CN102614549B - Ferroferric oxide calcium phosphate nuclear shell magnetic nanoparticle and preparation method thereof by biological mineralization method - Google Patents
Ferroferric oxide calcium phosphate nuclear shell magnetic nanoparticle and preparation method thereof by biological mineralization method Download PDFInfo
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Abstract
The invention discloses a ferroferric oxide calcium phosphate nuclear shell magnetic nanoparticle and a preparation method thereof by a biological mineralization method and belongs to the technical field of magnetic particles. A magnetic ferroferric oxide nanoparticle serves as a core, wherein the mean grain size of the particle is 27 to 38nm; and a calcium phosphate material serves as a shell layer, wherein the thickness of the shell layer is 4 to 20nm. The preparation method comprises the following steps that the ferroferric oxide magnetic nanoparticle is prepared and then is modified by a surface modifier; the modified ferroferric oxide magnetic nanoparticle is added into simulated human body fluid which is prepared and has the concentration of 1 to 10 times; the modified ferroferric oxide magnetic nanoparticle is mineralized; and the product is washed, subjected to magnetic separation and dried to obtain the ferroferric oxide calcium phosphate nuclear shell magnetic nanoparticle. The preparation method is simple in operation, mild in preparation process condition, wide in raw material source and environment friendly. The prepared nuclear shell nanoparticle has biological activity and has good application prospect in the field of biomedicine, such as tissue engineering and medicine carrying.
Description
Technical field
The present invention relates to a kind of magnetic nanoparticle with bioactive nucleocapsid structure and preparation method thereof, particularly biomineralization legal system, for ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle, belongs to magnetic particle technical field.
Technical background
Ferroso-ferric oxide is a kind of very important magnetic material, is Emission in Cubic inverse spinel structure.The electricity of its uniqueness and magnetic performance, make it be widely used in magnetic fluid and magnetic recording material etc.For the ferroso-ferric oxide of nanoscale, because it has and the compatibility of biological tissue, electricity and the magnetic performance relevant with pattern with size, at biomedicine field, be widely applied.There is the superparamagnetism iron Oxides Nanoparticles of suitable surface chemical property can be applied to application in numerous bodies, as live body magnetic resonance contrast enhancing, tissue repair, immunoassay, removing toxic substances, thermotherapy, drug conveying and cell separation.
Osseous tissue is a kind of connective tissue of densification.Organic substance and inorganic matter are the main components of bone, and wherein Organic substance is mainly protein as collagen etc., and inorganic matter is mainly calcareous and phosphorus matter, and certain hardness is provided.Calcium phosphate bioceramic (also can be called for short calcium phosphate) has the composition close with bone mineral and good biocompatibility, it mainly comprises hydroxyapatite (HA), calcium phosphate dibasic dihydrate (DCPD), tricalcium phosphate (α-TCP, β-TCP), calcium pyrophosphate (CPPD), tetracalcium phosphate (TTCP), five water OCPs (OCP), amorphous calcium phosphate (ACP) and composition thereof etc.At the tissue of at present scientific research and clinical practice, replace in biomaterial, calcium phosphate provides a kind of selectivity or additional material for grafting and has participated in therapeutic process for surgeon.
Studies have reported that [JOURNAL OF BIO SCIENCE AND BIOENGINEERING. Vol.104, No.5,371-378.2007], by ferroso-ferric oxide compound particle and the co-culture of cells of coated biologically active material, particle is attached on cell or by cellular uptake, and under the effect of externally-applied magnetic field, cell energy multilamellar closely attaches growth, thereby improved the density of unit volume inner cell, formed fine and close cell thin film.Adopt calcium phosphate coated ferriferrous oxide nano-particle, formed core-shell structure nanometer particle has had the superparamagnetism of nano ferriferrous oxide and the good biocompatibility of calcium phosphate concurrently, itself and skeletonization relevant cell have excellent affinity, utilize magnetic field to be easy to realize the cultivation of cellular layer, for osteanagenesis, repair significant.
