CN1380133A - Silicone dioxide magnetic microsphere and its preparation method - Google Patents
Silicone dioxide magnetic microsphere and its preparation method Download PDFInfo
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- CN1380133A CN1380133A CN 02111035 CN02111035A CN1380133A CN 1380133 A CN1380133 A CN 1380133A CN 02111035 CN02111035 CN 02111035 CN 02111035 A CN02111035 A CN 02111035A CN 1380133 A CN1380133 A CN 1380133A
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Abstract
The present invention discloses a silicon dioxide magnetic microsphere and its preparation method. The described silicon dioxide magnetic microsphere possesses high stability, can provide higher bonding capability, is easy to functionate, has no nude magnetic particles, its magnetic layer thickness is large, it has strong responsiveness to magnetic field and good uniformity. At the same time said silicon dioxide magnetic microsphere has good dispersity for various aqueous solutions, can be connected with various biological active substances, such as antibody, antigen, enzyme, protein or nucleic acid, and specially is applicable to separation and purification of biological and medicine products.
Description
Technical field
The present invention relates to a kind of silicone dioxide magnetic microsphere and preparation method thereof, particularly a kind of silicone dioxide magnetic microsphere of multi-layer core-shell formula and its preparation method.
Background technology
Silicone dioxide magnetic microsphere separates from suspension under the outside magnetic field easily, does not show any remanent magnetism and remove these microballoons of external magnetic field, therefore is applicable to cell separation, affinity purification, dna probe detection and magnetic EIA enzyme immunoassay etc.
Silicon dioxide granule is a kind of generally acknowledged adsorbent and the carrier of adsorbent.This carrier can with centrifugal, filter and similarly method reuse, but when isolating adsorbate or extract, adopts centrifugal, post separates or similar method, need the cost plenty of time, and the equipment that adopts is relatively more expensive, uses inconvenience.
U.S. Pat P 5,734,020 (1998) disclosed a kind of method, with the inorganic silicon material soaking of porous in magnetic fluid, place adsorption equilibrium on the shaking table, centrifugally remove unnecessary magnetic fluid, make magnetic microsphere after the washing, utilize the magnetisable material in the hole, carry out the separation of target organism material by magnetic field.Yet the character of these magnetic microspheres can not fully be controlled, and reason is that specific area, the magnetic content of material of diameter of micro ball, bore dia, pore volume, microballoon is difficult to be consistent.
In order to keep the character unanimity of magnetic microsphere; U.S. Pat P 6; 103; 379 (2000) disclose another kind of preparation method; ferriferrous oxide nano-particle is coated on the surface of macromolecule (as polystyrene, polymethyl methacrylate, the polychlorostyrene methyl styrene) microballoon of single size by the precipitation method; form the core-shell type magnetic polymer microsphere, outside magnetic microsphere, coat silicon dioxide layer of protection with the silane hydrolyzate method then.Yet the precipitation method can not keep the high iron oxide magnetosphere of polymer microsphere surface, cause magnetisable material content low, need it could be separated with very strong magnetic separator.
The method of employing layer upon layer electrostatic self assembly can improve the shell of hud typed microballoon.Document (Caruso F, Susha A, Giersig M, M hwald H.Magnetic Core-shell Particles:Preparation of Magnetite Multilayers onPolymer Latex Microspheres, Adv.Mater.1999 11:950-952) has reported that the method that adopts the layer upon layer electrostatic self assembly is assembled in nano ferriferrous oxide the research of polymer microsphere.But the magnetic macromolecular microsphere skin that obtains like this is the magnetic particle that exposes entirely, to a lot of biological toxic effects of type material of living, has limited its range of application.
Summary of the invention
One of purpose of the present invention be propose a kind ofly to have superparamagnetism, magnetic particle/depolymerization electrolyte is wrapped in the silicon dioxide microsphere surface layer by layer, and outermost layer wraps up single dispersion of nanometer titanium dioxide silicon structure, the silicone dioxide magnetic microsphere of narrow distribution again, solves above-mentioned problems of the prior art;
Two of purpose of the present invention is the preparation method of the described silicone dioxide magnetic microsphere of one of open purpose.
