CN103663399A - Method for induced synthesis of hydroxyapatite employing gel template - Google Patents
Method for induced synthesis of hydroxyapatite employing gel template Download PDFInfo
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- CN103663399A CN103663399A CN201310677659.6A CN201310677659A CN103663399A CN 103663399 A CN103663399 A CN 103663399A CN 201310677659 A CN201310677659 A CN 201310677659A CN 103663399 A CN103663399 A CN 103663399A
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- hydroxyapatite
- mediated
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Abstract
The invention discloses a method for induced synthesis of hydroxyapatite employing a gel template. The method comprises the following steps: (1) preparation of an alginate solution; (b) preparation of alginate gel; and (c) preparation of hydroxyapatite, wherein the size of the hydroxyapatite is nanoscale. The invention develops a novel preparation method of hydroxyapatite. Auxiliary reaction additives such as a surfactant and the like are not added in the preparation process. The method is simple in preparation technology, mild in reaction condition, and controllable in preparation condition, and hydroxyapatite nano materials with different particle sizes and shapes can be obtained according to the requirements.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic materials, be specifically related to a kind of method of gel template-mediated synthesizing hydroxylapatite.
Background technology
(Hydroxyapatite, chemical molecular formula is Ca to hydroxyapatite
10(PO
4)
6(OH)
2) be the important materials in biomedical sector, be widely used in clinically the reparation that consistency bone is damaged and fill the bone material of shaping and the aspects such as weighting material of tooth, hydroxyapatite is the main object of researcher research always.
Hydroxyapatite is the main inorganic composition in vertebrate bone and tooth, has good biocompatibility, and chemical stability is high, does not produce objectionable impurities after degraded.The preparation method of hydroxyapatite has chemical precipitation method, hydrothermal synthesis method, sol-gel method and microemulsion method at present.Adopt different preparation methods, can obtain the hydroxyapatite of different-shape and structure.The hydroxyapatite of different shape is the key that its excellent properties is fully used.
In prior art, Chinese patent CN 101032630B discloses a kind of under certain temperature of reaction and ultrasonic environment, the cetyl trimethylammonium bromide (CTAB) of take is template, the method of preparing hollow ball shaped nanometer hydroxylapatite, but the method adopts chemical feedstocks, and the hollow ball obtaining contains hydroxyapatite and two kinds of components of unformed calcium phosphate; Chinese patent CN102070131B discloses a kind ofly take eggshell as raw material, utilizes hydro-thermal synthesis process to prepare the method for hydroxyapatite, and synthetic hydroxy apatite powder has the constitutional features similar to natural bone HA; Chinese patent application CN1903706A discloses a kind of method that adopts spray-drying process to prepare hydroxyapatite tiny balloon, in preparation process, adopt be dried-thermal treatment two-step approach of spraying to prepare hydroxyapatite micro-sphere, but products therefrom size is inhomogeneous, and the hollow rate of hydroxyapatite micro-sphere is lower.Above method be take inorganic materials as template substrate, keeps off actual human body situation, and finally by pyroprocessing, removes template, need to be by the equipment of complex and expensive.In addition, what pellet of Fujian Normal University is according to biomineralization principle, adopt biomimetic synthesis, the polysaccharide (chitosan, chondroitin sulfate and Propiram, agarose) of take is template, to preparing different-shape hydroxyapatite crystal nano material, study, the dissolution conditions of selected template solution is harsh, and the hydroxyapatite crystal of preparation be inhomogeneous sheet (He Dan. the bionical study on the synthesis of hydroxyapatite crystal under polysaccharide effect. Fujian Normal University, 2008).
In addition, at occurring in nature, organism is a kind of typical gelling system, is by Supramolecular Assembling, to form gel matrix network by organic macromolecule, this network matrix applies special impact to the mineralisation process of crystal, can intervene the nucleation of mineral and growth.Alginates is a kind of natural polysaccharide, there is good biocompatibility, be easy to be combined with divalent cation form gel, the hydroxyapatite crystal that utilizes alginates gel template to prepare is the main inorganic composition in bone and tooth in human body, there is good chemical stability and biocompatibility, can be widely used in bone tissue restoration and substitute waiting biomedical sector.But utilize alginates gel to there is not yet play-by-play as the research of the growth of template-mediated hydroxyapatite crystal.