The method of traditional inorganic core-shell structure nanometer particle of preparation has sol-gal process, coprecipitation, ball-milling method, reverse microemulsion process etc., and the structure of the core-shell material that these methods are synthetic and material form to be needed further to improve.For example, core-shell particles shell prepared by coprecipitation and ball-milling method is inhomogeneous, and dispersibility is poor; Sol-gal process preparation process is more, and colloidal sol, the colloidal sol that need carry out predecessor is converted into the steps such as gel, dry and heat treatment.Meanwhile, the calcium phosphate compound material that traditional preparation method obtains forms can not meet the biocompatibility close and good with bone mineral.And the correlational study of ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle prepared by employing biomineralization method rarely has report, this preparation method is optimized, and the selection of material mostly is inorganic salts, and wide material sources are also environmentally friendly.
Summary of the invention
The present invention forms the technical problems such as poor in order to solve the material structure and the material that exist in prior art, and a kind of magnetic nanoparticle with bioactive nucleocapsid structure and preparation method thereof is provided.
For this reason, the present invention adopts a kind of method of biomineralization, has prepared a kind of ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle, and the method technique is simple, mild condition is controlled, environmentally friendly.
Ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle provided by the present invention, is characterized in that, the ferriferrous oxide nano-particle of magnetic of take is core, and its mean diameter is 27-38nm, and calcium phosphate material is shell, and shell thickness is 4-20nm.
The composition of calcium phosphate material shell described above can be hydroxyapatite (HA), calcium phosphate dibasic dihydrate (DCPD), tricalcium phosphate (α-TCP, β-TCP), calcium pyrophosphate (CPPD), tetracalcium phosphate (TTCP), five water OCPs (OCP), amorphous calcium phosphate (ACP) etc.
The saturation magnetization of ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle provided by the present invention is 8-48emu/g.
The present invention also provides a kind of biomineralization method preparation method of ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle, and it comprises following steps:
(1) prepare ferriferrous oxide nano magnetic particle: divalent iron salt is made in aqueous solution, join in dispersant solution, at the uniform velocity stir, then to mixed liquor slowly to drip aqueous slkali, oxidant hydrogen peroxide, the pH of guarantee system is 10-11, heating, constant temperature 60-160 ℃ after stirring reaction 1-8 hour, utilize externally-applied magnetic field by product separation, washing, lyophilization, makes ferriferrous oxide nano magnetic particle;
(2) ferriferrous oxide nano magnetic particle surface modification: ferriferrous oxide nano magnetic particle and the surface modifier of step (1) gained are added in deionized water, and ultrasonic agitation ground obtains the ferriferrous oxide nano magnetic particle of surperficial introducing carboxyl.
(3) prepare ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle: by NaCl, NaHCO
3, KCl, K
2hPO
43H
2o, MgCl
2, CaCl
2, Na
2sO
410H
2o is dissolved in deionized water, 37 ± 0.5 ℃ of constant temperature, adding buffer agent or continuing to pass into carbon dioxide is also 6.30-7.40 with hydrochloride adjusted solution pH value, makes the simulated body fluid (1-10 that the concentration that is simulated body fluid is human body fluid doubly) of 1-10 times of concentration; By the ferriferrous oxide nano magnetic particle of the surface modification obtaining in step (2) mineralising in lasting mechanical agitation joins above-mentioned simulated body fluid, obtain ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle after product washing, magnetic is separated, dry.
The preferred technical scheme of the present invention is: the divalent iron salt described in step (1) is a kind of in ferrous chloride or ferrous sulfate, dispersant solution is a kind of in Polyethylene Glycol, polyvinyl acetate or polyvinylpyrrolidone aqueous solution, and alkali is a kind of in ammonia spirit, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
Surface modifier described in step (2) is a kind of in citric acid or sodium citrate, and the mass ratio of itself and ferroso-ferric oxide is 50: 1-10: 1; The described ultrasonic agitation time is 12-15 hour.
