CN107245196A - Multilayer assembles the preparation method of micron size polystyrene magnetic composite microsphere - Google Patents
Multilayer assembles the preparation method of micron size polystyrene magnetic composite microsphere Download PDFInfo
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Abstract
The invention belongs to polymer-function material technical field, the preparation method of micron size polystyrene magnetic composite microsphere is assembled there is provided a kind of multilayer, the preparation method of the polystyrene magnetic composite microsphere of the present invention prepares sulfonic group or carboxyl polystyrene microsphere that monodispersed surface is rich in negative electrical charge using dispersin polymerization, then utilizes the Fe that it is modified with strong cationic polyelectrolytes, sodium citrate3O4Electrostatic interaction between nano-particle, finally prepares micron size Magnetic Polystyrene Microsphere.Particle diameter high uniformity, particle diameter are resulted in micron-sized monodisperse polystyrene magnetic microsphere by the preparation method of the present invention, the application demand in the fields such as chemiluminescence immunoassay, cell separation and protein purification can be met, the preparation method of the present invention also has the advantages that easy to operate, energy-saving consumption-reducing, suitable for Industry Promotion application.
Description
Technical field
The invention belongs to polymer-function material technical field, and in particular to a kind of multilayer assembles micron size polyphenyl
The preparation method of ethene magnetic composite microsphere.
Background technology
Magnetic macromolecular microsphere is a kind of new advanced macromolecule complex function magnetic material that developed recently gets up, and is
There is the compound of certain magnetic and special construction by what magnetic inorganic particle and organic polymer were combined to form by proper method
Microballoon.Magnetic macromolecular microsphere has the surface-functional of magnetic responsiveness and common polymer microsphere simultaneously, in medical science, bioid
Learn, the numerous areas such as immunoassays and molecular biology has a wide range of applications, especially in immobilised enzymes, targeted drug and thin
Had broad application prospects in terms of born of the same parents' separation.
At present, preparing the method for magnetic macromolecular microsphere mainly has microemulsion polymerization method, emulsion polymerization, dispersion copolymerization method
And suspension polymerization etc., these methods respectively have feature, and many scholars are carried out to these methods for different application fields
Research.In these methods, microemulsion polymerization method and emulsion polymerization can for preparing the preferable magnetic microsphere of monodispersity,
But microspherulite diameter is typically submicron order, larger-size micron order complex microsphere is if desired prepared, it will usually using scattered poly-
Legal, suspension polymerization.But the microspherulite diameter wider distribution that existing method is obtained, it is not suitable in terms of biomedicine
Extensive use, and monodispersity be weigh high molecule magnetic microsphere important indicator, especially when applied to chemiluminescence immunoassay,
When cell separation and protein purification art.
Based on above background context, what the preparation method generally existing of magnetic macromolecular microsphere in the art was prepared
Magnetic macromolecular microsphere particle diameter distribution is wider, without the deficiency such as monodispersity, application field scope be limited.
The content of the invention
In order to solve the above mentioned problem of prior art presence, the present invention provides a kind of multilayer assembling micron size polyphenyl
The preparation method of ethene magnetic composite microsphere.Monodispersed micron order magnetic coupling is resulted in by the preparation method of the present invention
Microballoon, and coverage rate is controllable, preparation method is easy to operate, the popularization and application suitable for industrialization.
The core technology of the present invention is contemplated that, the sulfonic group that monodispersed surface is rich in negative electrical charge is prepared using dispersin polymerization
Or carboxyl polystyrene microsphere, then utilize the Fe that it is modified with strong cationic polyelectrolytes, sodium citrate3O4Nano-particle it
Between electrostatic interaction, finally prepare micron size Magnetic Polystyrene Microsphere.
Based on the design of above core technology, the present invention is realized especially by following technical scheme：
A kind of multilayer of the present invention assembles the preparation method of micron size polystyrene magnetic composite microsphere, including such as
Lower step：(1) surface is the preparation of the polystyrene microsphere of positive charge：Mono dispersed micrograde polystyrene microsphere is prepared, to institute
Obtain mono dispersed micrograde polystyrene microsphere to be handled, obtain the polystyrene microsphere that surface is positive charge；(2) surface is negative
The Fe of electric charge3O4The preparation of nano-particle：Prepare Fe3O4Nano-particle, by gained Fe3O4Nano-particle is handled, and obtains table
Face is the Fe of negative electrical charge3O4Nano-particle；(3) preparation of polystyrene magnetic composite microsphere：It is the poly- of positive charge by gained surface
Phenylethylene micro ball and the Fe that surface is negative electrical charge3O4Nano-particle is mixed, that is, obtains the polystyrene magnetic coupling micro-
Ball.
In the present invention, prepare by modes such as dispersin polymerizations that particle diameter is monodispersed, highly homogeneous micron in step (1)
Polystyrene microballoon, then adds positive charge by the surface treatment of mono dispersed micrograde polystyrene microsphere again.In step (1)
The mode that the surface treatment of specially mono dispersed micrograde polystyrene microsphere obtains positive charge has two kinds：The first uses two steps
Method is carried out, first the first step, and the surface of mono dispersed micrograde polystyrene microsphere first is carried out into sulfonation processing, negative electrical charge is taken；
Secondly second step, then by strong cationic polyelectrolytes to the mono dispersed micrograde polystyrene microsphere with negative electrical charge at
Manage the lotus that becomes positively charged.Second more easy, is carried out using one-step method, and direct single step reaction processing obtains surface with positive charge
Mono dispersed micrograde polystyrene microsphere.In the present invention, the band that will respectively be obtained in step (1) and (2) by electrostatic interaction
There are the mono dispersed micrograde polystyrene microsphere and Fe of dissimilar charges3O4Self-assembly is combined with each other, final to obtain single
Scattered micron order magnetic composite microsphere and whole preparation method process operation is easy, magnetic nano particle coverage rate is high and has
There is certain controllability.
