CN1488574A - Method for preparing biomedical amorphous nano calcium phosphate - Google Patents
Method for preparing biomedical amorphous nano calcium phosphate Download PDFInfo
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- CN1488574A CN1488574A CNA031420044A CN03142004A CN1488574A CN 1488574 A CN1488574 A CN 1488574A CN A031420044 A CNA031420044 A CN A031420044A CN 03142004 A CN03142004 A CN 03142004A CN 1488574 A CN1488574 A CN 1488574A
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Abstract
The invention discloses a manufacturing method for amorphous nano calcium phosphate in medical field. The method uses phosphor-contained compound and calcium-contained compound as raw materials, uses polymer as stabilizer, carries on reaction under 0-20 DEG C in water solution and produces into amorphous calcium phosphate.
Description
Technical field
The present invention relates to a kind of as the preparation method, particularly biological activity of biological bone alternate material and the preparation method of the adjustable amorphous calcium phosphate of biodegradation rate.
Background technology
Calcium phosphate material because of its have with bone in inorganic mutually similar chemical constitution, and be widely used as the bone equivalent material.Amorphous calcium phosphate and is widely used in biomedical sectors such as biological coating, bone cement because it has than crystalline calcium phosphate superior bioactive and biodegradability more, more and more is subjected to investigator's attention.Amorphous calcium phosphate is a kind of intermediate product that exists when preparing hydroxyapatite in the aqueous solution, is easy to be transformed into crystalline calcium phosphate.All the time, the investigator attempts to find a kind of method more easily to obtain amorphous calcium phosphate in the aqueous solution.More common method is to add stablizer in the aqueous solution of preparation calcium phosphate.(Polymeric amorphous calcium phosphate compositions.Antonucci etal.US5508342) adds materials such as Calcium Pyrophosphate and magnesium chloride and obtains amorphous calcium phosphate as stablizer people such as Antonucci in the aqueous solution of preparation calcium phosphate.But the calcium phosphate that this method obtains not only contains impurity such as pyrophosphate and magnesium ion, but also is (Synthesis of reactive amorphouscalcium phosphates, Lee, the et a1.US5683461) of reactionlessness.Therefore obtain pure amorphous calcium phosphate and can only utilize physical method such as crystalline calcium phosphate high-temperature fusion-quick cooling to obtain, the amorphous calcium phosphate Ca/P that this method obtains is than unadjustable, and complex process, costs an arm and a leg.
Summary of the invention
The object of the present invention is to provide the preparation method of the amorphous nano-calcium phosphate powder of a kind of bio-medical.This method preparation process condition is simple, and prepared amorphous calcium phosphate inclusion-free ion has good biological activity and biological degradability.
The method for preparing the amorphous nano-calcium phosphate powder of bio-medical provided by the invention may further comprise the steps:
1) P contained compound is soluble in water, being mixed with concentration is the A solution of 0.1M～5M, places under 0～20 ℃;
2) calcium containing compound is soluble in water, being mixed with concentration is the B solution of 0.1M～5M, places under 0～20 ℃;
3) an amount of polymkeric substance is dissolved in formation C solution in the B solution, places under 0～20 ℃, wherein the addition of polymkeric substance is, the mol ratio of polymkeric substance and calcium ion is 1: 10～10: 1, and polymkeric substance calculates with the mole number of structural unit;
4) be 1.00～2.00 by the Ca/P mol ratio, the A drips of solution is added in the C solution, drip basic solution during reaction and regulate pH value 7～12, be reflected at constantly and carry out under the stirring, temperature of reaction is 0 ℃～20 ℃, and the reaction times is 5min～48h, separation, washing, drying obtain amorphous calcium phosphate.
Among the present invention, described P contained compound can be ammonium hydrogen phosphate or sodium phosphate or phosphoric acid or potassiumphosphate.Calcium containing compound can be nitrocalcite or calcium chloride or calcium hydroxide.Polymkeric substance is to have the functional group that can produce complexing action with metallic cation, preferably is selected from polyoxyethylene glycol (PEG) or polyvinyl alcohol (PVA) or polyacrylic acid (PAA) or poly-(vinylformic acid-Propylene glycol monoacrylate).The basic solution that is used to regulate the pH value can adopt ammoniacal liquor or sodium hydroxide or potassium hydroxide solution, and the speed that drips basic solution is generally 1～20ml/min.