Described in step (3), buffer agent is Tris, and the mass ratio of buffer agent and NaCl is 1: 8-1: 4; In 1-10 simulated body fluid doubly, the molar concentration of each ion is: Ca
2+2.5-25.0mmol/L, HPO
4 2-1.0-10.0mmol/L, Na
+142.0-1000.0mmol/L, K
+5.0-25.0mmol/L, Mg
2+1.5-7.7mmol/L, Cl
-148.0-750.0mmol/L, HCO
3 -4.2-42.0mmol/L, SO
4 2-0.5-5.0mmol/L; Wherein the mineralising response time is 0.5-60 hour.Above-mentioned preferably along with the multiple increase of simulated body fluid, its mineralising time is reducing, and just can obtain the shell of suitable thickness, can be just ferriferrous oxide nano-particle superior performance.
Remarkable result of the present invention is: the standby ferriferrous oxide nano-particle of hydrothermal oxidization legal system of the present invention has superparamagnetism, high saturation magnetization and uniformly particle size distribution, adopt the method for biomineralization to simulate human body environment, by ferroso-ferric oxide functionalisation of surfaces, by biomineralization at core chemical absorption of surface calcium, phosphonium ion forms calcium phosphate inorganic substances, bi-material is combined closely by chemical bond with nucleocapsid form, in ferroso-ferric oxide surface coverage one deck calcium phosphate inorganic mineral, shell classes of compounds is abundant, this material can be the adhesion of osteocyte, growth and propagation provide condition preferably.The core-shell nano of preparation has superparamagnetism and biological activity concurrently, can be applicable to the biomedical sectors such as organizational project, medicine carrying.
Accompanying drawing explanation
Fig. 1 is the XRD figure of ferroso-ferric oxide calcium phosphate nano particle described in embodiment 1;
Fig. 2 is the TEM figure of ferroso-ferric oxide calcium phosphate nano particle described in embodiment 1;
Fig. 3 is the VSM figure of ferroso-ferric oxide calcium phosphate nano particle described in embodiment 1.
The specific embodiment
Embodiment 1
(1) 1.5g Polyethylene Glycol (Mw=4000) is dissolved in 15ml deionized water, mechanical agitation is more than 12 hours.Take 1.789g ferrous chloride, be dissolved in 15ml deionized water, be stirred to whole dissolvings, add in polyglycol solution.The churned mechanically while slowly drips the ammonia spirit of 17ml 2.5%; Then drip the hydrogen peroxide of 5ml3%; Add again 50ml deionized water.The pH of guarantee system 11 is transferred to the water-bath of 60 ℃ by above-mentioned mixed solution, continues mechanical agitation 1 hour.After reaction finishes, utilize externally-applied magnetic field that gained precipitation is separated from reaction medium, use washed with de-ionized water 5 times.Finally precipitation is put into freeze drying box dry, both obtained ferriferrous oxide nano magnetic particle.
(2) ready ferriferrous oxide nano magnetic particle and sodium citrate are put into deionized water by the mass ratio of 1: 10, ultrasonic agitation 12 hours.Centrifugal to products therefrom, remove the supernatant, lower sediment is the ferroferric oxide magnetic nano-particles of sodium citrate surface modification.
(3) take the ferroferric oxide magnetic nano-particles of 0.04g surface modification, be dispersed in deionized water.Take 39.972g NaCl, 1.764g NaHCO
3, 1.118g KCl, 1.141g K
2hPO
43H
2o, 1.565gMgCl
2, 1.410g CaCl
2with 0.355g Na
2sO
410H
2o is dissolved in 1L deionized water successively, continues to pass into CO
2gas also uses the hydrochloride adjusted solution pH value of 1mol/l to 6.42 left and right, makes 5 times of simulated body fluids.The aqueous solution that contains ferriferrous oxide nano-particle is joined in 5 times of simulated body fluids under continuing mechanical agitation, 37 ± 0.5 ℃ of constant temperature, mineralising 12 hours, obtains ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle by product washing, after separated, dry.The crystal formation of shell bridge layer calcium phosphate mineral is mainly calcium phosphate dibasic dihydrate.The mean diameter of ferroso-ferric oxide particle is 27.5nm, and shell thickness is 4nm.Saturation magnetization is 47.2emu/g.