Two-step method obtains method of the surface for the polystyrene microsphere of positive charge in specific further optimization, step (1)
For：Sulfonation processing first is carried out to mono dispersed micrograde polystyrene microsphere, the polystyrene microsphere that surface is negative electrical charge is obtained；Again
By the sulfonated polystyrene microsphere and strong cationic polyelectrolytes reaction for handling obtained surface for negative electrical charge, obtaining surface is
The polystyrene microsphere of positive charge.More specifically preferred scheme：By dispersin polymerization, butanol system, ethanol-water system or
In person's ethanol-ethylene glycol monomethyl ether system, using polyvinyl pyrrolidone as stabilizer, trigger benzene second by initiator of azodiisobutyronitrile
Alkene monomer polymerization obtains mono dispersed micrograde polystyrene microsphere；The concentrated sulfuric acid is reused to mono dispersed micrograde polystyrene microsphere
Sulfonation processing is carried out, the polystyrene microsphere that surface is negative electrical charge is obtained；Again to surface in the polystyrene microsphere of negative electrical charge
PAH such as PDDA is introduced, processing obtains the polystyrene that surface is positive charge
Microballoon.
Being obtained for the two steps method can adopt in the specific practical operation of method of the surface for the polystyrene microsphere of positive charge
With following two kinds preferred specific implementations：According to the specific embodiment of the present invention, the first is optional specific excellent
The scheme is selected to be：Polyvinyl pyrrolidone is added in butanol, stirring obtains homogeneous phase solution；Azodiisobutyronitrile is dissolved in styrene
In monomer, then the styrene for being dissolved with azodiisobutyronitrile is added in the homogeneous phase solution；Under inert gas shielding, in 68
Stirring reaction under the conditions of~72 DEG C；Reaction terminates rear centrifugal treating, removes supernatant, scattered using ethanol, is dried to obtain single point
Dissipate micron order polystyrene microsphere；Mono dispersed micrograde polystyrene microsphere is added in acetic acid, the concentrated sulfuric acid is then added,
Ultrasound obtains homogeneous phase solution, and the homogeneous phase solution is added in frozen water, after centrifugal treating, supernatant is removed, water-dispersible to obtain surface
For the polystyrene microsphere of negative electrical charge, surface is dispersed into water for the polystyrene microsphere of negative electrical charge；By poly dimethyl two
Allyl ammonium chloride and sodium chloride is soluble in water obtains mixed liquor, then adds mixed liquor the polyphenyl for containing that surface is negative electrical charge
In the water of ethene microballoon, centrifugal treating after concussion, remove supernatant, it is water-dispersible obtain surface be positive charge polystyrene it is micro-
Ball.According to two other specific embodiment of the present invention, second of optional specific preferred scheme is：By polyvinyl pyrrolidone,
Ethanol and ethylene glycol monomethyl ether add reaction vessel, and stirring obtains homogeneous phase solution；Azodiisobutyronitrile is dissolved in styrene monomer
In, then the styrene for being dissolved with azodiisobutyronitrile is added in the homogeneous phase solution；Under inert gas shielding, in 68~72
Stirring reaction under the conditions of DEG C；Reaction terminates rear centrifugal treating, removes supernatant, scattered using ethanol, is dried to obtain single dispersing micro-
Meter level polystyrene microsphere；Mono dispersed micrograde polystyrene microsphere is added in acetic acid, the concentrated sulfuric acid is then added, ultrasound
Homogeneous phase solution is obtained, the homogeneous phase solution is added in frozen water, after centrifugal treating, supernatant is removed, the water-dispersible surface that obtains is negative
The polystyrene microsphere of electric charge, surface is dispersed into water for the polystyrene microsphere of negative electrical charge；By the allyl of poly dimethyl two
Ammonium chloride and sodium chloride is soluble in water obtains mixed liquor, then adds mixed liquor the polystyrene for containing that surface is negative electrical charge
In the water of microballoon, centrifugal treating after concussion removes supernatant, water-dispersible to obtain the polystyrene microsphere that surface is positive charge.
According to described previously, specific further optimization, the present invention is also provided directly to be prepared by using one-step method
Surface is the polystyrene microsphere of positive charge, and operation can be further simplified using one-step method, and lifting process efficiency, reduction is damaged
Consumption.Specifically method is：Using ethanol-ethylene glycol monomethyl ether system as reaction medium, with acrylic resin and sodium sulfo-succinate two
Monooctyl ester is stabilizer, triggers styrene polymerization using benzoyl peroxide or azodiisobutyronitrile as initiator, then again by drawing
Enter PAH such as PDDA, it is micro- that processing obtains the polystyrene that surface is positive charge
Ball.
