CN104225674A - Preparation method for fluid shear stress-mediated hydroxyapatite - Google Patents
Preparation method for fluid shear stress-mediated hydroxyapatite Download PDFInfo
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- CN104225674A CN104225674A CN201410433439.3A CN201410433439A CN104225674A CN 104225674 A CN104225674 A CN 104225674A CN 201410433439 A CN201410433439 A CN 201410433439A CN 104225674 A CN104225674 A CN 104225674A
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Abstract
The invention discloses a preparation method for fluid shear stress-mediated hydroxyapatite, and belongs to the technical field of biological medical materials. According to the method, on the basis of preparing hydroxyapatite from an aqueous solution by a direct precipitation method, a fluid shear stress with a constant direction is applied to a reaction system for transforming amorphous calcium phosphate to hydroxyapatite by virtue of a principle of biomimetic synthesis and through simulating a biomechanic micro-environment in which the formation process of hydroxyapatite in bone tissues in a body is carried out to regulate calcium and phosphate ions to be rearranged, thus obtaining a hydroxyapatite crystal with a complete structure in the aqueous solution. According to the preparation method disclosed by the invention, the shortage of low purity of hydroxyapatite prepared by the precipitation method is improved, and a novel biological medical material is obtained, which has good biocompatibility, a mechanical property matched with the bone tissues of the human body, and is very hopeful for being widely applied to the field of bone defect repair.
Description
Technical field
The invention belongs to biology medical material technical field, or rather, the present invention relates to the preparation method of the hydroxyapatite of a kind of hydrodynamic shear mediation.
Background technology
The wound caused along with natural disaster, industry, traffic, sports etc. increases, and the problem of an aging population that Chinese society faces, and the disease of closing with bone photo has nowadays become a global problem with damage.Artificial bone repair materials is the another bone injury repairing and treating means occurred clinically after bone collection, and annual ever-increasing Cranial defect patient has urgent demand to artificial bone repair materials, and its market demand is very huge.Hydroxyapatite is the host inorganic ingredient of body bone tissue.In sclerotin, hydroxyapatite accounts for 60%, shows as the acicular crystal of length 20 ~ 40 nanometer, thickness 1.5 ~ 3.0 nanometer.Structurally, hydroxyapatite belongs to hexagonal crystal system, space group P6
3/ m, molecular formula is Ca
10(PO
4)
6(OH)
2, Ca/P atomic ratio is 1.67, and structure is hexagonal cylinder.Thermodynamically, hydroxyapatite is the most stable in aqueous one of calcium phosphate.In recent years, because hydroxyapatite has good biocompatibility, bone conductibility and synosteosis ability, add and have no side effect, be thus widely used as Bone Defect Repari and packing material.
The method preparing hydroxyapatite at present has a variety of, mainly comprises hydro-thermal reaction method (if publication number is the Chinese patent of CN 103407979A), sol-gel process (if publication number is the Chinese patent of CN 102491299B), the sedimentation method, auto-combustion method, microemulsion method, microwave method etc.Wherein, the sedimentation method are one of typical methods preparing hydroxyapatite crystal, normally certain density calcium salt and microcosmic salt mix and blend, control ph is greater than 9, then certain hour is reacted in the solution, make it that chemical reaction occurs and generate precipitation, after filtration, dry, obtain hydroxyapatite crystal powder (if publication number is the Chinese patent of CN 103112837A).But, consider that body bone tissue belongs to typical mechanical-chemical coupling body, these synthetic methods above-mentioned have ignored hydroxyapatite biomechanics microenvironment residing in forming process in vivo, cause the material synthesized to be difficult to reappear the stuctures and properties of hydroxyapatite in natural bone tissue.Therefore, Biomechanical factor is introduced the preparation process of hydroxyapatite, significant to Development of Novel biomimetic prosthetic bone renovating material.
Summary of the invention
The object of the invention is to improve the deficiencies in the prior art, Biomechanical factor is included in the preparation process of hydroxyapatite, provide a kind of newly workable, the preparation method of reaction condition gentleness.