The amorphous calcium phosphate of high reaction activity if desired, can be with the above-mentioned amorphous calcium phosphate that makes with the temperature rise rate of 5 ℃/min～50 ℃/min at 300 ℃～500 ℃ following thermal treatment 10min～5h.
The present invention can regulate the biological activity and the biological degradability of amorphous calcium phosphate by conditioned reaction thing Ca/P mol ratio and reaction times.
In the preparation process of the present invention, adopt methods such as suction filtration or centrifugation to separate, drying can adopt vacuum-drying or lyophilize or spraying drying.The granular size of amorphous calcium phosphate can be regulated between 10nm～1000nm by changing preparation process condition.
The present invention has the following advantages:
1) amorphous calcium phosphate of the present invention's preparation does not contain other inorganics impurity;
2) there is polymkeric substance in the amorphous calcium phosphate surface of the present invention's preparation, does not need the additional surface modification promptly to can be used as the weighting agent of matrix material.
3) amorphous calcium phosphate of the present invention's preparation can recently be regulated its biological activity and biological degradability by regulating the Ca/P mole.
4) amorphous calcium phosphate of the present invention's preparation still keeps amorphous after Overheating Treatment, does not contain any impurity, and the reactive behavior height; Even particle distribution is not reunited, and disperses easily.
5) particle size of the amorphous calcium phosphate of the present invention's preparation can be regulated between 10nm～1000nm.
6) preparation process condition of the present invention's employing is simple, simple to operate, and cost is low, is easy to industrialization.
Embodiment
Embodiment 1
Na
3PO
412H
2O is dissolved in that to form phosphorus concentration after the stirring and dissolving in the distilled water of 100ml be the A solution of 0.173M; With CaCl
2Be dissolved in that to form calcium concn in the distilled water of 200ml be the B solution of 0.130M, in B solution, add an amount of PEG (PEG: CaCl
2=3: 1, mol ratio, polymkeric substance calculates with the mole number of structural unit, down with) the dissolving back forms C solution, and A and C solution are placed on 5 ℃ of refrigerations down.Treat behind the temperature-stable under 5 ℃ the speed of A solution with 2ml/min to be added drop-wise in the C solution, pH regulates with ammoniacal liquor and remains on 10, reacts 30min under magnetic agitation, and the Ca/P ratio is 1.50.Throw out is through suction filtration, washing, and lyophilize 48 hours gets amorphous calcium phosphate, takes out and puts into the moisture eliminator storage.
Embodiment 2
Na
3PO
412H
2O is dissolved in that to form phosphorus concentration after the stirring and dissolving in the distilled water of 100ml be the A solution of 0.173M; With CaCl
2Be dissolved in that to form calcium concn in the distilled water of 200ml be the B solution of 0.130M, in B solution, add an amount of PVA (PVA: CaCl
2=3: 1, mol ratio, polymkeric substance calculates with the mole number of structural unit, down with) the dissolving back forms C solution, and A and C solution are placed on 5 ℃ of refrigerations down.Treat behind the temperature-stable under 5 ℃ the speed of A solution with 2ml/min to be added drop-wise in the C solution, pH regulates with ammoniacal liquor and remains on 10, reacts 30min under magnetic agitation, and the Ca/P ratio is 1.50.Throw out during spraying drying, gets amorphous calcium phosphate through centrifugation, washing, takes out and puts into the moisture eliminator storage.
Embodiment 3
Na
3PO
412H
2O is dissolved in that to form phosphorus concentration after the stirring and dissolving in the distilled water of 100ml be the A solution of 0.162M; With CaCl
2Be dissolved in that to form calcium concn in the distilled water of 200ml be the B solution of 0.130M, in B solution, add an amount of PAA (PAA: CaCl
2=3: 1, mol ratio, polymkeric substance calculates with the mole number of structural unit, down with) the dissolving back forms C solution, and A and C solution are placed on 5 ℃ of refrigerations down.Treat behind the temperature-stable under 5 ℃ the speed of A solution with 2ml/min to be added drop-wise in the C solution, pH regulates with ammoniacal liquor and remains on 10, reacts 30min under magnetic agitation, and the Ca/P ratio is 1.60.Throw out is through suction filtration, washing, and lyophilize 48 hours gets amorphous calcium phosphate, takes out and puts into the moisture eliminator storage.