According to one embodiment of present invention, used in the step of present invention is provided (1) specific method of one-step method for：Will
Acrylic resin, dioctylis sulfosuccinas natricus, ethanol and ethylene glycol monomethyl ether add reaction vessel, and stirring obtains homogeneous phase solution；
Initiator benzoyl peroxide or azodiisobutyronitrile are dissolved in styrene monomer, the benzene second of initiator then will be dissolved with
Alkene is added in the homogeneous phase solution；Under inert gas shielding, the stirring reaction under the conditions of 68~72 DEG C；Reaction terminate after respectively according to
Secondary use second alcohol and water is disperseed as dispersant, finally gives the polystyrene microsphere that surface is negative electrical charge.It is by surface
The polystyrene microsphere of negative electrical charge is dispersed into water；Obtain PDDA and sodium chloride are soluble in water
Mixed liquor, then adds mixed liquor in the water containing surface for the polystyrene microsphere of negative electrical charge, centrifugal treating after concussion is gone
It is water-dispersible to obtain the polystyrene microsphere that surface is positive charge except supernatant.
In specific Fe3O4In nano-particle preparation process, surface is negative electrical charge in the step of present invention is provided (2)
Fe3O4The method for optimizing of the preparation of nano-particle is：Under nitrogen protection with sodium hydroxide solution or concentrated ammonia liquor titration FeCl3·
6H2O and FeCl2·4H2O homogeneous phase aqueous solutions, obtain Fe3O4Nano-particle；Then with sodium citrate to Fe3O4Nano-particle is carried out
Surface modification, obtains the Fe that surface is negative electrical charge3O4Nano-particle.
It is further preferred that the stability in order to strengthen the polystyrene magnetic composite microsphere that the present invention is prepared, step
Suddenly the step of stablizing the polystyrene magnetic composite microsphere (4) is additionally provided with after (3), step (4) method is：Will be described poly-
Styrene magnetic composite microsphere Surface coating strong cationic polyelectrolytes.The polystyrene magnetic composite microsphere is surface coated
Strong cationic polyelectrolytes are preferably PAH such as PDDA.
The concrete technical scheme that the present invention is provided based on more than, the invention has the advantages that：
First, the core idea based on the present invention, the present invention prepares monodispersed micron order polyphenyl second using dispersin polymerization
Alkene microballoon, then Surfaces of Polystyrene Microparticles is handled into the lotus that becomes positively charged, and by it and through handling the Fe with negative electrical charge3O4Nanometer
Particle attracts each other to be combined by electrostatic interaction carries out electrostatic self-assembled, finally prepares micron size polystyrene magnetic
Property microballoon.Of the invention whole preparation method is easy to operate is used suitable for Industry Promotion, and is obtained it is crucial that can prepare
Monodispersed, particle diameter high uniformity micron order Magnetic Polystyrene Microsphere, be Magnetic Polystyrene Microsphere in chemiluminescence
Basic preparation has been carried out in the application in the field such as immune, cell separation and protein purification.
Secondly, a kind of one-step method is additionally provided in the present invention and prepares the mono dispersed micrograde polyphenyl that surface is rich in carboxylic group
The method of ethene microballoon, need not be again to the further functionalized modification of polystyrene microsphere microsphere surface by this method, can be direct
As the base material for preparing polystyrene magnetic composite microsphere, further significantly simplify operation, reduction loss.
3rd, additionally provide using strong cationic polyelectrolytes to the Magnetic Polystyrene Microsphere for preparing in the present invention
The method being further processed, passes through the further processing of strong cationic polyelectrolytes so that Magnetic Polystyrene Microsphere table
Face is all similarly charged, based on the mutually exclusive principle of like charges so that Magnetic Polystyrene Microsphere keeps certain each other
Distance, it is to avoid the mutual excessive aggregation of Magnetic Polystyrene Microsphere, while it also avoid Fe3O4Nano-particle is from polyphenyl second
Disengaging in alkene magnetic microsphere.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1~Fig. 4 is polyphenyl second of the surface made from one-step method rich in carboxyl negative electrical charge during preparation method of the present invention
The electron-microscope scanning figure of alkene microballoon；
Fig. 5~Fig. 7 is that the Electronic Speculum of the polystyrene magnetic composite microsphere for the multilayer assembling that preparation method of the present invention is obtained is swept
Tracing；
Fig. 8 is the Dynamic laser scattering grain size analysis datagram of the polystyrene microsphere in preparation method of the present invention；
Fig. 9 is the Dynamic laser scattering grain size analysis data of the Magnetic Polystyrene Microsphere obtained by preparation method of the present invention
Figure.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical scheme will be carried out below
Detailed description.Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are resulting on the premise of creative work is not made to be owned
Other embodiment, belongs to the scope that the present invention is protected.
Embodiment 1：
The present embodiment provides the preparation method that a kind of multilayer assembles micron size polystyrene magnetic composite microsphere, tool
Body step is as follows：
(1) synthesis of polystyrene microsphere：250ml round-bottomed flask is taken, 3g polyvinyl pyrrolidones (Mw=is added
55000), 100mL ethanol and 10mL water, stirring obtain homogeneous phase solution.0.08g azodiisobutyronitriles are weighed to dissolve as initiator
In the styrene monomer that 8mL distills.The styrene monomer solution for being dissolved with azodiisobutyronitrile is added into gained above homogeneous
In solution, nitrogen protection is led in stirring, and rise reaction temperature is reacted 20 hours to 70 DEG C under 150rpm/min.After reaction time arrives
Centrifugal treating, removes supernatant, then scattered with ethanol, repeats to be dried in vacuo 24 hours at disperseing six times, 30 DEG C, obtains particle diameter about
For 1 μm of polystyrene microsphere.