The object of the invention is to be achieved through the following technical solutions: the hydroxyapatite prepared under a kind of fluid shearing force environment, its preparation method comprises following each step:
(1) calcium salt soln, phosphate solution are weighed by calcium phosphorus mol ratio 1.67, be dissolved in deionized water solution respectively;
(2) dropwise instilled in phosphate solution by calcium salt soln, regulate pH>7 by ammonia or sodium hydroxide therebetween, obtaining pale precipitation is amorphous calcium phosphate precursor;
(3) suspension containing amorphous calcium phosphate precursor is transferred in stress loading experimental provision carry out ageing, apply the constant direction hydrodynamic shear of different time and different size simultaneously;
(4) stress loading is complete, collecting precipitation, and repeatedly cleans with deionized water;
(5) precipitation is placed in-80 DEG C of refrigerator and cooled and freezes 2 ~ 4 hours, then to transfer in freezer dryer lyophilization 24 ~ 48 hours, obtain the hydroxyapatite material of hydrodynamic shear mediation.
Calcium salt soln described in said method is one or more in lime nitrate, calcium chloride and calcium hydroxide, and described phosphate solution is one or more in diammonium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid.
The calcium phosphorus mol ratio of the precursor of amorphous calcium phosphate described in said method is 1.1 ~ 1.6.
The experimental provision of stress loading described in said method is for providing the Cone & Plate viscosity instrument of constant direction hydrodynamic shear, flat flow chamber or syringe pump-pump line circulating device.
The load time of hydrodynamic shear described in said method is 0.5 ~ 24 hour, and loading size is 0.1 ~ 2.5 handkerchief.
The hydroxyapatite of the mediation of hydrodynamic shear described in said method, its microscopic pattern is needle-like, and length is 50 ~ 300 nanometers, and calcium phosphorus mol ratio is 1.5 ~ 1.67.
Compared with prior art, its major advantage is in the present invention:
(1) method of bio-mimetic syntheses is utilized, biomechanics microenvironment is introduced in the process that amorphous calcium phosphate changes to hydroxyapatite, by the transformation that it distributes calcium and phosphorus ions, improve the calcium-phosphorus ratio that aqueous solution direct precipitation method prepares hydroxyapatite, the i.e. integrity of structure, improves aqueous solution direct precipitation method and prepares the low deficiency of hydroxyapatite purity.
(2) preparation method is simple, and reaction condition is gentle, and hydrodynamic shear load mode is workable, and product is easy to reclaim.
(3) hydroxyapatite material of a kind of novelty that what the present invention obtained is, had both had good biocompatibility, had had again the mechanical property matched with body bone tissue, and got a good chance of being used widely in bone defect healing field.
Accompanying drawing explanation
Accompanying drawing Fig. 1 is the schematic diagram of hydrodynamic shear mediation hydroxyapatite synthesis.
Detailed description of the invention
The present invention is further illustrated below in conjunction with specific embodiments, but these embodiments do not limit the scope of the invention.
Embodiment 1: the synthesis of hydrodynamic shear mediation hydroxyapatite
Take 2.36 grams of calcium nitrate tetrahydrates and 0.79 gram of diammonium phosphate respectively, be dissolved in respectively in 20 ml deionized water.Dropwise instilled in ammonium dibasic phosphate solution by calcium nitrate solution, period uses ammonia adjust ph to be 7 ~ 8.Treat that two kinds of solution mix completely, obtaining pale precipitation is amorphous calcium phosphate precursor.Get 3.9 milliliters of amorphous calcium phosphate precursor suspensions to join in Cone & Plate viscosity instrument reactive tank, constant fluid shearing force 0.5 handkerchief is set, 6 hours action time.Treat that stress loading is complete, suspension is transferred in centrifuge tube, centrifugal and with the supreme clear liquid of washed with de-ionized water in neutral.Precipitation is placed in-80 DEG C of refrigerator and cooled and freezes 2 hours, then to transfer in freezer dryer lyophilization 24 hours, obtain the hydroxyapatite of hydrodynamic shear mediation.
