CN101220187A - Magnetic composite microsphere with nucleocapsid structure and method for producing the same - Google Patents
Magnetic composite microsphere with nucleocapsid structure and method for producing the same Download PDFInfo
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Abstract
The invention belongs to the technical field of bioseparation material, in particular to a magnetic composite microsphere with nucleocapsid structure and a preparation method thereof. Nano ferroferric oxide decorated by oleic acid is firstly used as raw material, and is polymerized through template fine emulsion so as to prepare the monodisperse magnetic composite microsphere with high magnet content; and then the monodisperse micosphere is polymerized through seed emulsion and is added with different amount of shell monomer to prepare the magnetic composite microsphere with the nucleocapsid structure and the magnet content of 20wt percent to 80wt percent. The grain size of nucleocapsid composite microsphere is in narrow distribution, and the magnet content of the microsphere is controllable and the surface has functional reactive group; therefore, the microsphere of the invention can be surface-modified into a magnetic carrier of biological active molecule by chemical crosslinking to be applied in the biomedicine field. The method of the invention can be simply operated and the process of which can be controlled, thus having industrialized prospect.
Description
Technical field
The invention belongs to bioseparation material technology field, be specifically related to a kind of preparation method with magnetic composite microsphere of nucleocapsid structure.
Technical background
In recent years, hybrid inorganic-organic complex microsphere, especially magnetic composite microsphere more and more are subjected to people's attention.Because magnetic macromolecular microsphere has the magnetic responsiveness and the organic macromolecule surface-functional of inorganic magnetic material simultaneously, can be easily and fast under externally-applied magnetic field, efficiently from medium separate targets biomolecules.In addition, the macromolecule surface of magnetic composite microsphere can on purpose reasonably be modified, and therefore, shows application prospects in fields such as medical science, biological chemistry, molecular biology and industrial application.Consider that from the angle of diagnostics the ideal magnetic microsphere should have high magnetic content (fast magnetic responsiveness), the size of particles of homogeneous, the surface of functionalization, thereby realize efficiently, separating bio target molecule fast.
At present, the magnetic content of the magnetic composite microsphere by methods such as traditional letex polymerization, dispersion polymerization, suspension polymerization preparations is no more than 30wt%, and, too wide by magnetic microsphere or size distribution that these methods are prepared, reveal magnetic nano-particle easily, thereby limited the application of magnetic microsphere.Comparatively speaking, mini-emulsion polymerization is because its unique droplet nucleation mechanism is higher in field efficient such as preparation hybrid inorganic-organic materials.Usually, in mini-emulsion polymerization, lipophilic inorganic nano-particle directly is distributed in the monomer droplet, and these monomers that are dispersed with inorganic nano-particle become the polymeric main place.In polymerization process, monomer droplet and polymer microballoon remain 1: 1 replication relation, and therefore, by mini-emulsion polymerization, various inorganic nano-particles can be coated in the polymer microballoon uniformly.In order to prepare the complex microsphere of high magnetic content, people such as Ramirez and Landfester is by three step miniemulsion polymerizations, obtain magnetic composite microsphere (the Ramirez L.P. that magnetic content is 40wt%, Landfester K.Macromol.Chem.Phys., 2003,204:2231), but prepared magnetic composite microsphere size distribution broad.Recently, people such as Xu Hong by two step miniemulsions and a step letex polymerization step, have prepared monodispersed magnetic composite microsphere (the Xu H. of magnetic content up to 80wt% by means of film emulsifier unit (SPG); Cui L.L.; TongN.H., Gu H.C.J.Am.Chem.Soc.2006,128:15582); People such as Montagne prepare magnetic composite microsphere (the Montagne F. of the 60wt% magnetic content of narrow distribution by means of the Ku Aite emulsification instrument by seeded emulsion polymerization; Mondain-Monval O.; Pichot C.; Elaissari A.J.Polym.Sci., PartA:Polym.Chem.2006,44:2642).Though these methods can obtain high magnetic content, narrow distribution magnetic composite microsphere, these methods need multiple step, special instrument, thereby make that preparation process is loaded down with trivial details, production cost increases, and have reduced production efficiency.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of preparation process, efficient height, and the preparation method of the controlled magnetic composite microsphere with nucleocapsid structure of magnetic content.
The preparation method of the magnetic composite microsphere with nucleocapsid structure that the present invention proposes is as follows: at first, prepare the nano ferriferrous oxide particle of oleic acid modified with coprecipitation method; Then adopt the template mini-emulsion polymerization, the monodispersed Z 250/polymer composite microsphere of preparation high magnetic content; Adopt seeded emulsion polymerization then, the stratum nucleare magnetic composite microsphere is carried out the surface-functionalized coating of shell, be prepared into magnetic composite microsphere with nucleocapsid structure; Wherein, the magnetic content of the magnetic composite microsphere of nucleocapsid structure is between 20wt%-80wt%.