(2) sulfonation of polystyrene microsphere：100mL round-bottomed flasks are taken, adds and step (1) is added under 5mL acetic acid, ice-water bath
Ultrasound 10min at the 50mL concentrated sulfuric acids, 20 DEG C is slowly added under the polystyrene microsphere 1g of synthesis, normal temperature and obtains homogeneous phase solution, will
The homogeneous phase solution being added in intensively stirred 1L frozen water slowly, intensively stirred rotating speed is about 500r/min；Centrifugal treating,
Supernatant is removed, it is water-dispersible, in triplicate, finally it is scattered in 200mL pure water, the surface after obtaining containing sulfonation carries negative electricity
The aqueous of lotus polystyrene microsphere.
(3) preparation of positive charge polystyrene microsphere：200mL is contained into the dense of 4mL PDDAs
What the NaCl solution spent for 0.5M/L was added to that step (2) obtains carries negative electrical charge polystyrene microsphere containing the surface after sulfonation
Aqueous in, normal temperature shake 3 hours, centrifugal treating, remove supernatant, it is water-dispersible, in triplicate, be finally scattered in 1L pure water
In, obtain the aqueous containing positive charge polystyrene microsphere.
(4)Fe3O4The synthesis of nano-particle：250ml round-bottomed flask is taken, 2.7gFeCl is added3·6H2O、1.0g
FeCl2·4H2O and 80ml water, leads to nitrogen protection, and stirring obtains homogeneous phase solution；3g sodium hydroxides are weighed, hydrogen is made into 20ml water
Sodium hydroxide solution, is slowly added drop-wise in homogeneous phase solution, and temperature is raised to 100 DEG C, is reacted 2 hours under strong agitation, intensively stirred
Rotating speed is about 500r/min；Separated with magnet in black particle, the salpeter solution for being re-dispersed into 50mL 1M/L；It is then centrifuged for
Contain Fe3O4The HNO of nano-particle3Solution, is dispersed back into 150mL pure water；Fe will be contained3O4The aqueous solution of nano-particle adds
Heat adds 2g sodium citrates to 90 DEG C, under stirring and reacted 2 hours, is then naturally cooling to normal temperature；150mL acetone is added,
Fe is separated with magnet3O4Nano-particle, redisperse is obtained containing with negative electrical charge Fe into 200mL water3O4The water of nano-particle
Liquid.
(5) preparation of polystyrene magnetic composite microsphere：By step (3) prepare containing positive charge polystyrene microsphere
Aqueous is divided into 5 parts, is separately added into containing with negative electrical charge Fe for 12.5mL steps (4) preparation3O4The aqueous of nano-particle,
Normal temperature shakes 30min；Microballoon of the electrostatic from after combining is isolated with magnet, is subsequently dispersed in 200mL water, scattered three are repeated
It is secondary, that is, obtain, containing polystyrene magnetic composite microsphere, gained polystyrene magnetic composite microsphere then being distributed into 200mL water
It is middle to preserve.
(6) stabilization of polystyrene magnetic composite microsphere：100mL is contained into 4mL PDDAs
Concentration is dispersed with the aqueous of polystyrene magnetic composite microsphere for what 0.5M/L NaCl solution was added to that step (5) obtains,
Normal temperature shakes 30min.Microballoon is isolated with magnet, is subsequently dispersed in 200mL water, repeats scattered three times, is finally distributed to
In 200mL water, the aqueous containing stable polystyrene magnetic composite microsphere is obtained.
Embodiment 2：
The present embodiment provides the preparation method that a kind of multilayer assembles micron size polystyrene magnetic composite microsphere, tool
Body step is as follows：
(1) synthesis of polystyrene microsphere：250ml round-bottomed flask is taken, 2.0g polyvinyl pyrrolidones (Mw=is added
55000) with 120mL ethanol, stirring obtains homogeneous phase solution.0.2g azodiisobutyronitriles are weighed as initiator and are dissolved in 30mL steamings
In the styrene monomer evaporated.The styrene monomer solution for being dissolved with azodiisobutyronitrile is added in gained homogeneous phase solution above,
Stirring, leads to nitrogen protection, and rise reaction temperature is reacted 20 hours to 68 DEG C under 150rpm/min.After reaction time arrives at centrifugation
Reason, removes supernatant, then scattered with ethanol, is dried in vacuo 24 hours at repeating six times, 30 DEG C, obtains the polyphenyl that particle diameter is 3 μm
Ethene microballoon.
(2) sulfonation of polystyrene microsphere：100mL round-bottomed flasks are taken, adds and step (1) is added under 5mL acetic acid, ice-water bath
Ultrasound 10min at the 50mL concentrated sulfuric acids, 20 DEG C is slowly added under the polystyrene microsphere 1g of synthesis, normal temperature and obtains homogeneous phase solution, will
The homogeneous phase solution being added in intensively stirred 1L frozen water slowly, intensively stirred rotating speed is about 500r/min；Centrifugal treating,
Supernatant is removed, it is water-dispersible, in triplicate, finally it is scattered in 200mL pure water, the surface after obtaining containing sulfonation carries negative electricity
The aqueous of lotus polystyrene microsphere.
(3) preparation of positive charge polystyrene microsphere：200mL is contained into the dense of 4mL PDDAs
What the NaCl solution spent for 0.5M/L was added to that step (2) obtains carries negative electrical charge polystyrene microsphere containing the surface after sulfonation
Aqueous in, normal temperature shake 3 hours, centrifugal treating, remove supernatant, it is water-dispersible, in triplicate, be finally scattered in 1L pure water
In, obtain the aqueous containing positive charge polystyrene microsphere.