Summary of the invention
The object of the invention is to provide a kind of preparation method of gel template-mediated synthesizing hydroxylapatite.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of gel template-mediated synthesizing hydroxylapatite, comprises the steps:
(a) preparation of alginate solution: it is 0.01%～60% the alginates aqueous solution that water miscible alginates is mixed with to massfraction;
(b) preparation of alginates gel: the alginates aqueous solution prepared by step (a) is added drop-wise in the inorganic calcium salt aqueous solution by the speed of 0.01～100mL/min, reaction 5min～6h, washing, obtains alginates gel; The mass ratio of described alginates and inorganic calcium salt is 1: 0.1～0.01: 1;
(c) preparation of hydroxyapatite: preparing aqueous phosphatic and regulating the pH value of aqueous phosphatic is 1～12, then the alginates gel of being prepared by step (b) is put into aqueous phosphatic, room temperature standing and reacting 30min～7 day again, then through washing, alcohol wash, filtration, dry, the nanocrystal obtaining is hydroxyapatite.
In technique scheme, alginates is selected from a kind of in sodium alginate, potassium alginate, Lalgine magnesium, alginate calcium and ammonium alginate in described step (a).
In technique scheme, in described step (b), inorganic calcium salt is selected from CaCl
2, Ca (OH)
2, Ca (NO
3)
2, Ca (OC
2h
5)
2in a kind of.
In technique scheme, in described step (c), phosphoric acid salt is selected from (NH
4)
2hPO
4, H
3pO
4, Na
3pO
4, K
2hPO
4in a kind of; The concentration of described aqueous phosphatic is 0.01M～saturated.
In technique scheme, in described step (c), regulating the reagent of aqueous phosphatic pH value is hydrochloric acid, citric acid, Sorbic Acid, sodium hydroxide or ammoniacal liquor, is preferably hydrochloric acid or ammoniacal liquor; During alcohol wash, the mass concentration of alcoholic solution is 50%～100%, and alcohol is methyl alcohol, ethanol or Virahol, preferred alcohol.
In technique scheme, in described step (c), the dry temperature of hydroxyapatite is 20～120 ℃, and be 1～72 h time of drying.
In technique scheme, in described step (c), the particle size range of hydroxyapatite is 10～500nm.
The present invention asks for protection the hydroxyapatite being prepared by aforesaid method simultaneously.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the starting material that the present invention adopts are alginatess, belong to natural polysaccharide, and wide material sources are cheap, have significantly reduced the preparation cost of hydroxyapatite;
In preparation process of the present invention without supplementary additives such as any tensio-active agents, preparation technology is simple, reaction conditions is gentle, preparation condition is controlled, can obtain as required the hydroxyapatite nanoparticle of different-grain diameter and pattern, has positive realistic meaning.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of hydroxide radical phosphorite nanocrystalline body in the embodiment of the present invention one.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment mono-
The preparation method of sodium alginate gel template-mediated synthesizing hydroxylapatite, comprises the steps:
(1) 2g sodium alginate is joined in deionized water, magnetic agitation 1h, standing 24h then, makes massfraction and is 2% sodium alginate soln;
(2) by 11 g CaCl
2join in deionized water, be mixed with the CaCl of 1mol/L
2solution, then, is 0.5:1 according to sodium alginate/calcium chloride mass ratio, and sodium alginate soln is utilized to 5 mL syringes, is slowly added drop-wise in the calcium chloride solution of 1mol/L according to the speed of 0.5ml/min, is prepared into sodium alginate gel;
(3) by 13.2g (NH
4)
2hPO
4join in deionized water, be prepared into (the NH of 1mol/L
4)
2hPO
4the aqueous solution, then, regulates (NH with ammoniacal liquor
4)
2hPO
4aqueous solution pH=10, puts into sodium alginate gel (the NH of 1mol/L
4)
2hPO
4in the aqueous solution, standing and reacting 6h under room temperature condition, takes out and filters, and with deionized water and dehydrated alcohol, cleans respectively 10 min, 20 ℃ of baking 48h, obtains hydroxyapatite powder.
The scanning electron microscope (SEM) photograph of the above-mentioned hydroxyapatite making is referring to accompanying drawing 1, as seen from the figure: the pattern of hydroxyapatite is block, and yardstick is nano level.