This core-shell type complex microsphere particle diameter presents that monodispersity, magnetic content are controlled, the surface has functional reactive group, can surface modification becoming the magnetic carrier by the chemically crosslinked bioactive molecules, is a kind of biomagnetism parting material that application prospect is arranged very much.
The concrete operations step is as follows:
1. nano ferriferrous oxide (the Fe for preparing oleic acid modified with coprecipitation method
3O
4) particle, the steps include: under 75-85 ℃ to containing Fe
2+And Fe
3+Add excess of ammonia water in the aqueous solution of salt, and then adding accounts for Fe in system
3O
4The oleic acid of weight 1-40% behind the insulation reaction 2.5-3.5h, leads to vaporized nitrogen excess of ammonia water, obtains the nano ferriferrous oxide nanoparticle of oleic acid modification, washs to remove unnecessary oleic acid, octane extraction, preparation Fe with deionized water, ethanol, propyl alcohol respectively
3O
4Content is the magnetic fluid of 10-80wt%.
2. prepare Z 250/polymer composite microsphere, the steps include: under ultrasound condition, the nano ferriferrous oxide particle magnetic fluid of step (1) preparation is distributed in the solution that contains tensio-active agent, ultrasonic emulsification, the ultrasonic power scope is 200-600W, ultrasonic time is 1-25min, obtains stable magnetic miniemulsion template; Then monomer is joined in the magnetic miniemulsion template, swelling 1-2h obtains being rich in the monomer droplet of magnetic nano-particle; Add initiator then, about 20 hours, obtain the monodispersed Z 250/polymer composite microsphere of high magnetic content in 65-75 ℃ of polymerization.
3. the magnetic composite microsphere for preparing nucleocapsid structure, the complex microsphere that step (2) is obtained carries out the magnetic separation, the aqueous solution (concentration can be 0.1wt%) washing with sodium lauryl sulphate, after magnetic separates, redispersion is in the aqueous solution (concentration can be 0.1wt%) of sodium lauryl sulphate, add shell monomers then,, obtain having the magnetic composite microsphere of nucleocapsid structure in 65-75 ℃ of polymerization 10-15h.
The magnetic composite microsphere of nucleocapsid structure of the present invention, magnetic content 20wt%-80wt%, controlled.
Fe of the present invention
3+Salt is iron trichloride, Fe
2+Salt is a kind of in iron protochloride and the ferrous sulfate.
Magnetic nano-particle of the present invention is the Z 250 particle of oleic acid modification or the Z 250 particle/octane dispersion liquid of oleic acid modification.
Tensio-active agent of the present invention is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or allyloxy Nonyl pheno (10) ether ammonium sulfate (DNS-86), one or more in plasma type and the nonionic emulsifier.
Monomer of the present invention is one or more in vinylbenzene such as vinylbenzene, methyl methacrylate, Vinylstyrene and (methyl) acrylate monomer.
Initiator of the present invention is a kind of in Potassium Persulphate, ammonium persulphate or the Diisopropyl azodicarboxylate.
Shell monomers of the present invention is one or more in vinylbenzene (St), methyl methacrylate (MMA), glycidyl methacrylate (GMA), hydroxyethyl methylacrylate (HEMA), (methyl) vinylformic acid and Vinylstyrene vinyl monomers such as (DVB) and the linking agent.
At present magnetic composite microsphere main exists that magnetic content is low, the uneven first-class problem of size distribution.The present invention prepares high magnetic content, monodispersed magnetic composite microsphere by magnetic template mini-emulsion polymerization, and prepares the magnetic composite microsphere of the nucleocapsid structure of the different magnetic content with functional group surface by seeded emulsion polymerization.Zhi Bei microballoon has following characteristics by this method: (1) template mini-emulsion polymerization can be used as a kind of method in common and prepares organic/inorganic hybridization material; (2) magnetic content height, the narrow diameter distribution of magnetic composite microsphere; (3) reactive group of function is rich on the surface of the magnetic composite microsphere of nucleocapsid structure; (4) the magnetic content of the magnetic composite microsphere of nucleocapsid structure is controlled; (5) preparation process of the magnetic composite microsphere of nucleocapsid structure is simple, efficient.