(4)Fe3O4The synthesis of nano-particle：250ml round-bottomed flask is taken, 2.7gFeCl is added3·6H2O、1.0g
FeCl2·4H2O and 80ml water, leads to nitrogen protection, and stirring obtains homogeneous phase solution；The concentrated ammonia liquor of mass concentration 25% is taken, is slowly dripped
It is added in homogeneous phase solution, temperature is raised to 100 DEG C, is reacted 2 hours under strong agitation, intensively stirred rotating speed is about 500r/min；
Separated with magnet in black particle, the salpeter solution for being re-dispersed into 50mL 1M/L；It is then centrifuged for containing Fe3O4Nano-particle
HNO3Solution, is dispersed back into 150mL pure water；Fe will be contained3O4The aqueous solution of nano-particle is heated to 90 DEG C, stirs shape
2g sodium citrates are added under state to react 2 hours, are then naturally cooling to normal temperature；150mL acetone is added, Fe is separated with magnet3O4Receive
Rice corpuscles, redisperse is obtained containing with negative electrical charge Fe into 200mL water3O4The aqueous of nano-particle.
(5) preparation of polystyrene magnetic composite microsphere：By step (3) prepare containing positive charge polystyrene microsphere
Aqueous is divided into 5 parts, is separately added into containing with negative electrical charge Fe for 12.5mL steps (4) preparation3O4The aqueous of nano-particle,
Normal temperature shakes 30min；Microballoon of the electrostatic from after combining is isolated with magnet, is subsequently dispersed in 200mL water, scattered three are repeated
It is secondary, that is, obtain, containing polystyrene magnetic composite microsphere, gained polystyrene magnetic composite microsphere then being distributed into 200mL water
It is middle to preserve.
Embodiment 3：
The present embodiment provides the preparation method that a kind of multilayer assembles micron size polystyrene magnetic composite microsphere, tool
Body step is as follows：
(1) synthesis of polystyrene microsphere：250ml round-bottomed flask is taken, 4.0g polyvinyl pyrrolidones (Mw=is added
55000), 40mL ethanol and 60mL ethylene glycol monomethyl ethers, stirring obtain homogeneous phase solution.0.3g azodiisobutyronitriles are weighed as initiation
Agent is dissolved in the styrene monomer of 30mL distillations.The styrene monomer solution for being dissolved with azodiisobutyronitrile is added into institute above
Obtain in homogeneous phase solution, stirring, lead to nitrogen protection, rise reaction temperature is to 72 DEG C, reaction 20 hours under 150rpm/min.During reaction
Between arrive rear centrifugal treating, remove supernatant, then scattered with ethanol, be dried in vacuo 24 hours at repeating six times, 30 DEG C, obtain particle diameter
For 6 μm of polystyrene microsphere.
(2) sulfonation of polystyrene microsphere：100mL round-bottomed flasks are taken, adds and step (1) is added under 5mL acetic acid, ice-water bath
Ultrasound 10min at the 50mL concentrated sulfuric acids, 20 DEG C is slowly added under the polystyrene microsphere 1g of synthesis, normal temperature and obtains homogeneous phase solution, will
The homogeneous phase solution being added in intensively stirred 1L frozen water slowly, intensively stirred rotating speed is about 500r/min；Centrifugal treating,
Supernatant is removed, it is water-dispersible, in triplicate, finally it is scattered in 200mL pure water, the surface after obtaining containing sulfonation carries negative electricity
The aqueous of lotus polystyrene microsphere.
(3) preparation of positive charge polystyrene microsphere：200mL is contained into the dense of 4mL PDDAs
What the NaCl solution spent for 0.5M/L was added to that step (2) obtains carries negative electrical charge polystyrene microsphere containing the surface after sulfonation
Aqueous in, normal temperature shake 3 hours, centrifugal treating, remove supernatant, it is water-dispersible, in triplicate, be finally scattered in 1L pure water
In, obtain the aqueous containing positive charge polystyrene microsphere.
(4)Fe3O4The synthesis of nano-particle：250ml round-bottomed flask is taken, 2.7gFeCl is added3·6H2O、1.0g
FeCl2·4H2O and 80ml water, leads to nitrogen protection, and stirring obtains homogeneous phase solution；3g sodium hydroxides are weighed, hydrogen is made into 20ml water
Sodium hydroxide solution, is slowly added drop-wise in homogeneous phase solution, and temperature is raised to 100 DEG C, is reacted 2 hours under strong agitation, intensively stirred
Rotating speed is about 500r/min；Separated with magnet in black particle, the salpeter solution for being re-dispersed into 50mL 1M/L；It is then centrifuged for
Contain Fe3O4The HNO of nano-particle3Solution, is dispersed back into 150mL pure water；Fe will be contained3O4The aqueous solution of nano-particle adds
Heat adds 2g sodium citrates to 90 DEG C, under stirring and reacted 2 hours, is then naturally cooling to normal temperature；150mL acetone is added,
Fe is separated with magnet3O4Nano-particle, redisperse is obtained containing with negative electrical charge Fe into 200mL water3O4The water of nano-particle
Liquid.
(5) preparation of polystyrene magnetic composite microsphere：By step (3) prepare containing positive charge polystyrene microsphere
Aqueous is divided into 5 parts, is separately added into containing with negative electrical charge Fe for 12.5mL steps (4) preparation3O4The aqueous of nano-particle,
Normal temperature shakes 30min；Microballoon of the electrostatic from after combining is isolated with magnet, is subsequently dispersed in 200mL water, scattered three are repeated
It is secondary, that is, obtain, containing polystyrene magnetic composite microsphere, gained polystyrene magnetic composite microsphere then being distributed into 200mL water
It is middle to preserve.