Embodiment 2: the synthesis of hydrodynamic shear mediation hydroxyapatite
Take 2.36 grams of calcium nitrate tetrahydrates and 0.79 gram of sodium hydrogen phosphate respectively, be dissolved in respectively in 20 ml deionized water.Dropwise instilled in disodium phosphate soln by calcium nitrate solution, period uses sodium hydroxide adjust ph to be 7 ~ 8.Treat that two kinds of solution mix completely, obtaining pale precipitation is amorphous calcium phosphate precursor.Get 3.9 milliliters of amorphous calcium phosphate precursor suspensions to join in Cone & Plate viscosity instrument reactive tank, constant fluid shearing force 0.5 handkerchief is set, 6 hours action time.Treat that stress loading is complete, suspension is transferred in centrifuge tube, centrifugal and with the supreme clear liquid of washed with de-ionized water in neutral.Precipitation is placed in-80 DEG C of refrigerator and cooled and freezes 2 hours, then to transfer in freezer dryer lyophilization 24 hours, obtain the hydroxyapatite of hydrodynamic shear mediation.
Embodiment 3: the synthesis of hydrodynamic shear mediation hydroxyapatite
Take 2.36 grams of calcium nitrate tetrahydrates and 0.79 gram of diammonium phosphate respectively, be dissolved in respectively in 20 ml deionized water.Dropwise instilled in ammonium dibasic phosphate solution by calcium nitrate solution, period uses ammonia adjust ph to be 7 ~ 8.Treat that two kinds of solution mix completely, obtaining pale precipitation is amorphous calcium phosphate precursor.Get 3.9 milliliters of amorphous calcium phosphate precursor suspensions to join in Cone & Plate viscosity instrument reactive tank, constant fluid shearing force 1.0 handkerchief is set, 6 hours action time.Treat that stress loading is complete, suspension is transferred in centrifuge tube, centrifugal and with the supreme clear liquid of washed with de-ionized water in neutral.Precipitation is placed in-80 DEG C of refrigerator and cooled and freezes 2 hours, then to transfer in freezer dryer lyophilization 24 hours, obtain the hydroxyapatite of hydrodynamic shear mediation.
Embodiment 4: the synthesis of hydrodynamic shear mediation hydroxyapatite
Take 2.36 grams of calcium nitrate tetrahydrates and 0.79 gram of diammonium phosphate respectively, be dissolved in respectively in 20 ml deionized water.Dropwise instilled in ammonium dibasic phosphate solution by calcium nitrate solution, period uses ammonia adjust ph to be 7 ~ 8.Treat that two kinds of solution mix completely, obtaining pale precipitation is amorphous calcium phosphate precursor.Get 3.9 milliliters of amorphous calcium phosphate precursor suspensions to join in Cone & Plate viscosity instrument reactive tank, constant fluid shearing force 0.5 handkerchief is set, 9 hours action time.Treat that stress loading is complete, suspension is transferred in centrifuge tube, centrifugal and with the supreme clear liquid of washed with de-ionized water in neutral.Precipitation is placed in-80 DEG C of refrigerator and cooled and freezes 2 hours, then to transfer in freezer dryer lyophilization 24 hours, obtain the hydroxyapatite of hydrodynamic shear mediation.
Embodiment 5: the synthesis of hydrodynamic shear mediation hydroxyapatite
Take 2.36 grams of calcium nitrate tetrahydrates and 0.79 gram of diammonium phosphate respectively, be dissolved in respectively in 20 ml deionized water.Dropwise instilled in ammonium dibasic phosphate solution by calcium nitrate solution, period uses ammonia adjust ph to be 7 ~ 8.Treat that two kinds of solution mix completely, obtaining pale precipitation is amorphous calcium phosphate precursor.Get 10 milliliters of amorphous calcium phosphate precursor suspensions to join in flat flow chamber circulating device, constant fluid shearing force 0.5 handkerchief is set, 6 hours action time.Treat that stress loading is complete, suspension is transferred in centrifuge tube, centrifugal and with the supreme clear liquid of washed with de-ionized water in neutral.Precipitation is placed in-80 DEG C of refrigerator and cooled and freezes 2 hours, then to transfer in freezer dryer lyophilization 24 hours, obtain the hydroxyapatite of hydrodynamic shear mediation.