Fig. 1 is the XRD figure of embodiment 1 gained ferroso-ferric oxide calcium phosphate nano particle; Fig. 2 is the TEM figure of embodiment 1 gained ferroso-ferric oxide calcium phosphate nano particle; Fig. 3 is the VSM figure of embodiment 1 gained ferroso-ferric oxide calcium phosphate nano particle;
Comparative example 1: in mineralization process, do not continue to pass into CO
2gas, other conditions are with embodiment 1, and reaction finishes rear generation hydroxyapatite micrometre particle, can not form nucleocapsid structure with ferroso-ferric oxide.
Embodiment 2
(1) 1.5g Polyethylene Glycol (Mw=4000) is dissolved in 15ml deionized water, mechanical agitation is more than 12 hours.Take 1.789g ferrous chloride, be dissolved in 15ml deionized water, be stirred to whole dissolvings, add in polyglycol solution.The churned mechanically while slowly drips the ammonia spirit of 17ml 2.5%; Then drip the hydrogen peroxide of 5ml3%; Add again 50ml deionized water.The pH of guarantee system 11 is transferred to the water-bath of 160 ℃ by above-mentioned mixed solution, continues mechanical agitation 1 hour.After reaction finishes, utilize externally-applied magnetic field that gained precipitation is separated from reaction medium, use washed with de-ionized water 5 times.Finally precipitation is put into freeze drying box dry, both obtained ferriferrous oxide nano magnetic particle.
(2) ready ferriferrous oxide nano magnetic particle and sodium citrate are put into deionized water by the mass ratio of 1: 10, ultrasonic agitation 12 hours.Centrifugal to products therefrom, remove the supernatant, lower sediment is the ferroferric oxide magnetic nano-particles of sodium citrate surface modification.
(3) take the ferroferric oxide magnetic nano-particles of 0.04g surface modification, be dispersed in deionized water.Take 39.972g NaCl, 1.764g NaHCO
3, 1.118g KCl, 1.141g K
2hPO
43H
2o, 1.565gMgCl
2, 1.410g CaCl
2with 0.355g Na
2sO
410H
2o is dissolved in 1L deionized water successively, adds 10g Tris buffer agent and uses the hydrochloride adjusted solution pH value of 1mol/l to 6.42 left and right, obtains 5 times of simulated body fluids; The aqueous solution that contains ferriferrous oxide nano-particle is joined in 5 times of simulated body fluids under continuing mechanical agitation to 37 ± 0.5 ℃ of constant temperature.Mineralising 1 hour, obtains ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle by product washing, after separated, dry.The crystal formation of shell calcium phosphate mineral is mainly unbodied hydroxyapatite.The mean diameter of ferroso-ferric oxide particle is 32.5nm, and shell thickness is 4nm.Saturation magnetization is 47.3emu/g.
Comparative example 2: mineralization process does not add Tris buffer agent, and other conditions, with embodiment 2, should finish rear generation hydroxyapatite micrometre particle, can not form nucleocapsid structure with ferroso-ferric oxide.
Embodiment 3
(1) 1.5g Polyethylene Glycol (Mw=4000) is dissolved in 15ml deionized water, mechanical agitation is more than 12 hours.Take 1.789g ferrous chloride, be dissolved in 15ml deionized water, be stirred to whole dissolvings, add in polyglycol solution.The churned mechanically while slowly drips the ammonia spirit of 17ml 2.5%; Then drip the hydrogen peroxide of 5ml3%; Add again 50ml deionized water.The pH of guarantee system 10 is transferred to the water-bath of 100 ℃ by above-mentioned mixed solution, continues mechanical agitation 1 hour.After reaction finishes, utilize externally-applied magnetic field that gained precipitation is separated from reaction medium, use washed with de-ionized water 5 times.Finally precipitation is put into freeze drying box dry, both obtained ferriferrous oxide nano magnetic particle.
