxins trace nano material of density imprinted sites, high selectivity, high-affinity and fast binding kinetics.And, this hair
The molecular engram material of bright formation has Magnetic Isolation enrichment function, phosphorescence detection function and urges simultaneously to object Algae toxins
Change and remove function.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various changes and modification without departing from the spirit and scope of the present invention.So, if these modifications of the invention and modification
Belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these changes and modification
It is interior.
Claims (10)
1. a kind of synthetic method of magnetic phosphorescence Microcystin imprinted material, it is characterised in that：Methods described includes：
(1) crosslinking agent, mechanical agitation 10-15h is added to be subsequently adding Mn doping ZnS phosphorus in the aqueous solution of magnetic nanoparticle
Light quanta point, continues to stir 2-24h, and magnetic nanoparticle and Mn doping ZnS phosphorescence quantum dot crosslinkings are obtained into nano combined
Material；By Magneto separate, the Mn doping ZnS phosphorescence quantum dots not being crosslinked with magnetic nanoparticle are removed；
(2) nano composite material and Algae toxins that will be obtained in step (1) are soluble in water, and ultrasonic 2-20min is subsequently adding poly- second
Alkene imines and crosslinking agent, continue to stir 2-24h, the unnecessary amino of phosphorescence quantum dot surface in the nano composite material and poly-
The amino crosslinking of aziridine, the magnetic nanoparticle surface in the nano composite material forms ground floor Algae toxins trace material
Material, product is purified by Magneto separate；The ground floor Algae toxins imprinted material is repeated into n times above step (2), in magnetic Nano
Particle surface forms multilayer Algae toxins imprinted material；
(3) by the multilayer Algae toxins imprinted material refluxing extraction template molecule Algae toxins obtained by step (2), dry, obtain algae poison
Plain molecular engram nano composite material.
2. the synthetic method of magnetic phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that：It is described
In step (1), when the dosage of magnetic nanoparticle is 1-10mg, crosslinking agent dosage is 0.5-5mL, Mn doping ZnS phosphorescence amounts
The dosage of son point is 5-50mg.
3. the synthetic method of magnetic phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that：It is described
In step (2), the mass ratio of the nano composite material and Algae toxins is：0.4-40, the nano composite material and polyethylene
The mass ratio of imines is：2.5-250.
4. the synthetic method of magnetic phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that：It is described
In step (1) and (2), the crosslinking agent is selected from glutaraldehyde, isocyanates and vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan).
5. the synthetic method of magnetic phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that：It is described
In step (3), the solvent of the backflow includes the mixed liquor of the first solvent and the second solvent, and first solvent is selected from second
Alcohol, second solvent is selected from acetonitrile, water and toluene.
6. the synthetic method of magnetic phosphorescence Microcystin imprinted material according to claim 5, it is characterised in that：It is described
In step (3), the volume ratio of first solvent and the second solvent is 8-10：1.
7. the synthetic method of magnetic phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that：It is described
In step (1), the synthetic method of the magnetic nanoparticle includes：Iron chloride is added in ethylene glycol solution, is subsequently adding
Sodium acetate and polyethyleneimine, stirring, obtain homogeneous solution, and the solution then is reacted into 2-10h at 100-200 DEG C,
Through cooling, washing is dried to obtain the magnetic nanoparticle.
8. the synthetic method of the magnetic phosphorescence Microcystin imprinted material according to claim 1 or 7, it is characterised in that：
The molecular weight of the polyethyleneimine is selected from 1800,6000 and 12000.
9. the synthetic method of magnetic phosphorescence Microcystin imprinted material according to claim 1, it is characterised in that：It is described
In step (1), the synthesis of the Mn doping ZnS phosphorescence quantum dots includes：A () is by Zn (Ac)2With Mn (Ac)2Ultrasonic dissolution is going
In ionized water, it is stirred at room temperature down, after inert gas shielding 10-100 minutes, Na is slowly added under conditions of air is completely cut off2S water
Solution, reactant continues to react 2-10h, obtains Mn doping ZnS quantum points, washs, and is vacuum dried standby；B () mixes the Mn
Miscellaneous ZnS quantum dot is dissolved in absolute ethyl alcohol, adds cysteamine, continues to stir 20-30h, and the product for obtaining is purified with absolute ethyl alcohol,
It is centrifuged off half excessive Guang ammonia, product drying.
10. the synthetic method of magnetic phosphorescence Microcystin imprinted material according to claim 9, it is characterised in that：Institute
State Zn (Ac)2With Mn (Ac)2The molar ratio of consumption is：10:1, the Zn (Ac)2And Na2The molar ratio of S consumptions is：2-
10:1。
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