Realize the technical scheme of the object of the invention:
Silicone dioxide magnetic microsphere of the present invention is a kind of hud typed microballoon of multilayer.Wherein kernel is a silicon dioxide microsphere, and nuclear is outer to be that organic material and magnetic nanoparticle replace the adsorbent serial layer.For example, ABABA, wherein A is a cationic polyelectrolyte, B is a magnetic nanoparticle.The sequence number of plies is unrestricted.Last one deck organic layer outside is the nano silicon colloidal particle.
Described silicon dioxide microsphere is that the average grain diameter of single size is the silicon dioxide microsphere of 0.05-10 μ m, and only is that average grain diameter is the silicon dioxide microsphere of 0.1-2 μ m.
Described organic material is the polymer that contains the functional group of a plurality of ions or ionogenic band identical charges, as polyelectrolyte.Cationic polyelectrolyte particularly, as poly (diallyldimethylammonium chloride) (" PDDA "), poly (N-methyl-4-vinylpyridinium bromide), or poly (D-lysinehydrobromide).
Said magnetic nanoparticle can comprise the nanometer Fe of superparamagnetism
3O
4Particle, nanometer γ-Fe
2O
3Particle or mix transition metal such as chromium, cobalt, copper, magnesium, manganese, nickel, zinc and their mixture nanometer ferrite particle etc., only is nanometer Fe
3O
4Particle.
The average grain diameter that said nano silicon colloidal particle is a single size is the silicon dioxide colloid particle of 1-20nm, and optimum is the silicon dioxide colloid particle of 5-15nm.
The preparation method of silicone dioxide magnetic microsphere of the present invention comprises the steps:
(1) (it is synthetic referring to J.Colloid InterfaceSci.1968 with silicon dioxide microsphere, (26) 62-69 " Controlled Growth of MonodisperseSilica Spheres in the Micron Size Range ") add in the aqueous solution of being made up of organic material and soluble-salt, the quality ratio of the silicon dioxide microsphere and the aqueous solution is 0.01-0.1; Organic concentration is 0.1-5g/L in the aqueous solution; The concentration of soluble-salt is 0.2-0.6M, and the adjusting pH value of aqueous solution is 9-11.Stir down 5-100min at 5-50 ℃, form the water-soluble suspension of silicon dioxide microsphere absorption organic material, after this suspension adopts centrifugal method to remove clear liquid, with deionized water washing/centrifugal/disperse again 3-5 all over after water-soluble silica suspension.(2) will contain the magnetic nanoparticle mass percent is that the water-soluble magnetic fluid of 0.5-10% adds by in the water-soluble silica suspension of step (1) gained, the volume ratio of water-soluble magnetic fluid and water-soluble silica suspension is 0.01-0.05, remove unnecessary magnetic fluid with centrifugal method behind the stirring 5-100min down at 5-50 ℃, with deionized water washing/centrifugal/disperse the centrifugal again deposit that obtains again 3-5 time.(3) will add again in the above-mentioned aqueous solution of forming by organic material and soluble-salt by step (2) gained deposit, except that without the adjust pH, other set by step (1) carry out once again, water-soluble silica suspension.The water-soluble magnetic fluid that will contain the magnetic nanoparticle mass percent again and be 0.5-10% adds repeating step (2) in the water-soluble silica suspension of gained, so circulate repeatedly, the outermost layer that obtains microballoon is the water-soluble silica suspension of organic matter absorption.(4) the pH value of regulating by the water-soluble silica suspension of step (3) gained with alkali is 9-11, add the nano silicon colloidal particle, the quality ratio of nano silicon colloidal particle and silicon dioxide microsphere is 0.1-2, promptly gets silicone dioxide magnetic microsphere of the present invention.
Specific implementation method
1) nanometer Fe of superparamagnetism
3O
4The preparation of particle or other ferrite particle:
The ammoniacal liquor or the NaOH aqueous solution are added FeCl
2With FeCl
3In the mixed liquor (or containing the molysite of part transition metal salt), be 8-11, be preferably 10-11 until the pH value with corresponding valence states of mole such as replacing.Then, stirred 0.5-5 hour down at 55-90 ℃.The mol ratio of divalence and trivalent metal salt is 0.4-0.6.Obtain the nanometer Fe of particle diameter less than the superparamagnetism of 30nm
3O
4Particle or other ferrite particle suspension.The soap that adds the 5-10% weight ratio again as enuatrol, behind the slaking 30-60min, is cooled to room temperature, with acid, transfers pH to 4-6 as HCl, filter then, and washing, alcohol is washed again, and last 80 ℃ of dryings obtain the nanometer Fe of superparamagnetism
3O
4Particle or other ferrite particle.
