CN104071763B - The preparation method of polyion type osteoid apatite and polyion type osteoid apatite - Google Patents
The preparation method of polyion type osteoid apatite and polyion type osteoid apatite Download PDFInfo
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Abstract
The invention belongs to technical field of biological material, in particular to the preparation method of polyion type osteoid apatite, and the polyion type osteoid apatite obtained by this preparation method. The Chemical Composition of the inorganic phase of present invention natural bone and ratio, take soluble inorganic salt as raw material, employing self-assembly method or chemical precipitation method manually prepare the polyion type bone-like apatite stone material of the polyion doping of the rule or irregular shape looks in vitro, there is the chemistry composition inorganic mutually identical with natural bone, similar physical and chemical performance and biology performance, it is possible to for the filling reparation (as tooth is filled and reparation, bone filling and reparation etc.) of osseous tissue.
Description
Technical field
The invention belongs to technical field of biological material, in particular to the preparation method of polyion type osteoid apatite, and the polyion type osteoid apatite obtained by this preparation method.
Background technology
In natural bone, the inorganic phase composition of mineralising is osteoid apatite. Osteoid apatite is that hydroxyapatite (HA) is through Na+, K+, Mg2+, Cl-, F-The mixture formed after assorted conjunction Deng mineral ion. The molecular formula of HA is Ca10(PO4)6(OH)2, many ionic radius and Ca2+, PO4 3-, OH-Close positively charged ion and negatively charged ion can both enter the nucleating growth of the lattice participation crystal of HA. HA after assorted conjunction just becomes osteoid apatite, and crystalline structure has also turned into hexagonal system from original folk prescription crystallographic system. In natural bone, osteoid apatite is the storage vault of mineral ion in organism, remains chemical equilibrium with biological fluid. Various mineral ion plays a very important role for the normal activities maintaining organism, such as: 1) Na+, maintain acid base equilibrium in body, contribute to nerve, muscle, the normal operation of blood pressure, the Na in bone+About account for the 1/3 of whole organism. The people such as EdelmanIS (U.S.) are found by radioisotope method, within 24 hours, and the Na of about 40% in bone+Can participate in the middle of metabolic processes. 2) K+, maintain membrane permeability pressure, keep muscle irritability, in bone mineralising and Biochemical processes, there is activity. 3) Mg2+, mainly it is distributed in cell, the activity of multiple enzyme in organism can be activated. Mg2+60%��65% is present in bone and tooth, and 27% is present in soft tissue. The people such as NeumannWF (U.S.) find the Mg existed in bone2+Ion has 90% on the surface of phosphorite crystal. 4) Cl-It is negatively charged ion maximum in organism, participates in transmembrane transport, for bone resorption process provides sour environment, activate the activity of osteoclast. 5) F-, a small amount of fluorion can stablize the crystalline structure of phosphatic rock, prevents the formation of decayed tooth. The people such as KannanS (Portugal) have studied the HA having prepared the single hydridization of above-mentioned mineral ion or being total to hydridization, and product is better than the HA of non-hydridization on a certain physical and chemical performance. In natural bone, osteoid apatite is in the process of nucleating growth, except the hybridization affect being subject to mineral ion, is also subject to the induction nucleation of some protein molecules in body inner bone tissues and regular growth. These protein molecules are collagen and noncollagen protein matter mainly, containing numerous polypeptide key on molecular chain, and carboxyl key, organophosphorus, the chemical groups such as sulfydryl, it is possible to the Ca in body fluid2+, Mg2+, P ion plasma is by the mutual key of electrostatic attraction weak interaction force and is assembled into osteoid apatite. In simulating nature bone of the present invention, the chemistry composition of osteoid apatite and composition ratio, utilize self-assembly method or chemical precipitation method to prepare the polyion type osteoid apatite of ion doping of rule and irregular shape in vitro.
Summary of the invention
An object of the present invention is to provide one to utilize self-assembly method or chemical precipitation method, in the method for external preparation rule and the polyion type osteoid apatite of irregular shape, prepare the polyion type osteoid apatite and there is the chemistry composition inorganic mutually identical with natural bone, similar physical and chemical performance and biology performance, it is possible to be directly used in the reparation of body bone tissue.