(2) ready ferriferrous oxide nano magnetic particle and sodium citrate are put into deionized water by the mass ratio of 1: 20, ultrasonic agitation 12 hours.Centrifugal to products therefrom, remove the supernatant, lower sediment is the ferroferric oxide magnetic nano-particles of sodium citrate surface modification.
(3) take the ferroferric oxide magnetic nano-particles of 0.04g surface modification, be dispersed in deionized water.Take 39.972g NaCl, 1.764g NaHCO
3, 1.118g KCl, 1.141g K
2hPO
43H
2o, 1.565gMgCl
2, 1.410g CaCl
2with 0.355g Na
2sO
410H
2o is dissolved in 1L deionized water successively, adds 5g Tris buffer agent and uses the hydrochloride adjusted solution pH value of 1mol/l to 6.42 left and right, obtains 5 times of simulated body fluids; The aqueous solution that contains ferriferrous oxide nano-particle is joined in 5 times of simulated body fluids under continuing mechanical agitation to 37 ± 0.5 ℃ of constant temperature.Mineralising 3 hours, obtains ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle by product washing, after separated, dry.The crystal formation of shell calcium phosphate mineral is mainly unbodied hydroxyapatite.The mean diameter of ferroso-ferric oxide particle is 30nm, and shell thickness is 20nm.Saturation magnetization is 8.0emu/g.
Comparative example 3: prepare in ferriferrous oxide nano-particle process system pH lower than 10, its condition is with embodiment 3, and the product obtaining after reaction finishes is iron sesquioxide calcium phosphate core-shell nano.
Embodiment 4
(1) 0.5g polyvinyl acetate (Mw=30000) is dissolved in 15ml deionized water, mechanical agitation is more than 12 hours.Take 2.499g ferrous sulfate, be dissolved in 15ml deionized water, be stirred to whole dissolvings, add in polyvinyl acetate ester solution.The churned mechanically while slowly drips the sodium hydroxide solution of 17ml 2.5%; Then drip the hydrogen peroxide of 5ml 3%; Add again 50ml deionized water.The pH of guarantee system 11 is transferred to the water-bath of 160 ℃ by above-mentioned mixed solution, continues mechanical agitation 8 hours.After reaction finishes, utilize externally-applied magnetic field that gained precipitation is separated from reaction medium, use washed with de-ionized water 5 times.Finally precipitation is put into freeze drying box dry, both obtained ferriferrous oxide nano magnetic particle.
(2) ready ferriferrous oxide nano magnetic particle and citric acid are put into deionized water by the mass ratio of 1: 25, ultrasonic agitation 15 hours.Centrifugal to products therefrom, remove the supernatant, lower sediment is the ferroferric oxide magnetic nano-particles of citric acid surface modification.
(3) take the ferroferric oxide magnetic nano-particles of 0.04g surface modification, be dispersed in deionized water.Take 13.324g NaCl, 0.588g NaHCO
3, 0.377g KCl, 0.380g K
2hPO
43H
2o, 0.522gMgCl
2, 0.470g CaCl
2with 0.118g Na
2sO
410H
2o is dissolved in 1L deionized water successively, adds 5g Tris buffer agent and uses the hydrochloride adjusted solution pH value of 1mol/l to 7.25 left and right, obtains 1.5 times of simulated body fluids; The aqueous solution that contains ferriferrous oxide nano-particle is joined in 1.5 times of simulated body fluids under continuing mechanical agitation to 37 ± 0.5 ℃ of constant temperature.Mineralising 60 hours, obtains ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle by product washing, after separated, dry.The crystal formation of shell calcium phosphate mineral is mainly unbodied hydroxyapatite.The mean diameter of ferroso-ferric oxide particle is 37.5nm, and shell thickness is 15nm.Saturation magnetization is 22.5emu/g.
Comparative example 4: do not add citric acid to carry out surface modification, its condition is with embodiment 4, and reaction finishes rear generation hydroxyapatite nano particle, can not form nucleocapsid structure with ferroso-ferric oxide.