Claims (8)
1. be applicable to a hydroxyapatite material for osseous tissue defect repair and other biomedical applications, it is characterized in that, described hydroxyapatite is mediated by hydrodynamic shear and is formed, and has good mechanics compliance.
2. a preparation method for the hydroxyapatite of hydrodynamic shear mediation, is characterized in that comprising following each step:
(1) calcium salt soln, phosphate solution are weighed by calcium phosphorus mol ratio 1.67, be dissolved in deionized water solution respectively;
(2) dropwise instilled in phosphate solution by calcium salt soln, regulate pH>7 by ammonia or sodium hydroxide therebetween, obtaining pale precipitation is amorphous calcium phosphate precursor;
(3) suspension containing amorphous calcium phosphate precursor is transferred in stress loading experimental provision carry out ageing, apply the constant direction hydrodynamic shear of different time and different size simultaneously;
(4) stress loading is complete, collecting precipitation, and repeatedly cleans with deionized water;
(5) precipitation is placed in-80 DEG C of refrigerator and cooled and freezes 2 ~ 4 hours, then to transfer in freezer dryer lyophilization 24 ~ 48 hours, obtain the hydroxyapatite material of hydrodynamic shear mediation.
3. the preparation method of hydroxyapatite of hydrodynamic shear mediation according to claim 2, is characterized in that, described calcium salt soln is one or more in lime nitrate, calcium chloride and calcium hydroxide.
4. the preparation method of hydroxyapatite of hydrodynamic shear mediation according to claim 2, is characterized in that, described phosphate solution is one or more in diammonium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid.
5. the preparation method of the hydroxyapatite of hydrodynamic shear mediation according to claim 2, it is characterized in that, the calcium phosphorus mol ratio of described amorphous calcium phosphate precursor is 1.1 ~ 1.6.
6. the preparation method of the hydroxyapatite of hydrodynamic shear mediation according to claim 2, it is characterized in that, described stress loading experimental provision is for providing the Cone & Plate viscosity instrument of constant direction hydrodynamic shear, flat flow chamber or syringe pump-pump line circulating device.
7. the preparation method of the hydroxyapatite of hydrodynamic shear mediation according to claim 2, it is characterized in that, the load time of described hydrodynamic shear is 0.5 ~ 24 hour, and loading size is 0.1 ~ 2.5 handkerchief.
8. according to hydroxyapatite crystal prepared by the arbitrary preparation method of claim 2 ~ 7, it is characterized in that, the microscopic pattern of described hydroxyapatite is needle-like, and length is 50 ~ 300 nanometers, and calcium phosphorus mol ratio is 1.5 ~ 1.67.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6024985A (en) * | 1992-07-20 | 2000-02-15 | University Of Reading | Bone materials |
| CN1270841A (en) * | 2000-04-19 | 2000-10-25 | 西安交通大学 | Composite hydrothermal synthesis process for preparing nanometer-level hydroxyl apatite biological painting |
| CN103330959A (en) * | 2013-06-04 | 2013-10-02 | 东南大学 | Prestress-reinforced light high-strength controllable-degradation medical composite material and preparation method thereof |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6024985A (en) * | 1992-07-20 | 2000-02-15 | University Of Reading | Bone materials |
| CN1270841A (en) * | 2000-04-19 | 2000-10-25 | 西安交通大学 | Composite hydrothermal synthesis process for preparing nanometer-level hydroxyl apatite biological painting |
| CN103330959A (en) * | 2013-06-04 | 2013-10-02 | 东南大学 | Prestress-reinforced light high-strength controllable-degradation medical composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨辉等: "共沉淀法制备高纯度纳米羟基磷灰石的研究", 《精细化工》 * |
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