The two of the object of the present invention are to provide a kind of polyion type osteoid apatite obtained by the preparation method of object one.
The preparation method of the polyion type osteoid apatite of the present invention comprises the following steps:
(1) cationic solution is prepared: be 0 DEG C��37 DEG C and when fully stirring in temperature, it is dissolved in deionized water to obtain mixed solution using as the sodium salt of cationic inorganic salt, sylvite, magnesium salt, mantoquita, zinc salt, molysite, calcium salt and strontium salt, wherein, the Na in mixed solution+Concentration be 0.001��1mol/l, K+Concentration be 0.001��0.01mol/l, Mg2+Concentration be 0.001��0.002mol/l, Cu2+Concentration be 0.0001��0.0004mol/l, Zn2+Concentration be 0.001��0.006mol/l, Fe3+Concentration be 0.001��0.0015mol/l, Ca2+Concentration be 0.0025��2mol/l, Sr2+Concentration be 0.001��0.6mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain cationic solution;
(2) prepare anion solutions: be 0 DEG C��37 DEG C and when fully stirring in temperature, it is dissolved in deionization to obtain mixed solution using as the villaumite of anionic inorganic salt, fluorine salt, carbonate, silicate, vitriol and microcosmic salt, wherein, the Cl in mixed solution-Concentration be 0.001��0.2mol/l, F-Concentration be 0.001��0.01mol/l, CO3 2-Concentration be 0.001��0.027mol/l, SiO3 2-Concentration be 0.0001��0.00015mol/l, SO4 2-Concentration be 0.0001��0.0005mol/l, PO4 3-Concentration be 0.002��1.2mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain anion solutions;
(3) it is 0.1��90 according to the volume ratio of anion solutions and cationic solution, cationic solution step (1) obtained is added drop-wise in the anion solutions that step (2) obtains according to the flow velocity of 0.1ml/h��5l/h and obtains mixed solution, or anion solutions step (2) obtained is added drop-wise in the cationic solution that step (1) obtains according to the flow velocity of 0.1ml/h��5l/h and obtains mixed solution; Stirring makes them fully mix, and regulates the pH of mixed solution between 6.5��13.5 with ammoniacal liquor, sodium hydroxide, potassium hydroxide, calcium hydroxide, HCl-Tris damping fluid, phosphate buffered saline buffer or Du Erbeike phosphate buffered saline buffer (DPBS) in the process stirred;
(4) temperature of reaction of the mixed solution of pH step (3) obtained between 6.5��13.5 regulates between 0 DEG C��90 DEG C, the sustained reaction 1 hour��7 days when leaving standstill or continue to stir (speed preferably continuing to stir is 50rpm��3000rpm); When step (3) is regulate the pH of mixed solution between 6.5��13.5 with ammoniacal liquor, sodium hydroxide, potassium hydroxide or calcium hydroxide in the process stirred, in the standing or lasting process stirred, continuous ammoniacal liquor, sodium hydroxide, potassium hydroxide, calcium hydroxide, HCl-Tris damping fluid, phosphate buffered saline buffer or Du Erbeike phosphate buffered saline buffer regulate the pH of mixed solution between 6.5��13.5; When step (3) is regulate the pH of mixed solution between 6.5��13.5 with HCl-Tris damping fluid, phosphate buffered saline buffer or Du Erbeike phosphate buffered saline buffer in the process stirred, without the need to regulating pH again in the standing or lasting process stirred; Reaction obtains white emulsion after terminating;
(5) white emulsion that step (4) obtains is separated into solid liquid two-phase (white emulsion being separated into solid liquid two-phase by decompress filter method or centrifugal), the white solid deionized water wash (preferably the number of times of washing is 1��5) obtained; Then by the white solid drying obtained (freeze-drying, high-temperature oven drying method or spray-drying process can be adopted), polyion type osteoid apatite is obtained.