Embodiment 5
(1) 0.5g polyvinylpyrrolidone (Mw=40000) is dissolved in 15ml deionized water, mechanical agitation is more than 12 hours.Take 2.499g ferrous sulfate, be dissolved in 15ml deionized water, be stirred to whole dissolvings, add in polyvinylpyrrolidonesolution solution.The churned mechanically while slowly drips the potassium hydroxide solution of 17ml 2.5%; Then drip the hydrogen peroxide of 5ml 3%; Add again 50ml deionized water.The pH of guarantee system 10 is transferred to the water-bath of 160 ℃ by above-mentioned mixed solution, continues mechanical agitation 4 hours.After reaction finishes, utilize externally-applied magnetic field that gained precipitation is separated from reaction medium, use washed with de-ionized water 5 times.Finally precipitation is put into freeze drying box dry, both obtained ferriferrous oxide nano magnetic particle.
(2) ready ferriferrous oxide nano magnetic particle and citric acid are put into deionized water by the mass ratio of 1: 30, ultrasonic agitation 15 hours.Centrifugal to products therefrom, remove the supernatant, lower sediment is the ferroferric oxide magnetic nano-particles of citric acid surface modification.
(3) take the ferroferric oxide magnetic nano-particles of 0.04g surface modification, be dispersed in deionized water.Take 7.994g NaCl, 0.353g NaHCO
3, 0.224g KCl, 0.228g K
2hPO
43H
2o, 0.313gMgCl
2, 0.282g CaCl
2with 0.071g Na
2sO
410H
2o is dissolved in 1L deionized water successively, adds 5g Tris buffer agent and uses the hydrochloride adjusted solution pH value of 1mol/l to 7.40 left and right.The aqueous solution that contains ferriferrous oxide nano-particle is joined in 1 times of simulated body fluid under continuing mechanical agitation to 37 ± 0.5 ℃ of constant temperature.Mineralising 7 days, obtains ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle by product washing, after separated, dry.The crystal formation of shell calcium phosphate mineral is mainly unbodied hydroxyapatite.The mean diameter of ferroso-ferric oxide particle is 35nm, and shell thickness is 8nm.Saturation magnetization is 40.1emu/g.
Comparative example 5: prepare in ferriferrous oxide nano-particle process and do not add dispersant, other conditions are with embodiment 5, and after reaction finishes, obtaining product is only calcium phosphate nano particle.
Embodiment 6
(1) 1.5g Polyethylene Glycol (Mw=4000) is dissolved in 15ml deionized water, mechanical agitation is more than 12 hours.Take 1.789g ferrous chloride, be dissolved in 15ml deionized water, be stirred to whole dissolvings, add in polyglycol solution.The churned mechanically while slowly drips the ammonia spirit of 17ml 2.5%; Then drip the hydrogen peroxide of 5ml3%; Add again 50ml deionized water.The pH of guarantee system 11 is transferred to the water-bath of 60 ℃ by above-mentioned mixed solution, continues mechanical agitation 1 hour.After reaction finishes, utilize externally-applied magnetic field that gained precipitation is separated from reaction medium, use washed with de-ionized water 5 times.Finally precipitation is put into freeze drying box dry, both obtained ferriferrous oxide nano magnetic particle.
(2) ready ferriferrous oxide nano magnetic particle and sodium citrate are put into deionized water by the mass ratio of 1: 50, ultrasonic agitation 12 hours.Centrifugal to products therefrom, remove the supernatant, lower sediment is the ferroferric oxide magnetic nano-particles of sodium citrate surface modification.
(3) take the ferroferric oxide magnetic nano-particles of 0.04g surface modification, be dispersed in deionized water.Take 56.1g NaCl, 1.764g NaHCO
3, 1.420g Na
2hPO
4with 2.775g CaCl
2be dissolved in successively in 1L deionized water, add 10g Tris buffer agent and to 6.30 left and right, obtain 10 times of simulated body fluids with the hydrochloride adjusted solution pH value of 1mol/l.The aqueous solution that contains ferriferrous oxide nano-particle is joined in 10 times of simulated body fluids under continuing mechanical agitation to 37 ± 0.5 ℃ of constant temperature.Mineralising 0.5 hour, obtains ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle by product washing, after separated, dry.The crystal formation of shell calcium phosphate mineral is mainly hydroxyapatite.The mean diameter of ferroso-ferric oxide particle is 27.5nm, and shell thickness is 10nm.Saturation magnetization is 39.1emu/g.