Embodiment bis-
The preparation method of potassium alginate gel template-mediated synthesizing hydroxylapatite, comprises the steps:
(1) 5g potassium alginate is put in deionized water, magnetic agitation 1h, standing 6h then, makes massfraction and is 5% potassium alginate solution;
(2) by 1.64g Ca (NO
3)
2join in deionized water, be mixed with the Ca (NO of 0.1mol/L
3)
2solution, then, is 1:0.5 according to potassium alginate/nitrocalcite mass ratio, by potassium alginate soln using 5 mL syringes, is slowly added drop-wise to the Ca (NO of 0.1mol/L according to the speed of 1.0ml/min
3)
2in solution, be prepared into potassium alginate gel;
(3) by 8.15g Na
3pO
4join in deionized water, be mixed with the Na of 0.5mol/L
3pO
4solution, then, uses hydrochloric acid conditioning solution pH=7, potassium alginate gel is put into the H of 0.5mol/L
3pO
4in solution, under room temperature condition, standing and reacting is 2 days, takes out filtration, with deionized water and dehydrated alcohol, cleans respectively 10min, 120 ℃ of baking 1h, obtains hydroxyapatite powder.
Embodiment tri-
The preparation method of ammonium alginate gel template-mediated synthesizing hydroxylapatite, comprises the steps:
(1) 20g ammonium alginate is joined in deionized water, magnetic agitation 0.5h, standing 12h then, makes massfraction and is 20% ammonium alginate solution;
(2) by 5.5g CaCl
2join in deionized water, be mixed with the CaCl of 0.5mol/L
2solution, then, is 0.1:1 according to ammonium alginate/calcium chloride mass ratio, by ammonium alginate soln using 10 mL syringes, is slowly added drop-wise to the CaCl of 0.5mol/L according to the speed of 2.5ml/min
2in solution, be prepared into ammonium alginate gel;
(3) by 4.56g K
2hPO
4join in deionized water, be prepared into the K of 2.0mol/L
2hPO
4solution, then, with ammoniacal liquor regulator solution pH=9, puts into ammonium alginate gel the K of 2.0mol/L
2hPO
4in solution, under room temperature condition standing 3 days, take out and filter, with deionized water and dehydrated alcohol, clean respectively 10min, 40 ℃ are dried 72h, acquisition hydroxyapatite powder material.
Embodiment tetra-
The preparation method of sodium alginate gel template-mediated synthesizing hydroxylapatite, comprises the steps:
(1) 10g sodium alginate is joined in deionized water, magnetic agitation 0.5h, standing 48h then, is prepared into massfraction and is 10% sodium alginate soln;
(2) by 1.64g Ca (NO
3)
2join in deionized water, be prepared into the Ca (NO of 1.0mol/L
3)
2solution, then, is 0.8:1 according to sodium alginate/nitrocalcite mass ratio, and sodium alginate soln is utilized to 10 mL syringes, is slowly added drop-wise to the Ca (NO of 1.0mol/L according to the speed of 5ml/min
3)
2solution, is prepared into sodium alginate gel;
(3) by K
2hPO
4join in deionized water, be prepared into oversaturated K
2hPO
4solution, then, uses hydrochloric acid conditioning solution pH=6, and sodium alginate gel is put into oversaturated K
2hPO
4in solution, still aging 48h under room temperature condition, takes out and filters, and with deionized water and methyl alcohol, cleans respectively 10min, and 60 ℃ are dried 50h, obtain hydroxyapatite powder material.
Claims (10)
1. a method for gel template-mediated synthesizing hydroxylapatite, is characterized in that, comprises the following steps:
(a) preparation of alginate solution: it is 0.01%～60% the alginates aqueous solution that water miscible alginates is mixed with to massfraction;
(b) preparation of alginates gel: the alginates aqueous solution prepared by step (a) is added drop-wise in the inorganic calcium salt aqueous solution by the speed of 0.01～100mL/min, reaction 5min～6h, washing, obtains alginates gel; The mass ratio of described alginates and inorganic calcium salt is 1: 0.1～0.01: 1;
(c) preparation of hydroxyapatite: preparing aqueous phosphatic and regulating the pH value of aqueous phosphatic is 1～12, then the alginates gel of being prepared by step (b) is put into aqueous phosphatic, room temperature standing and reacting 30min～7 day again, then through washing, alcohol wash, filtration, dry, the nanocrystal obtaining is hydroxyapatite.