The size of polyion type osteoid apatite prepared by the present invention is 10nm��150 ��m; Shape is spherical, semisphere, flowers shape, needle-like, bar-shaped or irregular shape.
Described will be dissolved in deionized water as the sodium salt of cationic inorganic salt, sylvite, magnesium salt, mantoquita, zinc salt, molysite, calcium salt and strontium salt, it will be preferred that be dissolved in deionized water according to the order of sodium salt, sylvite, magnesium salt, mantoquita, zinc salt, molysite, calcium salt and strontium salt.
Described will be dissolved in deionization as the villaumite of anionic inorganic salt, fluorine salt, carbonate, silicate, vitriol and microcosmic salt, it will be preferred that be dissolved in deionization according to the order of villaumite, fluorine salt, carbonate, silicate, vitriol and microcosmic salt.
The one that described sodium salt is selected from sodium-chlor, SODIUMNITRATE, sodium carbonate, sodium bicarbonate.
Described sylvite is Repone K or saltpetre.
Described magnesium salt is magnesium chloride or magnesium nitrate.
The one that described mantoquita is selected from cupric chloride, copper sulfate, cupric nitrate.
Described zinc salt is zinc nitrate or zinc chloride.
Described molysite is iron nitrate or iron(ic) chloride.
The one that described calcium salt is selected from nitrocalcite, calcium chloride, calcium hydroxide, secondary calcium phosphate, monocalcium phosphate, dicalcium phosphate, lime acetate, calcium carbonate.
Described strontium salt is strontium nitrate or strontium chloride.
Described villaumite is sodium-chlor or Repone K.
Described fluorine salt is Sodium Fluoride.
The one that described carbonate is selected from sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus.
Described silicate is water glass.
Described vitriol is sodium sulfate or potassium sulfate.
The one that described microcosmic salt is selected from Secondary ammonium phosphate, dipotassium hydrogen phosphate, Sodium phosphate dibasic, primary ammonium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC.
The Chemical Composition of the inorganic phase of present invention natural bone and ratio, take soluble inorganic salt as raw material, employing self-assembly method (leaving standstill) or chemical precipitation method (stirring) manually prepare the polyion type bone-like apatite stone material of the polyion doping of the rule or irregular shape looks in vitro, there is the chemistry composition inorganic mutually identical with natural bone, similar physical and chemical performance and biology performance, it is possible to for the filling reparation (as tooth is filled and reparation, bone filling and reparation etc.) of osseous tissue.
Accompanying drawing explanation
Fig. 1. the electron micrograph of the spherical polyion type osteoid apatite of the embodiment of the present invention 1.
Fig. 2. the electron micrograph of the spherical polyion type osteoid apatite of the half of the embodiment of the present invention 2.
Fig. 3. the electron micrograph of the flowers shape polyion type osteoid apatite of the embodiment of the present invention 3.
Fig. 4. the electron micrograph of the needle-like polyion type osteoid apatite of the embodiment of the present invention 4.
Fig. 5. the electron micrograph of the bar-shaped polyion type osteoid apatite of the embodiment of the present invention 5.
Fig. 6. the electron micrograph of the irregular polyion type osteoid apatite of the embodiment of the present invention 6.