Comparative example 6: the mineralising time surpasses 0.5h, and other conditions are with embodiment 6, and it is thicker that reaction finishes afterproduct shell, and saturation magnetization is too low.
Claims (7)
1. the biomineralization method preparation method of a ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle, described ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle is that to take the ferriferrous oxide nano-particle of magnetic be core, its mean diameter is 27-38nm, calcium phosphate material is shell, and shell thickness is 4-20nm; It is characterized in that, comprise following steps:
(1) prepare ferriferrous oxide nano magnetic particle: divalent iron salt is made in aqueous solution, join in dispersant solution, at the uniform velocity stir, then to mixed liquor slowly to drip aqueous slkali, oxidant hydrogen peroxide, the pH of guarantee system is 10-11, heating, constant temperature 60-160 ℃ after stirring reaction 1-8 hour, utilize externally-applied magnetic field by product separation, washing, lyophilization, makes ferriferrous oxide nano magnetic particle;
(2) ferriferrous oxide nano magnetic particle surface modification: ferriferrous oxide nano magnetic particle and the surface modifier of step (1) gained are added in deionized water, and ultrasonic agitation ground obtains the ferriferrous oxide nano magnetic particle of surperficial introducing carboxyl;
(3) prepare ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle: by NaCl, NaHCO
3, KCl, K
2hPO
43H
2o, MgCl
2, CaCl
2, Na
2sO
410H
2o is dissolved in deionized water, and 37 ± 0.5 ℃ of constant temperature add buffer agent or continue to pass into carbon dioxide, and are 6.30-7.40 with hydrochloride adjusted solution pH value, make the simulated body fluid of 1-10 times of concentration; By the ferriferrous oxide nano magnetic particle of the surface modification obtaining in step (2) mineralising in lasting mechanical agitation joins above-mentioned simulated body fluid, obtain ferroso-ferric oxide calcium phosphate core-shell nano magnetic particle after product washing, magnetic is separated, dry;
Wherein in the simulated body fluid of 1-10 times of concentration, the molar concentration of each ion is: Ca
2+2.5-25.0mmol/L, HPO
4 2-1.0-10.0mmol/L, Na
+142.0-1000.0mmol/L, K
+5.0-25.0mmol/L, Mg
2+1.5-7.7mmol/L, Cl
-148.0-750.0mmol/L, HCO
3 -4.2-42.0mmol/L, SO
4 2-0.5-5.0mmol/L.
2. according to the method for claim 1, it is characterized in that, divalent iron salt described in step (1) is a kind of in ferrous chloride or ferrous sulfate, dispersant solution is a kind of in Polyethylene Glycol, polyvinyl acetate or polyvinylpyrrolidone aqueous solution, and alkali is a kind of in ammonia spirit, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
3. according to the method for claim 1, it is characterized in that, the surface modifier described in step (2) is a kind of in citric acid or sodium citrate, and the mass ratio of itself and ferroso-ferric oxide is 50:1-10:1.
4. according to the method for claim 1, it is characterized in that, in step (2), the ultrasonic agitation time is 12-15 hour.
5. according to the method for claim 1, it is characterized in that, described in step (3), buffer agent is Tris, and the mass ratio of buffer agent and NaCl is 1:8-1:4.
6. according to the method for claim 1, it is characterized in that, along with the multiple increase of simulated body fluid, its mineralising time reduced in 0.5-60 hour.
7. according to the method for claim 1, it is characterized in that, calcium phosphate material shell consist of a kind of in hydroxyapatite (HA), calcium phosphate dibasic dihydrate (DCPD), tricalcium phosphate (α-TCP, β-TCP), calcium pyrophosphate (CPPD), tetracalcium phosphate (TTCP), five water OCPs (OCP), amorphous calcium phosphate (ACP).
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