Embodiment 4：
The present embodiment provides the preparation method that a kind of multilayer assembles micron size polystyrene magnetic composite microsphere, tool
Body step is as follows：
(1) synthesis of polystyrene carboxyl microballoon：500ml round-bottomed flask is taken, 20g acrylic resins, 10g sulfo groups is added
Sodium succinate dioctyl ester, 135mL ethanol and 135mL ethylene glycol monomethyl ethers, stirring obtain homogeneous phase solution；Weigh 1.5g benzoyl peroxide first
Acyl is dissolved in as initiator in the styrene monomer of 60mL distillations；The styrene monomer solution of benzoyl peroxide will be dissolved with
Add in gained homogeneous phase solution above, stirring, lead to nitrogen protection, 70 DEG C of reaction temperature is reacted 20 hours under 150rpm；At centrifugation
Reason, removes supernatant, then scattered with ethanol, repeats scattered six times, is finally scattered in 200mL pure water, obtains containing 1 μm of particle diameter
The negatively charged polystyrene carboxyl microballoon in surface aqueous, polystyrene carboxyl microsphere surface now is rich in a large amount of carboxylics
Base, shows negative electrical charge.
The negatively charged polystyrene carboxyl microballoon of the present embodiment surface modification is scanned using electron-microscope scanning instrument and clapped
According to taking pictures result as depicted in figs. 1 and 2, analysis chart 1 and Fig. 2 are understood, the polyphenyl as the step of the present embodiment 4 obtained by processing
The particle diameter of ethene microballoon is about 1 μm in micron order, and polystyrene microsphere particle diameter high uniformity, with monodispersity.
(2) preparation of positive charge polystyrene microsphere：200mL is contained into the dense of 4mL PDDAs
The NaCl solution spent for 0.5M/L is added to the water for the polystyrene carboxyl microballoon negatively charged containing surface that step (1) is obtained
In liquid, normal temperature shakes 3 hours, centrifugal treating, removes supernatant, water-dispersible, in triplicate, is finally scattered in 1L pure water,
Obtain the aqueous containing positive charge polystyrene microsphere.
(3)Fe3O4The synthesis of nano-particle：250ml round-bottomed flask is taken, 2.7gFeCl is added3·6H2O、1.0g
FeCl2·4H2O and 80ml water, leads to nitrogen protection, and stirring obtains homogeneous phase solution；3g sodium hydroxides are weighed, hydrogen is made into 20ml water
Sodium hydroxide solution, is slowly added drop-wise in homogeneous phase solution, and temperature is raised to 100 DEG C, is reacted 2 hours under strong agitation, intensively stirred
Rotating speed is about 500r/min；Separated with magnet in black particle, the salpeter solution for being re-dispersed into 50mL 1M/L；It is then centrifuged for
Contain Fe3O4The HNO of nano-particle3Solution, is dispersed back into 150mL pure water；Fe will be contained3O4The aqueous solution of nano-particle adds
Heat adds 2g sodium citrates to 90 DEG C, under stirring and reacted 2 hours, is then naturally cooling to normal temperature；150mL acetone is added,
Fe is separated with magnet3O4Nano-particle, redisperse is obtained containing with negative electrical charge Fe into 200mL water3O4The water of nano-particle
Liquid.
(4) preparation of polystyrene magnetic composite microsphere：By step (2) prepare containing positive charge polystyrene microsphere
Aqueous is divided into 5 parts, is separately added into containing with negative electrical charge Fe for 12.5mL steps (3) preparation3O4The aqueous of nano-particle,
Normal temperature shakes 30min；Microballoon of the electrostatic from after combining is isolated with magnet, is subsequently dispersed in 200mL water, scattered three are repeated
It is secondary, that is, obtain, containing polystyrene magnetic composite microsphere, gained polystyrene magnetic composite microsphere then being distributed into 200mL water
It is middle to preserve.
The scanning of gained polystyrene magnetic composite microsphere is taken pictures using electron-microscope scanning instrument, result of taking pictures such as Fig. 5~Fig. 7 institutes
Show, analysis chart 5 understands that the particle diameter of the polystyrene magnetic composite microsphere as obtained by the processing of the present embodiment 4 is maintained at micron
Level, and polystyrene magnetic composite microsphere particle diameter keeps high uniformity, and with monodispersity and magnetic content height, this also can
It is confirmed in the Fig. 6 and Fig. 7 further amplified.
(5) stabilization of polystyrene magnetic composite microsphere：100mL is contained into 4mL PDDAs
Concentration is dispersed with the aqueous of polystyrene magnetic composite microsphere for what 0.5M/L NaCl solution was added to that step (4) obtains,
Normal temperature shakes 30min.Microballoon is isolated with magnet, is subsequently dispersed in 200mL water, repeats scattered three times, is finally distributed to
In 200mL water, the aqueous containing stable polystyrene magnetic composite microsphere is obtained.
Embodiment 5：
The present embodiment is embodiment 1 and the stable polystyrene magnetic composite microsphere coating dopamine of the gained of embodiment 4
Application examples, specific step is as follows：The polystyrene magnetic coupling containing stabilization prepared using embodiment 1 or embodiment 4 is micro-
The aqueous 200mL of ball, adds the dilution of 200mL water, then adds 100mL Tris solution (containing 0.6g Tris), and concussion is mixed；
Then concussion reaction 8 hours under 1mL aqueous dopamine solution (containing 100mg dopamines), normal temperature are added；Isolated with magnet micro-
Ball, is subsequently dispersed in 200mL water, repeats scattered three times, is finally distributed in 200mL water, obtains coated containing dopamine
The aqueous of Magnetic Polystyrene Microsphere.