Embodiment
Embodiment 1
(1) cationic solution is prepared: be 0 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 100ml deionized water as the sodium-chlor of cationic inorganic salt, Repone K, magnesium chloride, cupric chloride, zinc chloride, iron(ic) chloride, nitrocalcite and strontium nitrate according to said sequence, wherein, the Na in mixed solution+Concentration be 1.0mol/l, K+Concentration be 0.01mol/l, Mg2+Concentration be 0.002mol/l, Cu2+Concentration be 0.0004mol/l, Zn2+Concentration be 0.006mol/l, Fe3+Concentration be 0.0015mol/l, Ca2+Concentration be 0.0025mol/l, Sr2+Concentration be 0.001mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain cationic solution;
(2) anion solutions is prepared: be 0 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 10ml deionized water as the sodium-chlor of anionic inorganic salt, Sodium Fluoride, sodium bicarbonate, water glass, potassium sulfate and Secondary ammonium phosphate according to said sequence, wherein, the Cl in mixed solution-Concentration be 0.001mol/l, F-Concentration be 0.01mol/l, CO3 2-Concentration be 0.027mol/l, SiO3 2-Concentration be 0.00015mol/l, SO4 2-Concentration be 0.0005mol/l, PO4 3-Concentration be 0.002mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain anion solutions;
(3) it is 0.1 according to the volume ratio of anion solutions and cationic solution, cationic solution step (1) obtained is added drop-wise in the anion solutions that step (2) obtains according to the flow velocity of 0.1ml/h and obtains mixed solution, or anion solutions step (2) obtained is added drop-wise in the cationic solution that step (1) obtains according to the flow velocity of 0.1ml/h and obtains mixed solution; Stirring makes them fully mix, and regulates the pH of mixed solution to be 7.4 with HCl-Tris damping fluid in the process stirred;
(4) by the pH that step (3) obtains be 7.4 the temperature of reaction of mixed solution be adjusted to 90 DEG C, sustained reaction 7 days standing when; Reaction obtains white emulsion after terminating;
(5) white emulsion is separated into solid liquid two-phase, the white solid deionized water wash obtained 1 time by decompress filter method or centrifugal by white emulsion step (4) obtained; Then adopt freeze-drying, high-temperature oven drying method or spray-drying process to be dried the white solid obtained, obtain the polyion type osteoid apatite that size is 400nm��700nm; Shape is spherical; The SEM of product is as shown in Figure 1.
Embodiment 2
(1) cationic solution is prepared: be 20 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 200ml deionized water as the sodium-chlor of cationic inorganic salt, Repone K, magnesium chloride, cupric chloride, zinc chloride, iron(ic) chloride, calcium chloride and strontium nitrate according to said sequence, wherein, the Na in mixed solution+Concentration be 1.0mol/l, K+Concentration be 0.01mol/l, Mg2+Concentration be 0.001mol/l, Cu2+Concentration be 0.0001mol/l, Zn2+Concentration be 0.001mol/l, Fe3+Concentration be 0.001mol/l, Ca2+Concentration be 0.0025mol/l, Sr2+Concentration be 0.6mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain cationic solution;
(2) anion solutions is prepared: be 20 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 100ml deionized water as the sodium-chlor of anionic inorganic salt, Sodium Fluoride, sodium bicarbonate, water glass, potassium sulfate and Sodium phosphate dibasic according to said sequence, wherein, the Cl in mixed solution-Concentration be 0.01mol/l, F-Concentration be 0.001mol/l, CO3 2-Concentration be 0.001mol/l, SiO3 2-Concentration be 0.0001mol/l, SO4 2-Concentration be 0.0001mol/l, PO4 3-Concentration be 0.002mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain anion solutions;
(3) it is 0.5 according to the volume ratio of anion solutions and cationic solution, cationic solution step (1) obtained is added drop-wise in the anion solutions that step (2) obtains according to the flow velocity of 5l/h and obtains mixed solution, or anion solutions step (2) obtained is added drop-wise in the cationic solution that step (1) obtains according to the flow velocity of 5l/h and obtains mixed solution; Stirring makes them fully mix, and regulates the pH of mixed solution to be 7.0 with Du Erbeike phosphate buffered saline buffer (DPBS) in the process stirred;
(4) by the pH that step (3) obtains be 7.0 the temperature of reaction of mixed solution be adjusted to 60 DEG C, sustained reaction 3 days standing when; Reaction obtains white emulsion after terminating;
(5) white emulsion is separated into solid liquid two-phase, the white solid deionized water wash obtained 5 times by decompress filter method or centrifugal by white emulsion step (4) obtained; Then adopt freeze-drying, high-temperature oven drying method or spray-drying process to be dried the white solid obtained, obtain the polyion type osteoid apatite that size is 10 ��m��100 ��m; Shape is semisphere; The SEM of product is as shown in Figure 2.