2. the method for gel template-mediated synthesizing hydroxylapatite according to claim 1, is characterized in that: the alginates in described step (a) is selected from a kind of in sodium alginate, potassium alginate, Lalgine magnesium, alginate calcium and ammonium alginate.
3. the method for gel template-mediated synthesizing hydroxylapatite according to claim 1, is characterized in that: in described step (b), inorganic calcium salt is selected from CaCl
2, Ca (OH)
2, Ca (NO
3)
2, Ca (OC
2h
5)
2in a kind of.
4. the method for gel template-mediated synthesizing hydroxylapatite according to claim 1, is characterized in that: in described step (c), phosphoric acid salt is selected from (NH
4)
2hPO
4, H
3pO
4, Na
3pO
4, K
2hPO
4in a kind of; The concentration of described aqueous phosphatic is 0.01M～saturated.
5. the method for gel template-mediated synthesizing hydroxylapatite according to claim 1, is characterized in that: in described step (c), regulating the reagent of aqueous phosphatic pH value is hydrochloric acid, citric acid, Sorbic Acid, sodium hydroxide or ammoniacal liquor.
6. the method for gel template-mediated synthesizing hydroxylapatite according to claim 5, is characterized in that: in described step (c), regulating the reagent of aqueous phosphatic pH value is hydrochloric acid or ammoniacal liquor.
7. the method for gel template-mediated synthesizing hydroxylapatite according to claim 1, is characterized in that: the alcohol in described step (c) during alcohol wash is methyl alcohol, ethanol or Virahol.
8. the method for gel template-mediated synthesizing hydroxylapatite according to claim 1, is characterized in that: in described step (c), the drying temperature of hydroxyapatite is 20～120 ℃, and be 1～72 h time of drying.
9. the method for gel template-mediated synthesizing hydroxylapatite according to claim 1, is characterized in that: in described step (c), the particle diameter of hydroxyapatite is 10～500nm.
10. the hydroxyapatite preparing according to the method for any one gel template-mediated synthesizing hydroxylapatite described in claim 1～9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110339403A (en) * | 2019-07-15 | 2019-10-18 | 四川大学 | Spherical nano hydroxyapatite/natural polymer biomimetic scaffolds and preparation method |
| CN111217598A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Hydroxyapatite forming method, hydroxyapatite and application |
| CN111690155A (en) * | 2020-01-11 | 2020-09-22 | 天津科技大学 | Preparation method of nano-cellulose/hydroxyapatite nanospheres |
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| CN102020777A (en) * | 2010-11-29 | 2011-04-20 | 同济大学 | Method for preparing nano hydroxyl apatite calcium alginate injectable hydrogel and application thereof |
| CN102491299A (en) * | 2011-11-14 | 2012-06-13 | 苏州大学 | Preparation method of nano hydroxyapatite |
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Patent Citations (2)
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|---|---|---|---|---|
| CN102020777A (en) * | 2010-11-29 | 2011-04-20 | 同济大学 | Method for preparing nano hydroxyl apatite calcium alginate injectable hydrogel and application thereof |
| CN102491299A (en) * | 2011-11-14 | 2012-06-13 | 苏州大学 | Preparation method of nano hydroxyapatite |
Non-Patent Citations (1)
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| 肖海军等: "纳米羟基磷灰石/羧甲基壳聚糖-海藻酸钠复合骨水泥与骨髓基质细胞的生物相容性", 《中国组织工程研究》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217598A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Hydroxyapatite forming method, hydroxyapatite and application |
| CN111217598B (en) * | 2018-11-27 | 2021-09-21 | 中国科学院大连化学物理研究所 | Hydroxyapatite forming method, hydroxyapatite and application |
| CN110339403A (en) * | 2019-07-15 | 2019-10-18 | 四川大学 | Spherical nano hydroxyapatite/natural polymer biomimetic scaffolds and preparation method |
| CN110339403B (en) * | 2019-07-15 | 2020-06-12 | 四川大学 | Spherical nano hydroxyapatite/natural polymer bionic scaffold and preparation method thereof |
| CN111690155A (en) * | 2020-01-11 | 2020-09-22 | 天津科技大学 | Preparation method of nano-cellulose/hydroxyapatite nanospheres |
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