Embodiment 4
Na
3PO
412H
2O is dissolved in that to form phosphorus concentration after the stirring and dissolving in the distilled water of 100ml be the A solution of 0.15M; With CaCl
2Be dissolved in that to form calcium concn in the distilled water of 200ml be the B solution of 0.15M, in B solution, add an amount of PEG (PEG: CaCl
2=5: 1, mol ratio, polymkeric substance calculates with the mole number of structural unit, down with) the dissolving back forms C solution, and A and C solution are placed on 5 ℃ of refrigerations down.Treat behind the temperature-stable under 5 ℃ the speed of A solution with 2ml/min to be added drop-wise in the C solution, pH regulates with ammoniacal liquor and remains on 10, reacts 30min under magnetic agitation, and the Ca/P ratio is 2.00.Throw out is through suction filtration, washing, and lyophilize 48 hours gets amorphous calcium phosphate, takes out and puts into the moisture eliminator storage.
Embodiment 5
Na
3PO
412H
2O is dissolved in that to form phosphorus concentration after the stirring and dissolving in the distilled water of 100ml be the A solution of 0.173M; With CaCl
2Be dissolved in that to form calcium concn in the distilled water of 200ml be the B solution of 0.130M, in B solution, add an amount of PVA (PVA: CaCl
2=10: 1) the dissolving back forms C solution, and A and C solution are placed on 5 ℃ of refrigerations down.Treat behind the temperature-stable under 5 ℃ the speed of A solution with 2ml/min to be added drop-wise in the C solution, pH regulates with ammoniacal liquor and remains on 10, reacts 30min under magnetic agitation, and the Ca/P ratio is 1.50.Throw out is through suction filtration, washing, and lyophilize 48 hours gets amorphous calcium phosphate, takes out and puts into the moisture eliminator storage.
Embodiment 6
Na
3PO
412H
2O is dissolved in that to form phosphorus concentration after the stirring and dissolving in the distilled water of 100ml be the A solution of 0.173M; With CaCl
2Be dissolved in that to form calcium concn in the distilled water of 200ml be the B solution of 0.13M, in B solution, add an amount of PAA (PAA: CaCl
2=5: 1, mol ratio, polymkeric substance calculates with the mole number of structural unit, down with) the dissolving back forms C solution, and A and C solution are placed on 5 ℃ of refrigerations down.Treat behind the temperature-stable under 5 ℃ the speed of A solution with 2ml/min to be added drop-wise in the C solution, pH regulates with sodium hydroxide solution and remains on 10, reacts 30min under magnetic agitation, and the Ca/P ratio is 1.50.Throw out is through suction filtration, washing, and lyophilize 48 hours gets amorphous calcium phosphate, takes out and puts into the moisture eliminator storage.
Embodiment 7
Place in the retort furnace under the condition of logical oxygen temperature rise rate with 10 ℃/min to be raised to 500 ℃ of following thermal treatments the amorphous calcium phosphate of gained in the foregoing description and take out cooling after 30 minutes.Obtain the amorphous calcium phosphate of no any impurity and high reaction activity.
Claims (7)
1. the preparation method of the amorphous nano-calcium phosphate of bio-medical is characterized in that may further comprise the steps:
1) P contained compound is soluble in water, being mixed with concentration is the A solution of 0.1M～5M, places under 0～20 ℃;
2) calcium containing compound is soluble in water, being mixed with concentration is the B solution of 0.1M～5M, places under 0～20 ℃;
3) an amount of polymkeric substance is dissolved in formation C solution in the B solution, places under 0～20 ℃, wherein the addition of polymkeric substance is that the mol ratio of polymkeric substance and calcium ion is 1: 10～10: 1, and polymkeric substance calculates with the mole number of structural unit;
4) be 1.00～2.00 by the Ca/P mol ratio, the A drips of solution is added in the C solution, drip basic solution during reaction and regulate pH value 7～12, be reflected at constantly and carry out under the stirring, temperature of reaction is 0 ℃～20 ℃, and the reaction times is 5min～48h, separation, washing, drying obtain amorphous calcium phosphate.
2. by the preparation method of the amorphous nano-calcium phosphate of the described bio-medical of claim 1, it is characterized in that described P contained compound is ammonium hydrogen phosphate or sodium phosphate or phosphoric acid or potassiumphosphate.
3. by the preparation method of the amorphous nano-calcium phosphate of the described bio-medical of claim 1, it is characterized in that described calcium containing compound is nitrocalcite or calcium chloride or calcium hydroxide.