Embodiment
Embodiment 1: magnetic content is the preparation of the core-shell structure magnetic complex microsphere of 76wt%
1, the Fe of oleic acid modification
3O
4The preparation of magnetic nano-particle
Get the FeCl of 25.0g
36H
2The FeCl of O and 15.0g
24H
2O, be dissolved in the deionized water of 50mL, be transferred in the four-hole boiling flask of 500mL, under condition of nitrogen gas, be warming up to 80 ℃, under stirring fast, add 50mL ammoniacal liquor rapidly, then add 4.0g oleic acid,, remove excess of ammonia water in 80 ℃ of logical nitrogen 30min again in 80 ℃ of reaction 3h, reduce to room temperature then, to remove unnecessary oleic acid, Fe is prepared in the octane extraction with deionized water, ethanol, propyl alcohol washing
3O
4Content is the magnetic fluid of 20-70wt%.
2, magnetic composite microsphere Fe
3O
4The preparation of/P (MMA/DVB)
Getting 1.0g magnetic content is the magnetic fluid of 25wt%, separates with magnetic behind the washing with acetone with ethanol respectively, and with the 50mL aqueous solution of the DNS-86 that is dissolved with 0.17g, ultrasonic emulsification obtains the magnetic miniemulsion then.Mix monomer with 2.3g MMA and 0.2gDVB joins in the external phase then, and swelling 1-2h forms and contains Fe
3O
4Monomer droplet.Letting nitrogen in and deoxidizing 30min adds 0.01g initiator KPS after being warming up to 70 ℃, and reaction 12h obtains magnetic Fe
3O
4/ P (MMA/DVB) complex microsphere.
3, the Fe that has nucleocapsid structure
3O
4/ P (the preparation of MMA/DVB) @P (St/GMA/DVB) complex microsphere
With Fe
3O
4The solution washing of the sodium lauryl sulphate of/P (MMA/DVB) complex microsphere usefulness 0.1wt% three times, after magnetic separates, redispersion is in the aqueous solution of the sodium lauryl sulphate of the 0.1wt% of 50ml, with it is seed, the shell monomers (mass ratio of shell monomers is: St: GMA: DVB=9: 8: 8) that adds 0.5g then in reaction system behind the logical nitrogen 30min, is replenished the KPS that adds 0.01-0.02g, keep 70 ℃ of reaction 12h, finally obtain the Fe that magnetic content is 76wt%
3O
4/ P (MMA/DVB) @P (St/GMA/DVB) complex microsphere.
Embodiment 2: magnetic content is the preparation of the core-shell structure magnetic complex microsphere of 66wt%
1, the Fe of oleic acid modification
3O
4The preparation of magnetic nano-particle is with described in the embodiment 1-1.
2, magnetic composite microsphere Fe
3O
4The preparation of/P (MMA/DVB) is with described in the embodiment 1-2.
3, the Fe that has nucleocapsid structure
3O
4(preparation of MMA/DVB) @P (St/GMA/DVB) complex microsphere is with described in the embodiment 1-3 for/P.Different is the shell monomers that adds 1.5g, and the magnetic content of the magnetic composite microsphere that finally obtains is 66wt%.
Embodiment 3: magnetic content is the preparation of the core-shell structure magnetic complex microsphere of 47wt%
1, the Fe of oleic acid modification
3O
4The preparation of magnetic nano-particle is with described in the embodiment 1-1.
2, magnetic composite microsphere Fe
3O
4The preparation of/P (MMA/DVB) is with described in the embodiment 1-2.
3, the Fe that has nucleocapsid structure
3O
4(preparation of MMA/DVB) @P (St/GMA/DVB) complex microsphere is with described in the embodiment 1-3 for/P.Different is the shell monomers that adds 2.0g, and the magnetic content of the magnetic composite microsphere that finally obtains is 47wt%.
Embodiment 4: magnetic content is the preparation of the core-shell structure magnetic complex microsphere of 28wt%
1, the Fe of oleic acid modification
3O
4The preparation of magnetic nano-particle is with described in the embodiment 1-1.
2, magnetic composite microsphere Fe
3O
4The preparation of/P (MMA/DVB) is with described in the embodiment 1-2.
3, the Fe that has nucleocapsid structure
3O
4(preparation of MMA/DVB) @P (St/GMA/DVB) complex microsphere is with described in the embodiment 1-3 for/P.Different is the shell monomers that adds 2.5g, and the magnetic content of the magnetic composite microsphere that finally obtains is 28wt%.
Embodiment 5: magnetic content is the preparation of the core-shell structure magnetic complex microsphere of 20wt%
1, the Fe of oleic acid modification
3O
4The preparation of magnetic nano-particle is with described in the embodiment 1-1.
2, magnetic composite microsphere Fe
3O
4The preparation of/P (MMA/DVB) is with described in the embodiment 1-2.