2) preparation of water-soluble magnetic fluid:
The nanometer Fe of the superparamagnetism that step 1) is obtained
3O
4Particle or other ferrite particle add that mass percent is the anion surfactant of 5-15%, as lauryl sodium sulfate, neopelex or dodecyl sodium sulfate mix, and are mixed with to contain the water-soluble magnetic fluid that magnetic nanoparticle is 0.5-10% (mass percent).
3) preparation of silicone dioxide magnetic microsphere:
I) with said organic material of technical scheme and soluble-salt, be mixed with solution A as NaCl or KCl etc.Organic concentration is 0.1-5g/L in the solution A, and the concentration of salt is 0.2-0.6M.
Ii) with the said silicon dioxide microsphere dispersed with stirring of technical scheme in solution A, use alkali, regulate pH value of aqueous solution as NaOH, the pH value is preferably between the 9-11.5-50 ℃ is stirred 10-30min down, forms the water-soluble suspension of silicon dioxide microsphere absorption organic material, and the quality ratio of silicon dioxide microsphere and solution A is 0.02-0.05.Use centrifugally then, remove supernatant, with deionized water washing/centrifugal/disperse again 3-5 time.
Iii) with step 2) in the water-soluble magnetic fluid that obtains join in the washed silica suspension, 5-50 ℃ is stirred 10-30min down, the volume ratio of magnetic fluid and silica suspension is 0.01-0.05.Use centrifugally then, remove unnecessary magnetic fluid, with deionized water washing/centrifugal/disperse the centrifugal again deposit that obtains again 3-5 time.
Iv) step I is obtained deposit in ii) and is dispersed in again in the solution A, except that without the adjust pH, other set by step ii) operation carry out once again.
V) with step 2) in the water-soluble magnetic fluid that obtains join in the suspension that step I v) obtains, by step continuation absorption magnetic nanoparticle iii), by step adsorb organic compound iv), so circulate repeatedly, the outermost layer that obtains microballoon is the suspension of organic matter absorption.
Vi) use alkali, as the pH value that NaOH regulates suspension, the pH value is preferably between the 9-11.Add the said nano silicon colloidal particle of technical scheme again.The quality ratio of nano silicon colloidal particle and silicon dioxide microsphere is 0.2-1.
The above-mentioned silicone dioxide magnetic microsphere that makes has following characteristics: (1) stability is than magnetic macromolecular microsphere height, and swelling easily takes place in organic solution magnetic macromolecular microsphere; What (2) outermost layer coated is the silicon dioxide granule of 1-20nm, therefore, compares with the smooth magnetic microsphere of same diameter, and its specific area is big, and higher bonding power can be provided; (3) Biao Mian chemical composition is a silica, is very easy to functionalization; (4) do not have exposed magnetic particle, this silicone dioxide magnetic microsphere of 1g is immersed among the HCl of 10mL1M, and 70 ℃ are soaked 2h, and iron concentration is lower than 10ppm; (5) magnetic coating thickness is big, can be by the control of assembling number of times.As assemble nanometer Fe 10 times
3O
4Particle, magnetic coating thickness can reach 150-200nm, and (but this is not as restriction of thickness) is therefore, strong to magnetic responsiveness; (6) because the kernel silicon dioxide microsphere compares uniformity, therefore, the silicone dioxide magnetic microsphere after the assembling also can keep reasonable uniformity consistency.
This silicone dioxide magnetic microsphere is better dispersed to the various aqueous solution, and the active substances of can delivering a child is as antibody, antigen, enzyme, protein or nucleic acid.Be specially adapted to separating and the purifying aspect of biology and pharmaceutical products.