Embodiment 6：
The present embodiment is the application examples that the coated Magnetic Polystyrene Microsphere of the gained dopamine of embodiment 5 connects antibody.Tool
The step of body, is as follows：
The coated Magnetic Polystyrene Microsphere 1mg of the gained dopamine of Example 5, adds 100ml pure water, and vibration is mixed,
Carry out separation microballoon with magnetic frame, remove supernatant, wash twice, by the microballoon washed, with cross-linking buffer (10mmolPBS,
PH=7.4) it is diluted to 100ml.
The glutaraldehyde water of crosslinking agent 25% is added into the buffer solution of the coated Magnetic Polystyrene Microsphere of the dopamine of resuspension
Solution 2ml, shakes 0.5~1h of activation.Supernatant is removed using magnetic separtor after reaction, using connection buffer solution washing 1-2
It is secondary, then add connection buffer solution and be uniformly mixed so as to obtain the mixed liquid of connection.
Antibody is taken, and is adjusted antibody concentration to 2~10mg/ml with connection buffer solution, then will be dense containing antibody is mixed up
The connection buffer solution of degree is added in the mixed liquid of the connection, is mixed and is obtained reaction solution within 1~6 hour after room temperature reaction.
Take 100mgBSA to be dissolved in 1ml deionized waters and BSA solution for standby is made.
Take 50 μ LBSA solution to add in the reaction solution, mix after room temperature reaction 1~12 hour.Divide after completion of the reaction
The microballoon connected is separated out to produce.The microballoon connected is cleaned using 1ml deionized waters twice, is finally deposited using 0.5ml microballoons
It is stand-by after 2~8 DEG C of storages that the microballoon connected is resuspended in storage buffer solution.
The immunoassay situation of the microballoon connected of the gained of the present embodiment 6 is as follows：
Immunoassay method：Add 50 μ L PCT standard items or sample in reaction cup, exempt from made from 50 μ L the present embodiment 6
Epidemic disease magnetic bead, 50 μ L enzyme markers；15min is reacted in 37 DEG C；Wash 3 times with PBST cleaning solutions under magnetic field, every time 500 μ L.With
Different chemiluminescence detector devices detect luminous intensity, and testing result is listed in the table below 1.
Table 1
| Concentration | Unit | Rep1 | Rep2 | Rep3 | Mean | SD | CV | SNR |
| 0 | ng/ml | 4202 | 3891 | 4119 | 4071 | 161 | 3.96 | \ |
| 0.05 | ng/ml | 10353 | 9878 | 9596 | 9942 | 383 | 3.85 | 2.22 |
| 0.1 | ng/ml | 12229 | 13015 | 12381 | 12542 | 417 | 3.32 | 2.80 |
| 1 | ng/ml | 158232 | 156121 | 153041 | 155798 | 2611 | 1.68 | 34.75 |
| 10 | ng/ml | 1779602 | 1591769 | 1646021 | 1672464 | 96668 | 5.78 | 373.01 |
| 100 | ng/ml | 8367672 | 8721791 | 8487898 | 8525787 | 180074 | 2.11 | 1901.52 |
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. multilayer assembles the preparation method of micron size polystyrene magnetic composite microsphere, it is characterised in that including as follows
Step：
(1) surface is the preparation of the polystyrene microsphere of positive charge：Mono dispersed micrograde polystyrene microsphere is prepared, to gained list
Scattered micron order polystyrene microsphere is handled, and obtains the polystyrene microsphere that surface is positive charge；
(2) surface is the Fe of negative electrical charge3O4The preparation of nano-particle：Prepare Fe3O4Nano-particle, by gained Fe3O4Nano-particle
Handled, obtain the Fe that surface is negative electrical charge3O4Nano-particle；
(3) preparation of polystyrene magnetic composite microsphere：It is negative by polystyrene microsphere that gained surface is positive charge and surface
The Fe of electric charge3O4Nano-particle is mixed, that is, obtains the polystyrene magnetic composite microsphere.
2. multilayer according to claim 1 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, the method that processing obtains the polystyrene microsphere that surface is positive charge in step (1) is：First to single dispersing micron
Polystyrene microballoon carries out sulfonation processing, obtains the polystyrene microsphere that surface is negative electrical charge；Sulfonated processing is obtained again
Surface reacted for polystyrene microsphere and the strong cationic polyelectrolytes of negative electrical charge, obtain the polystyrene that surface is positive charge
Microballoon.
3. multilayer according to claim 2 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, surface is that the method for the preparation of the polystyrene microsphere of positive charge is in step (1)：By dispersin polymerization,
In butanol system, ethanol-water system or ethanol-ethylene glycol monomethyl ether system, using polyvinyl pyrrolidone as stabilizer, with azo two
Isobutyronitrile is that initiator triggers styrene monomer polymerization to obtain mono dispersed micrograde polystyrene microsphere；The concentrated sulfuric acid is reused to list
Scattered micron order polystyrene microsphere carries out sulfonation processing, obtains the polystyrene microsphere that surface is negative electrical charge；It is to surface again
PAH is introduced in the polystyrene microsphere of negative electrical charge, it is micro- that processing obtains the polystyrene that surface is positive charge
Ball.