Embodiment 3
(1) cationic solution is prepared: be 10 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 100ml deionized water as the sodium-chlor of cationic inorganic salt, Repone K, magnesium chloride, cupric chloride, zinc chloride, iron(ic) chloride, calcium chloride and strontium nitrate according to said sequence, wherein, the Na in mixed solution+Concentration be 0.1mol/l, K+Concentration be 0.005mol/l, Mg2+Concentration be 0.0015mol/l, Cu2+Concentration be 0.0003mol/l, Zn2+Concentration be 0.002mol/l, Fe3+Concentration be 0.0012mol/l, Ca2+Concentration be 0.1mol/l, Sr2+Concentration be 0.001mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain cationic solution;
(2) anion solutions is prepared: be 10 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 9000ml deionized water as the Repone K of anionic inorganic salt, Sodium Fluoride, sodium bicarbonate, water glass, sodium sulfate and dipotassium hydrogen phosphate according to said sequence, wherein, the Cl in mixed solution-Concentration be 0.005mol/l, F-Concentration be 0.005mol/l, CO3 2-Concentration be 0.0015mol/l, SiO3 2-Concentration be 0.0003mol/l, SO4 2-Concentration be 0.0002mol/l, PO4 3-Concentration be 0.5mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain anion solutions;
(3) it is 90 according to the volume ratio of anion solutions and cationic solution, cationic solution step (1) obtained is added drop-wise in the anion solutions that step (2) obtains according to the flow velocity of 200ml/h and obtains mixed solution, or anion solutions step (2) obtained is added drop-wise in the cationic solution that step (1) obtains according to the flow velocity of 200ml/h and obtains mixed solution; Stirring makes them fully mix, and regulates the pH of mixed solution to be 6.5 with phosphate buffered saline buffer in the process stirred;
(4) by the pH that step (3) obtains be 6.5 the temperature of reaction of mixed solution be adjusted to 80 DEG C, sustained reaction 2 days standing when; Reaction obtains white emulsion after terminating;
(5) white emulsion is separated into solid liquid two-phase, the white solid deionized water wash obtained 2 times by decompress filter method or centrifugal by white emulsion step (4) obtained; Then adopt freeze-drying, high-temperature oven drying method or spray-drying process to be dried the white solid obtained, obtain the polyion type osteoid apatite that size is 10 ��m��150 ��m; Shape is flowers shape; The SEM of product is as shown in Figure 3.
Embodiment 4
(1) cationic solution is prepared: be 37 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 400ml deionized water as the sodium-chlor of cationic inorganic salt, Repone K, magnesium chloride, cupric chloride, zinc chloride, iron(ic) chloride, calcium chloride and strontium nitrate, wherein, the Na in mixed solution+Concentration be 1.0mol/l, K+Concentration be 0.01mol/l, Mg2+Concentration be 0.002mol/l, Cu2+Concentration be 0.0001mol/l, Zn2+Concentration be 0.002mol/l, Fe3+Concentration be 0.001mol/l, Ca2+Concentration be 0.60mol/l, Sr2+Concentration be 0.3mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain cationic solution;
(2) anion solutions is prepared: be 37 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 250ml deionized water as the Repone K of anionic inorganic salt, Sodium Fluoride, sodium bicarbonate, water glass, sodium sulfate and dipotassium hydrogen phosphate, wherein, the Cl in mixed solution-Concentration be 0.10mol/l, F-Concentration be 0.006mol/l, CO3 2-Concentration be 0.027mol/l, SiO3 2-Concentration be 0.0001mol/l, SO4 2-Concentration be 0.0004mol/l, PO4 3-Concentration be 0.36mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain anion solutions;
(3) it is 0.625 according to the volume ratio of anion solutions and cationic solution, cationic solution step (1) obtained is added drop-wise in the anion solutions that step (2) obtains according to the flow velocity of 500ml/h and obtains mixed solution, or anion solutions step (2) obtained is added drop-wise in the cationic solution that step (1) obtains according to the flow velocity of 500ml/h and obtains mixed solution; Stirring makes them fully mix, and regulates the pH of mixed solution to be 9.0 with ammoniacal liquor in the process stirred;
(4) by the pH that step (3) obtains be 9.0 the temperature of reaction of mixed solution be adjusted to 25 DEG C, continue stirring reaction 1 hour when stir speed (S.S.) is 3000rpm; The process stirred constantly regulates with ammoniacal liquor the pH of mixed solution, makes pH be 9.0; Reaction obtains white emulsion after terminating;
(5) white emulsion is separated into solid liquid two-phase, the white solid deionized water wash obtained 4 times by decompress filter method or centrifugal by white emulsion step (4) obtained; Then adopt freeze-drying, high-temperature oven drying method or spray-drying process to be dried the white solid obtained, obtain the polyion type osteoid apatite that size is 10nm��700nm; Shape is needle-like; The SEM of product is as shown in Figure 4.