Further illustrate content of the present invention below in conjunction with embodiment, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
The FeCl that the 1.0mol/L NaOH aqueous solution is slowly added 1.0mol/L
2FeCl with 2.0mol/L
3In the mixed aqueous solution, be 10 until the pH value.Stir 1h down at 85 ℃ then, obtain the nanometer Fe of superparamagnetism
3O
4Particle suspension.Add the dispersant enuatrol of 10% weight ratio again, behind the slaking 40min, be cooled to room temperature, transfer pH to 5 with HCl again, filter then, washing, alcohol is washed, and 80 ℃ of dryings then obtain the nanometer Fe of superparamagnetism
3O
4Particle.Observe Fe with transmission electron microscope (TEM)
3O
4The particle diameter of particle is 8-12nm.
Embodiment 2
The nanometer Fe that embodiment 1 is made
3O
4Particle 2g, neopelex 0.2g, deionized water 100g mixes, and makes water-soluble magnetic fluid.
Embodiment 3
1) takes by weighing the silicon dioxide microsphere that the 2g average grain diameter is 220nm.Be poured in the small beaker of 100mL, adding 100mL concentration is cationic polyelectrolyte diallyl dimethyl ammoniumchloride (PDADMAC) (the containing 0.5M NaCl) aqueous solution of 1g/L.The NaOH aqueous solution that adds 4M, adjust pH to 10 stirs 20min under the room temperature.With centrifuge centrifugal 15min under 5000 rotating speeds that change.Remove supernatant.With deionized water washing/centrifugal/disperse again 4 times, obtain adsorbing the microballoon of one deck PDADMAC.
2) the water-soluble magnetic fluid 1mL that obtains among the embodiment 2 is joined in the washed silica suspension, stirring and adsorbing 15min under the room temperature uses centrifugally then, removes unnecessary magnetic fluid, with deionized water washing/centrifugal/disperse the centrifugal again nanometer Fe that obtains again 4 times
3O
4Particle is adsorbed on the microballoon deposit of the second layer.
3) add cationic polyelectrolyte diallyl dimethyl ammoniumchloride (PDADMAC) (the containing 0.5M NaCl) aqueous solution that 100mL concentration is 1g/L again.Adsorb 15min under the room temperature, use centrifugally then, remove supernatant,, obtain the microballoon that PDADMAC is adsorbed on the 3rd layer with deionized water washing/centrifugal/disperse again 4 times.
4) continuous repeating step 2), 3), obtain silicon dioxide microsphere outside first and third, five, seven, nine at last, eleventh floor is the PDADMAC adsorption layer, second, four, six, eight, ten layer is nanometer Fe
3O
4The particle adsorption layer.
5) be that 10% silica gel (the silica average grain diameter is 10nm) 5mL joins in the microsphere suspension liquid of the above-mentioned multilayer absorption of 100mL with mass ratio, the pH value of regulating suspension with NaOH is 10.Adsorb 15min under the room temperature, use centrifugally then, remove unnecessary silica gel,, obtain the silicone dioxide magnetic microsphere of outermost layer absorption Nano particles of silicon dioxide with deionized water washing/centrifugal/disperse again 4 times.The average grain diameter that records the magnetic silica microballoon after the absorption of silicon dioxide microsphere and multilayer before the absorption with the LS-230 of Coulter company laser particle analyzer is respectively 220nm and 548nm, and deviation factor is respectively 4.9% and 9.3%.This silicone dioxide magnetic microsphere of 1g is immersed among the HCl of 10mL1M, and 70 ℃ are soaked 2h, record iron concentration and be lower than 10ppm.
Embodiment 4
Except FeCl with 0.9mol/L
2NiCl with 0.1mol/L
2Mixed solution replace the FeCl of 1.0mol/L
2Outside the aqueous solution, other condition obtains the nanometer Ni of superparamagnetism with embodiment 1
0.1Fe
2.9O
4Particle.Observe with transmission electron microscope (TEM), its particle diameter still is 8-12nm.Press the step of embodiment 2 again, replace neopelex among the embodiment 2 with lauryl sodium sulfate, also water-soluble magnetic fluid.Press the step of embodiment 3 at last, select for use average grain diameter be 318nm silicon dioxide microsphere for nuclear, with the PDADMAC among the cationic polyelectrolyte PAH replacement embodiment 3, and alternately adsorbing PAH is 10 layers, the absorption magnetic nanoparticle is 9 layers, outermost absorption one deck nano-silicon dioxide particle obtains silicone dioxide magnetic microsphere.The average grain diameter that records the magnetic silica microballoon after the absorption of silicon dioxide microsphere and multilayer before the absorption with the LS-230 of Coulter company laser particle analyzer is respectively 318nm and 1025nm, and deviation factor is respectively 5.0% and 13.4%.This silicone dioxide magnetic microsphere of 1g is immersed among the HCl of 10mL1M, and 70 ℃ are soaked 2h, record iron concentration and be lower than 10ppm.