4. according to the preparation method of the amorphous nano-calcium phosphate of the described bio-medical of claim 1, it is characterized in that described polymkeric substance has the functional group that can produce complexing action with metallic cation, be selected from polyoxyethylene glycol or polyvinyl alcohol or polyacrylic acid or poly-(vinylformic acid-Propylene glycol monoacrylate).
5. according to the preparation method of the amorphous nano-calcium phosphate of the described bio-medical of claim 1, it is characterized in that the basic solution that step 4) is used to regulate the pH value is ammoniacal liquor or sodium hydroxide or potassium hydroxide solution.
6. according to the preparation method of the amorphous nano-calcium phosphate of the described bio-medical of claim 1, it is characterized in that the amorphous calcium phosphate that will make with the temperature rise rate of 5 ℃/min～50 ℃/min at 300 ℃～500 ℃ following thermal treatment 10min～5h.
7. according to the preparation method of the amorphous nano-calcium phosphate of the described bio-medical of claim 1, it is characterized in that said be separated into suction filtration or centrifugation, dry vacuum-drying or lyophilize or the spraying drying of adopting.
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| CN 03142004 CN1217855C (en) | 2003-07-28 | 2003-07-28 | Method for preparing biomedical amorphous nano calcium phosphate |
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| CN1302984C (en) * | 2005-09-28 | 2007-03-07 | 浙江大学 | Prepn process of nanometer tricalcium phosphate powder with slowly released metal ion |
| CN1314462C (en) * | 2005-04-25 | 2007-05-09 | 浙江大学 | Degradable biomedicine composite material in nanometer structure and its prepn process |
| CN100428963C (en) * | 2005-11-30 | 2008-10-29 | 浙江大学 | Preparation method of non-sizing nano-calcium phosphate powder for medical slow release metal ion |
| CN100444897C (en) * | 2006-03-06 | 2008-12-24 | 南京凯瑞尔纳米生物技术有限公司 | Nano complex eye drops containing liposoluble compound drug and its preparing method |
| CN102102242A (en) * | 2010-12-31 | 2011-06-22 | 中国科学院上海硅酸盐研究所 | Method for preparing polylactic acid-amorphous calcium phosphate nano composite fiber material |
| CN102286764A (en) * | 2011-07-01 | 2011-12-21 | 浙江大学 | Method for preparing periodical absorbable Hyaluronic Acid/acyl carrier protein (HA/ACP) composite coating on titanium implant surface |
| CN102320586A (en) * | 2011-09-07 | 2012-01-18 | 山东大学 | Synthesizing method of amorphous calcium phosphate |
| CN103027845A (en) * | 2013-01-06 | 2013-04-10 | 浙江大学 | Method for repairing demineralized dentin |
| CN103159198A (en) * | 2013-04-09 | 2013-06-19 | 厦门合众思创生物工程有限公司 | Preparation method of calcium phosphate |
| CN104856889A (en) * | 2014-09-22 | 2015-08-26 | 北京大学口腔医学院 | Preparation method for slow-release chlorhexidine amorphous calcium phosphate nanoparticles |
| CN104860284A (en) * | 2014-10-11 | 2015-08-26 | 北京大学口腔医学院 | Preparation method for amorphous calcium phosphate nanospheres |
| CN106473933A (en) * | 2016-10-13 | 2017-03-08 | 浙江大学 | The biomineralization material of bonding auxiliary and its application in biomimetic mineralization |
| CN107374980A (en) * | 2017-09-04 | 2017-11-24 | 苏州博瑞华仿生材料科技有限公司 | Controllable calcium phosphate gelatin nano composite material of a kind of component content and crystal structure and preparation method thereof |
| CN109401157A (en) * | 2018-11-30 | 2019-03-01 | 中国科学院金属研究所 | A kind of amorphous calcium phosphate-polyacrylic acid hybrid nano-material and its preparation method and application |
| CN109734066A (en) * | 2019-03-07 | 2019-05-10 | 中山职业技术学院 | A kind of preparation method of high-performance biomedicine amorphous calcium phosphate 3D printing material |
| CN110482585A (en) * | 2019-08-05 | 2019-11-22 | 浙江工业大学 | A kind of synthetic method of amorphous calcium carbonate |