Embodiment 5
(1) cationic solution is prepared: be 25 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 500ml deionized water as the sodium-chlor of cationic inorganic salt, Repone K, magnesium chloride, cupric chloride, zinc chloride, iron(ic) chloride, nitrocalcite and strontium nitrate according to said sequence, wherein, the Na in mixed solution+Concentration be 0.2mol/l, K+Concentration be 0.007mol/l, Mg2+Concentration be 0.002mol/l, Cu2+Concentration be 0.0002mol/l, Zn2+Concentration be 0.006mol/l, Fe3+Concentration be 0.001mol/l, Ca2+Concentration be 0.60mol/l, Sr2+Concentration be 0.2mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain cationic solution;
(2) anion solutions is prepared: be 10 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 400ml deionized water as the sodium-chlor of anionic inorganic salt, Sodium Fluoride, sodium bicarbonate, water glass, sodium sulfate and Sodium phosphate dibasic according to said sequence, wherein, the Cl in mixed solution-Concentration be 0.1mol/l, F-Concentration be 0.01mol/l, CO3 2-Concentration be 0.01mol/l, SiO3 2-Concentration be 0.0001mol/l, SO4 2-Concentration be 0.0002mol/l, PO4 3-Concentration be 0.36mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain anion solutions;
(3) it is 0.8 according to the volume ratio of anion solutions and cationic solution, cationic solution step (1) obtained is added drop-wise in the anion solutions that step (2) obtains according to the flow velocity of 1l/h and obtains mixed solution, or anion solutions step (2) obtained is added drop-wise in the cationic solution that step (1) obtains according to the flow velocity of 1l/h and obtains mixed solution; Stirring makes them fully mix, and regulates the pH of mixed solution to be 13.5 with sodium hydroxide in the process stirred;
(4) by the pH that step (3) obtains be 13.5 the temperature of reaction of mixed solution be adjusted to 80 DEG C, continue stirring reaction 24 hours when stir speed (S.S.) is 50rpm; The process stirred constantly regulates with sodium hydroxide the pH of mixed solution, makes pH be 13.5; Reaction obtains white emulsion after terminating;
(5) white emulsion is separated into solid liquid two-phase, the white solid deionized water wash obtained 3 times by decompress filter method or centrifugal by white emulsion step (4) obtained; Then adopt freeze-drying, high-temperature oven drying method or spray-drying process to be dried the white solid obtained, obtain the polyion type osteoid apatite that size is 600nm��10 ��m; Shape is bar-shaped; The SEM of product is as shown in Figure 5.