Claims (6)
1, a kind of silicone dioxide magnetic microsphere is characterized in that described silicone dioxide magnetic microsphere is hud typed microballoon, and its kernel is a silicon dioxide microsphere, nuclear is outer to be that organic material and magnetic nanoparticle replace the adsorbent serial layer, the sequence number of plies is unrestricted, and outermost layer is the nano silicon colloidal particle
Described organic material is the polymer that contains the functional group of a plurality of ions or ionogenic band identical charges;
Said magnetic nanoparticle is the nanometer Fe of superparamagnetism
3O
4Particle, nanometer γ-Fe
2O
3Particle or mix transition metal and composition thereof nanometer ferrite particle.
2, silicone dioxide magnetic microsphere according to claim 1, the average grain diameter that it is characterized by wherein said silicon dioxide microsphere and be single size is the silicon dioxide microsphere of 0.05-10 μ m; The average grain diameter that said nano silicon colloidal particle is a single size is the silicon dioxide colloid particle of 1-20nm.
3, silicone dioxide magnetic microsphere according to claim 1, it is characterized by wherein said organic material is cationic polyelectrolyte, described magnetic nanoparticle is a nanometer Fe
3O
4Particle.
4,, it is characterized by described method and comprise the steps: as the preparation method of described any one silicone dioxide magnetic microsphere of claim 1-3
(1) silicon dioxide microsphere is added in the aqueous solution of being made up of organic material and soluble-salt, the quality ratio of the silicon dioxide microsphere and the aqueous solution is 0.01-0.1; Organic concentration is 0.1-5g/L in the aqueous solution; The concentration of soluble-salt is 0.2-0.6M, the adjusting pH value of aqueous solution is 9-11, stir 5-100min down at 5-50 ℃, form the water-soluble suspension of silicon dioxide microsphere absorption organic material, after this suspension adopts centrifugal method to remove clear liquid, with deionized water washing/centrifugal/disperse again 3-5 all over after water-soluble silica suspension;
(2) will contain the magnetic nanoparticle mass percent is that the water-soluble magnetic fluid of 0.5-10% adds by in the water-soluble silica suspension of step (1) gained, the volume ratio of water-soluble magnetic fluid and water-soluble silica suspension is 0.01-0.05, remove unnecessary magnetic fluid with centrifugal method behind the stirring 5-100min down at 5-50 ℃, with deionized water washing/centrifugal/disperse the centrifugal again deposit that obtains again 3-5 time;
(3) will add again in the above-mentioned aqueous solution of forming by organic material and soluble-salt by step (2) gained deposit, except that without the adjust pH, other set by step (1) carry out once again, get water-soluble silica suspension, the water-soluble magnetic fluid that will contain the magnetic nanoparticle mass percent again and be 0.5-10% adds repeating step (2) in the water-soluble silica suspension of gained, and so circulation obtains the water-soluble silica suspension that the outermost layer of microballoon is organic matter absorption;
(4) the pH value of regulating by the water-soluble silica suspension of step (3) gained with alkali is 9-11, add the nano silicon colloidal particle, the quality ratio of nano silicon colloidal particle and silicon dioxide microsphere is 0.1-2, promptly gets silicone dioxide magnetic microsphere of the present invention.
5, preparation method as claimed in claim 4, it is characterized by wherein said soluble-salt is NaCl or KCl.
6, preparation method as claimed in claim 4, the quality ratio that it is characterized by the wherein said silicon dioxide microsphere and the soluble-salt aqueous solution is 0.02-0.05; The quality ratio of described silicon dioxide microsphere and nano silicon colloidal particle is 0.2-1.
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