| CN110693724A (en) * | 2019-11-05 | 2020-01-17 | 浙江大学 | Tooth mineralizing liquid and mineralizing method thereof |
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2003
- 2003-07-28 CN CN 03142004 patent/CN1217855C/en not_active Expired - Fee Related
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| CN1314462C (en) * | 2005-04-25 | 2007-05-09 | 浙江大学 | Degradable biomedicine composite material in nanometer structure and its prepn process |
| CN1302984C (en) * | 2005-09-28 | 2007-03-07 | 浙江大学 | Prepn process of nanometer tricalcium phosphate powder with slowly released metal ion |
| CN100428963C (en) * | 2005-11-30 | 2008-10-29 | 浙江大学 | Preparation method of non-sizing nano-calcium phosphate powder for medical slow release metal ion |
| CN100444897C (en) * | 2006-03-06 | 2008-12-24 | 南京凯瑞尔纳米生物技术有限公司 | Nano complex eye drops containing liposoluble compound drug and its preparing method |
| CN102102242A (en) * | 2010-12-31 | 2011-06-22 | 中国科学院上海硅酸盐研究所 | Method for preparing polylactic acid-amorphous calcium phosphate nano composite fiber material |
| CN102286764A (en) * | 2011-07-01 | 2011-12-21 | 浙江大学 | Method for preparing periodical absorbable Hyaluronic Acid/acyl carrier protein (HA/ACP) composite coating on titanium implant surface |
| CN102320586A (en) * | 2011-09-07 | 2012-01-18 | 山东大学 | Synthesizing method of amorphous calcium phosphate |
| CN102320586B (en) * | 2011-09-07 | 2013-10-23 | 山东大学 | Synthesizing method of amorphous calcium phosphate |
| CN103027845A (en) * | 2013-01-06 | 2013-04-10 | 浙江大学 | Method for repairing demineralized dentin |
| CN103159198A (en) * | 2013-04-09 | 2013-06-19 | 厦门合众思创生物工程有限公司 | Preparation method of calcium phosphate |
| CN103159198B (en) * | 2013-04-09 | 2015-04-01 | 厦门合众思创生物工程有限公司 | Preparation method of calcium phosphate |
| CN104856889A (en) * | 2014-09-22 | 2015-08-26 | 北京大学口腔医学院 | Preparation method for slow-release chlorhexidine amorphous calcium phosphate nanoparticles |
| CN104856889B (en) * | 2014-09-22 | 2017-05-10 | 北京大学口腔医学院 | Preparation method for slow-release chlorhexidine amorphous calcium phosphate nanoparticles |
| CN104860284A (en) * | 2014-10-11 | 2015-08-26 | 北京大学口腔医学院 | Preparation method for amorphous calcium phosphate nanospheres |
| CN104860284B (en) * | 2014-10-11 | 2017-07-04 | 北京大学口腔医学院 | A kind of preparation method of amorphous calcium phosphate nanosphere |
| CN106473933A (en) * | 2016-10-13 | 2017-03-08 | 浙江大学 | The biomineralization material of bonding auxiliary and its application in biomimetic mineralization |
| CN107374980A (en) * | 2017-09-04 | 2017-11-24 | 苏州博瑞华仿生材料科技有限公司 | Controllable calcium phosphate gelatin nano composite material of a kind of component content and crystal structure and preparation method thereof |
| CN107374980B (en) * | 2017-09-04 | 2021-02-02 | 苏州一佳一生物科技有限公司 | Calcium phosphate-gelatin nano composite material with controllable component content and crystal structure and preparation method thereof |
| CN109401157A (en) * | 2018-11-30 | 2019-03-01 | 中国科学院金属研究所 | A kind of amorphous calcium phosphate-polyacrylic acid hybrid nano-material and its preparation method and application |
| CN109734066A (en) * | 2019-03-07 | 2019-05-10 | 中山职业技术学院 | A kind of preparation method of high-performance biomedicine amorphous calcium phosphate 3D printing material |
| CN109734066B (en) * | 2019-03-07 | 2022-05-20 | 中山职业技术学院 | Preparation method of high-performance amorphous calcium phosphate 3D printing material for biomedicine |
| CN110482585A (en) * | 2019-08-05 | 2019-11-22 | 浙江工业大学 | A kind of synthetic method of amorphous calcium carbonate |
| CN110693724A (en) * | 2019-11-05 | 2020-01-17 | 浙江大学 | Tooth mineralizing liquid and mineralizing method thereof |
| CN111631970A (en) * | 2020-06-30 | 2020-09-08 | 湖南御家化妆品制造有限公司 | Nano calcium phosphate-loaded idebenone particle, preparation method thereof and cosmetic |
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