Embodiment 6
(1) cationic solution is prepared: be 20 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 1000ml deionized water as the sodium-chlor of cationic inorganic salt, Repone K, magnesium chloride, cupric chloride, zinc chloride, iron(ic) chloride, nitrocalcite and strontium nitrate according to said sequence, wherein, the Na in mixed solution+Concentration be 1.0mol/l, K+Concentration be 0.01mol/l, Mg2+Concentration be 0.002mol/l, Cu2+Concentration be 0.0001mol/l, Zn2+Concentration be 0.002mol/l, Fe3+Concentration be 0.001mol/l, Ca2+Concentration be 2.0mol/l, Sr2+Concentration be 0.001mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain cationic solution;
(2) anion solutions is prepared: be 20 DEG C and when fully stirring in temperature, mixed solution is obtained using being dissolved in 500ml deionized water as the Repone K of anionic inorganic salt, Sodium Fluoride, sodium bicarbonate, water glass, sodium sulfate and Secondary ammonium phosphate according to said sequence, wherein, the Cl in mixed solution-Concentration be 0.2mol/l, F-Concentration be 0.001mol/l, CO3 2-Concentration be 0.027mol/l, SiO3 2-Concentration be 0.00015mol/l, SO4 2-Concentration be 0.0004mol/l, PO4 3-Concentration be 1.20mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain anion solutions;
(3) it is 0.2 according to the volume ratio of anion solutions and cationic solution, cationic solution step (1) obtained is added drop-wise in the anion solutions that step (2) obtains according to the flow velocity of 200ml/h and obtains mixed solution, or anion solutions step (2) obtained is added drop-wise in the cationic solution that step (1) obtains according to the flow velocity of 200ml/h and obtains mixed solution; Stirring makes them fully mix, and regulates the pH of mixed solution to be 10.0 with potassium hydroxide in the process stirred;
(4) by the pH that step (3) obtains be 10.0 the temperature of reaction of mixed solution be adjusted to 60 DEG C, continue stirring reaction 18 hours when stir speed (S.S.) is 600rpm; The process stirred constantly regulates with potassium hydroxide the pH of mixed solution, makes pH be 10.0; Reaction obtains white emulsion after terminating;
(5) white emulsion is separated into solid liquid two-phase, the white solid deionized water wash obtained 3 times by decompress filter method or centrifugal by white emulsion step (4) obtained; Then adopt freeze-drying, high-temperature oven drying method or spray-drying process to be dried the white solid obtained, obtain the polyion type osteoid apatite that shape is irregular shape; The SEM of product is as shown in Figure 6; The result of product ultimate analysis is as shown in table 1.
Table 1
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Claims (7)
1. a preparation method for polyion type osteoid apatite, is characterized in that, described preparation method comprises the following steps:
(1) cationic solution is prepared: be 0 DEG C��37 DEG C and when fully stirring in temperature, it is dissolved in deionized water to obtain mixed solution using as the sodium salt of cationic inorganic salt, sylvite, magnesium salt, mantoquita, zinc salt, molysite, calcium salt and strontium salt, wherein, the Na in mixed solution+Concentration be 0.001��1mol/l, K+Concentration be 0.001��0.01mol/l, Mg2+Concentration be 0.001��0.002mol/l, Cu2+Concentration be 0.0001��0.0004mol/l, Zn2+Concentration be 0.001��0.006mol/l, Fe3+Concentration be 0.001��0.0015mol/l, Ca2+Concentration be 0.0025��2mol/l, Sr2+Concentration be 0.001��0.6mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain cationic solution;
(2) anion solutions is prepared: be 0 DEG C��37 DEG C and when fully stirring in temperature, it is dissolved in deionization to obtain mixed solution using as the villaumite of anionic inorganic salt, fluorine salt, carbonate, silicate, vitriol and phosphoric acid salt, wherein, the Cl in mixed solution-Concentration be 0.001��0.2mol/l, F-Concentration be 0.001��0.01mol/l, CO3 2-Concentration be 0.001��0.027mol/l, SiO3 2-Concentration be 0.0001��0.00015mol/l, SO4 2-Concentration be 0.0001��0.0005mol/l, PO4 3-Concentration be 0.002��1.2mol/l; By the mixed solution that obtains through 0 < aperture��0.45 ��m filter paper or filter-cloth filtering, obtain anion solutions;
(3) it is 0.1��90 according to the volume ratio of anion solutions and cationic solution, cationic solution step (1) obtained is added drop-wise in the anion solutions that step (2) obtains according to the flow velocity of 0.1ml/h��5l/h and obtains mixed solution, or anion solutions step (2) obtained is added drop-wise in the cationic solution that step (1) obtains according to the flow velocity of 0.1ml/h��5l/h and obtains mixed solution; Stirring makes them fully mix, and regulates the pH of mixed solution between 6.5��13.5 with HCl-Tris damping fluid, phosphate buffered saline buffer or Du Erbeike phosphate buffered saline buffer in the process stirred;
(4) temperature of reaction of the mixed solution of pH step (3) obtained between 6.5��13.5 regulates between 0 DEG C��90 DEG C, the sustained reaction 1 hour��7 days when leaving standstill or continue to stir; Without the need to regulating pH again in the standing or lasting process stirred; Reaction obtains white emulsion after terminating;
(5) white emulsion that step (4) obtains is separated into solid liquid two-phase, the white solid deionized water wash obtained; Then the white solid drying that will obtain, obtains polyion type osteoid apatite;
The shape of described polyion type osteoid apatite is spherical, semisphere or flowers shape, and size is 10nm��150 ��m.