3, the Fe that has nucleocapsid structure
3O
4(preparation of MMA/DVB) @P (St/GMA/DVB) complex microsphere is with described in the embodiment 1-3 for/P.Different is the shell monomers that adds 5.0g, and the magnetic content of the magnetic composite microsphere that finally obtains is 20wt%.
Claims (6)
1. magnetic composite microsphere with nucleocapsid structure, it is characterized in that this complex microsphere is a nuclear with Z 250/polymer composite microsphere, with the polymkeric substance that has functional group is shell, wherein, Z 250 process oleic acid modification as nuclear, as the polymer monomer of nuclear is in vinylbenzene and (methyl) CALCIUM ACRYLATE one or more, as the polymkeric substance of shell be in vinylbenzene, methyl methacrylate, glycidyl methacrylate, hydroxyethyl methylacrylate, (methyl) vinylformic acid and the Vinylstyrene one or more; Magnetic content is 20-80wt%.
2. the preparation method with magnetic composite microsphere of nucleocapsid structure as claimed in claim 1 is characterized in that concrete steps are: at first, prepare the nano ferriferrous oxide particle of oleic acid modified with coprecipitation method; Then adopt the template mini-emulsion polymerization, the monodispersed Z 250/polymer composite microsphere of preparation high magnetic content; Adopt seeded emulsion polymerization then, the stratum nucleare magnetic composite microsphere is carried out the surface-functionalized coating of shell, be prepared into magnetic composite microsphere with nucleocapsid structure; Wherein, in the magnetic composite microsphere of nucleocapsid structure magnetic content between 20wt%-80wt%.
3. the preparation method with magnetic composite microsphere of nucleocapsid structure according to claim 2 is characterized in that: the concrete operations step of nano ferriferrous oxide particle that described employing coprecipitation method prepares oleic acid modified is as follows:
Under 75-85 ℃ to containing Fe
2+And Fe
3+Add excess of ammonia water in the aqueous solution of salt, and then adding accounts for Fe in system
3O
4The oleic acid of weight 1-40%, insulation reaction 2.5-3.5h, logical then vaporized nitrogen excess of ammonia water, obtain the nano ferriferrous oxide nanoparticle of oleic acid modification, wash to remove unnecessary oleic acid then octane extraction, preparation Fe respectively with deionized water, ethanol, propyl alcohol
3O
4Content is the magnetic fluid of 10-80 wt%;
The concrete operations step that described employing template mini-emulsion polymerization prepares the monodispersed Z 250/polymer composite microsphere of high magnetic content is as follows:
Under ultrasound condition, magnetic nano-particle is distributed in the solution that contains tensio-active agent, ultrasonic emulsification, ultrasonic power scope are 200-600W, ultrasonic time is 1-25min, obtains stable magnetic miniemulsion template; Then polymer monomer is joined in the magnetic miniemulsion template, swelling 1-2h obtains being rich in the monomer droplet of magnetic nano-particle; Add initiator then,, obtain the monodispersed Z 250/polymer composite microsphere of high magnetic content in 65-75 ℃ of polymerization 15-25 hour;
Described employing seeded emulsion polymerization carries out the surface-functionalized coating of shell to the stratum nucleare magnetic microsphere, and preparation has the magnetic composite microsphere of nucleocapsid structure, and concrete operations are as follows:
The above magnetic composite microsphere magnetic that obtains is separated, solution washing with sodium lauryl sulphate, after magnetic separates, redispersion is in the aqueous solution of sodium lauryl sulphate, add shell monomers then, add initiator,, obtain having the magnetic composite microsphere of nucleocapsid structure in 65-75 ℃ of polymerization 10-15 hour.
4. the preparation method with magnetic composite microsphere of nucleocapsid structure according to claim 3 is characterized in that described Fe
3+Salt is iron trichloride, Fe
2+Salt is a kind of in iron protochloride and the ferrous sulfate.
5. the preparation method with magnetic composite microsphere of nucleocapsid structure according to claim 2, in the step that it is characterized in that adopting the template mini-emulsion polymerization to prepare the monodispersed Z 250/polymer composite microsphere of high magnetic content, described tensio-active agent is one or more in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or allyloxy Nonyl pheno (10) ether ammonium sulfate;
Described monomer is one or more in vinylbenzene and (methyl) acrylate monomer;
Described initiator is a Potassium Persulphate, a kind of in ammonium persulphate or the Diisopropyl azodicarboxylate.
6. the preparation method with magnetic composite microsphere of nucleocapsid structure according to claim 2, in the step that it is characterized in that adopting seeded emulsion polymerization to prepare the magnetic composite microsphere with nucleocapsid structure, described shell monomers is one or more in vinylbenzene, methyl methacrylate, glycidyl methacrylate, hydroxyethyl methylacrylate, (methyl) vinylformic acid and the Vinylstyrene.
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