4. multilayer according to claim 3 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, surface is specially for the method for the preparation of the polystyrene microsphere of positive charge in step (1)：By polyvinyl pyrrole
Ketone is added in butanol, and stirring obtains homogeneous phase solution；Azodiisobutyronitrile is dissolved in styrene monomer, idol then will be dissolved with
The styrene of nitrogen bis-isobutyronitrile is added in the homogeneous phase solution；Under inert gas shielding, the stirring reaction under the conditions of 68~72 DEG C；
Reaction terminates rear centrifugal treating, removes supernatant, scattered using ethanol, is dried to obtain mono dispersed micrograde polystyrene microsphere；
Mono dispersed micrograde polystyrene microsphere is added in acetic acid, the concentrated sulfuric acid is then added, ultrasound obtains homogeneous phase solution, by this
Homogeneous phase solution is added in frozen water, after centrifugal treating, removes supernatant, and water-dispersible to obtain the polystyrene that surface is negative electrical charge micro-
Ball, surface is dispersed into water for the polystyrene microsphere of negative electrical charge；By PDDA and sodium chloride
It is soluble in water to obtain mixed liquor, then mixed liquor is added in the water containing surface for the polystyrene microsphere of negative electrical charge, concussion
Centrifugal treating, removes supernatant afterwards, water-dispersible to obtain the polystyrene microsphere that surface is positive charge.
5. multilayer according to claim 3 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, surface is specially for the method for the preparation of the polystyrene microsphere of positive charge in step (1)：By polyvinyl pyrrole
Ketone, ethanol and ethylene glycol monomethyl ether add reaction vessel, and stirring obtains homogeneous phase solution；Azodiisobutyronitrile is dissolved in styrene list
In body, then the styrene for being dissolved with azodiisobutyronitrile is added in the homogeneous phase solution；Under inert gas shielding, in 68~
Stirring reaction under the conditions of 72 DEG C；Reaction terminates rear centrifugal treating, removes supernatant, scattered using ethanol, is dried to obtain single dispersing
Micron order polystyrene microsphere；Mono dispersed micrograde polystyrene microsphere is added in acetic acid, the concentrated sulfuric acid is then added, surpassed
Sound obtains homogeneous phase solution, and the homogeneous phase solution is added in frozen water, after centrifugal treating, supernatant is removed, the water-dispersible surface that obtains is
The polystyrene microsphere of negative electrical charge, surface is dispersed into water for the polystyrene microsphere of negative electrical charge；By poly dimethyl diene
Propyl ammonium chloride and sodium chloride is soluble in water obtains mixed liquor, then adds mixed liquor the polyphenyl second for containing that surface is negative electrical charge
In the water of alkene microballoon, centrifugal treating after concussion, remove supernatant, it is water-dispersible obtain surface be positive charge polystyrene it is micro-
Ball.
6. multilayer according to claim 1 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, surface is that the method for the preparation of the polystyrene microsphere of positive charge is in step (1)：With ethanol-ethylene glycol first
Ether system is reaction medium, using acrylic resin and dioctylis sulfosuccinas natricus as stabilizer, with benzoyl peroxide or idol
Nitrogen bis-isobutyronitrile is that initiator triggers styrene polymerization, and then again by introducing PAH, processing obtains surface
For the polystyrene microsphere of positive charge.
7. multilayer according to claim 6 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, surface is specially for the method for the preparation of the polystyrene microsphere of positive charge in step (1)：By acrylic acid tree
Fat, dioctylis sulfosuccinas natricus, ethanol and ethylene glycol monomethyl ether add reaction vessel, and stirring obtains homogeneous phase solution；By initiator
Benzoyl peroxide or azodiisobutyronitrile are dissolved in styrene monomer, and the styrene for being dissolved with initiator then is added into institute
State in homogeneous phase solution；Under inert gas shielding, the stirring reaction under the conditions of 68~72 DEG C；Reaction uses second successively respectively after terminating
Alcohol and water is disperseed as dispersant, finally gives the polystyrene microsphere that surface is negative electrical charge, is negative electrical charge by surface
Polystyrene microsphere is dispersed into water；Mixed liquor is obtained by PDDA and sodium chloride are soluble in water,
Then mixed liquor is added in the water containing surface for the polystyrene microsphere of negative electrical charge, centrifugal treating after concussion, removes supernatant
Liquid, it is water-dispersible to obtain the polystyrene microsphere that surface is positive charge.
8. multilayer according to claim 1 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, surface is the Fe of negative electrical charge in step (2)3O4The method of the preparation of nano-particle is：Hydrogen is used under nitrogen protection
Sodium hydroxide solution or concentrated ammonia liquor titration FeCl3·6H2O and FeCl2·4H2O homogeneous phase aqueous solutions, obtain Fe3O4Nano-particle；Then
With sodium citrate to Fe3O4Nano-particle carries out surface modification, obtains the Fe that surface is negative electrical charge3O4Nano-particle.
9. multilayer according to claim 1 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, the step of stablizing the polystyrene magnetic composite microsphere (4) is additionally provided with after step (3), step (4) side
Method is：By the polystyrene magnetic composite microsphere Surface coating strong cationic polyelectrolytes.
10. multilayer according to claim 9 assembles the preparation method of micron size polystyrene magnetic composite microsphere,
Characterized in that, the surface coated strong cationic polyelectrolytes of polystyrene magnetic composite microsphere are the allyl of poly dimethyl two
Ammonium chloride.
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