2. preparation method according to claim 1, it is characterized in that: described using being dissolved in deionized water as the sodium salt of cationic inorganic salt, sylvite, magnesium salt, mantoquita, zinc salt, molysite, calcium salt and strontium salt, it is be dissolved in deionized water according to the order of sodium salt, sylvite, magnesium salt, mantoquita, zinc salt, molysite, calcium salt and strontium salt;
Described using being dissolved in deionization as the villaumite of anionic inorganic salt, fluorine salt, carbonate, silicate, vitriol and phosphoric acid salt, it is be dissolved in deionization according to the order of villaumite, fluorine salt, carbonate, silicate, vitriol and phosphoric acid salt.
3. preparation method according to claim 1 and 2, is characterized in that: the one that described sodium salt is selected from sodium-chlor, SODIUMNITRATE, sodium carbonate, sodium bicarbonate; Described sylvite is Repone K or saltpetre; Described magnesium salt is magnesium chloride or magnesium nitrate; The one that described mantoquita is selected from cupric chloride, copper sulfate, cupric nitrate; Described zinc salt is zinc nitrate or zinc chloride; Described molysite is iron nitrate or iron(ic) chloride; The one that described calcium salt is selected from nitrocalcite, calcium chloride, secondary calcium phosphate, monocalcium phosphate, dicalcium phosphate, lime acetate, calcium carbonate; Described strontium salt is strontium nitrate or strontium chloride.
4. preparation method according to claim 1 and 2, is characterized in that: described villaumite is sodium-chlor or Repone K; Described fluorine salt is Sodium Fluoride; The one that described carbonate is selected from sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus; Described silicate is water glass; Described vitriol is sodium sulfate or potassium sulfate; The one that described phosphoric acid salt is selected from Secondary ammonium phosphate, dipotassium hydrogen phosphate, Sodium phosphate dibasic, primary ammonium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC.
5. preparation method according to claim 1, is characterized in that: the speed of described lasting stirring is 50rpm��3000rpm.
6. preparation method according to claim 1, is characterized in that: the described solid liquid two-phase that is separated into by the white emulsion that step (4) obtains adopts decompress filter method or centrifugal.
7. preparation method according to claim 1, is characterized in that: described drying adopts freeze-drying, high-temperature oven drying method or spray-drying process.
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| US20040241314A1 (en) * | 2003-05-30 | 2004-12-02 | Depuy Products, Inc. | Strontium-substituted apatite coating |
| WO2012117218A1 (en) * | 2011-03-02 | 2012-09-07 | Ceram Research Limited | Biomaterial |
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| US20040241314A1 (en) * | 2003-05-30 | 2004-12-02 | Depuy Products, Inc. | Strontium-substituted apatite coating |
| WO2012117218A1 (en) * | 2011-03-02 | 2012-09-07 | Ceram Research Limited | Biomaterial |
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| Novel synthesis and structural characterization of fluorine and chlorine co-substituted hydroxyapatites;S.Kannan et al.;《Journal of Inorganic Biochemistry》;20060627;第100卷;第1692–1697页 * |
| Sol–gel synthesis and spectrometric structural evaluation of strontium substituted hydroxyapatite;A.Balamurugan et al.;《Materials Science and Engineering C》;20080910;第29卷;第1006–1009页 * |
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