CN103738932B - A kind of nanometer hydroxyapatite and preparation method thereof - Google Patents
A kind of nanometer hydroxyapatite and preparation method thereof Download PDFInfo
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- CN103738932B CN103738932B CN201310677577.1A CN201310677577A CN103738932B CN 103738932 B CN103738932 B CN 103738932B CN 201310677577 A CN201310677577 A CN 201310677577A CN 103738932 B CN103738932 B CN 103738932B
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- fibroin
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Abstract
The invention discloses a kind of nanometer hydroxyapatite and preparation method thereof.Concrete preparation method is: directly dissolve regenerated silk fibroin film prepared by fibroin fiber for template with formic acid/calcium salt or hexafluoroisopropanol/calcium salt soln, prepare spherical nanometer hydroxyapatite under normal temperature in phosphate solution through ageing, filtration, washing, alcohol wash and drying.Preparation method and the equipment of the present invention's exploitation are simple, and cost is low, can realize continuous operation, thus effectively shorten preparation cycle; The hydroxyapatite material utilizing present method to prepare is superior in quality, stable performance, grain diameter are even, and pattern is mainly particulate state, and particle diameter is 10 ~ 500nm.
Description
Technical field
The present invention relates to a kind of inorganic nano material and preparation method thereof, be specifically related to a kind of nanometer hydroxyapatite and preparation method thereof.
Background technology
Hydroxyapatite is the important inorganic components forming human body hard tissue, have good biocompatibility, bone conduction performance, chemical stability is high, does not produce objectionable impurities after degraded, implanting and can promote the growth of new bone, is a kind of desirable embedded type solid support material.The preparation method of hydroxyapatite can be divided into dry process and wet-layer preparation.Wet-layer preparation mainly adopts chemical precipitation method, hydrothermal synthesis method and sol-gel method etc.
Along with the development of nano material preparation technology, the preparation of nanometer hydroxyapatite has welcome new opportunity to develop, utilize the technology such as biomimetic mineralization and template-mediated, nano-grade hydroxy apatite product can be obtained in normal temperature, normal pressure, water solution system, thus effectively improve the quality of products, reduce energy consumption.
Prior art discloses the multiple method preparing hydroxyapatite, utilize silk fibroin nano-fiber to mix with calcium source and phosphoric acid root as Chinese patent application CN102491298A discloses one, be obtained by reacting the method for nanometer hydroxyapatite; Chinese patent application CN102491299A discloses a kind of silk fibroin nanosphere gel that utilizes for the method for Template preparation nanometer hydroxyapatite, the method needs silk fibroin water solution to process under electrostatic field, first silk fibroin nanosphere gel is obtained, and then mix with calcium source and phosphoric acid root, be obtained by reacting nanometer hydroxyapatite; Chinese patent CN101880034B discloses a kind of preparation of porous hydroxyapatite, under the method utilizes the regulation and control of organic molecule acid, form vesicular structure by self-assembly, the width of the hydroxyapatite nano sheet of preparation is 50-200nm, and the aperture of material is 0.5-5 μm; It is raw material with eggshell that Chinese patent application CN102070131A discloses a kind of, and utilize hydro-thermal synthesis process to prepare the method for hydroxyapatite, the hydroxy apatite powder of synthesis has the constitutional features similar to natural bone HA; Chinese patent application CN102167300A discloses a kind of preparation method of hexagonal micro powder hydroxyapatite material, the method with calcium carbonate and secondary calcium phosphate for initial reactant, adopting case of wet attrition method and hydrothermal synthesis method, is the hexagonal column micro mist hydroxy apatite powder of 1-3 μm according to biomineralization principle synthesis particle diameter; In addition, the people such as NeyvisAlmora-Barrios adopt collagen as template, blending calcium source and phosphoric acid root under alkaline condition, prepare hydroxyapatite (see: NeyvisAlmora-Barrios, NoraH.DeLeeuw.Cryst.MolecularDynamicsSimulationoftheEarl yStagesofNucleationofHydroxyapatiteataCollagenTemplateGr owthDes.12 (2012) 756-763).Hydroxyapatite nanoparticle can be obtained with upper type, but preparation process is loaded down with trivial details, desired raw material price, is unsuitable for large-scale production.
Summary of the invention
The object of the invention is to provide a kind of preparation method of nanometer hydroxyapatite.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of nanometer hydroxyapatite, comprises the steps:
The preparation of (a) fibroin protein film: silk through coming unstuck, drying obtains fibroin fiber, fibroin fiber obtains silk fibroin protein solution through dissolving, then through super-dry, washing, dry again, is prepared into regenerated silk fibroin film;
The preparation of (b) hydroxyapatite: phosphoric acid salt is mixed with the aqueous phosphatic that concentration is 0.05mol/L ~ saturated, and regulate aqueous phosphatic pH value to be 4 ~ 11, then fibroin protein film prepared by step (a) is put into aqueous phosphatic, through still aging, filtration, washing, alcohol wash, drying, obtain nanometer hydroxyapatite.
In technique scheme, in described step (a), the dissolution mechanism of fibroin fiber is for dissolving fibroin fiber with formic acid/calcium salt mixing solutions or hexafluoroisopropanol/calcium salt mixing solutions; The mass ratio of fibroin fiber and calcium salt is 99:1 ~ 10:90; Wherein calcium salt is selected from CaCl
2, Ca (OH)
2, Ca (NO
3)
2, Ca (OC
2h
5)
2in one or more.
In technique scheme, in described step (a), the mass concentration of silk fibroin protein solution is 0.1% ~ 60%.
In technique scheme, in described step (b), phosphoric acid salt is selected from (NH
4)
2hPO
4, H
3pO
4, Na
3pO
4, K
2hPO
4in one or more; The reagent regulating phosphate solution pH value is ammoniacal liquor or hydrochloric acid; The still aging reaction times is 0.5 ~ 30 day, and drying temperature is 20 ~ 120 DEG C, and time of drying is 1 ~ 72h.
In technique scheme, in described step (b), the particle diameter of the hydroxyapatite of preparation is 10 ~ 500nm.
The present invention asks to protect the nanometer hydroxyapatite prepared by aforesaid method simultaneously.
Because technique scheme is used, the present invention compared with prior art has following advantages:
(1) this invention exploits a kind of method preparing nanometer hydroxyapatite newly, first prepare regenerated silk fibroin film; Then with this fibroin protein film for template, the formation of induced nano hydroxyapatite in the solution, raw materials usedly belongs to conventional products, cheap and easy to get;
(2) preparation method provided by the invention is simple, mild condition is controlled, and can obtain the nanometer hydroxyapatite of size and morphology controllable, has positive realistic meaning.
Accompanying drawing explanation
Fig. 1 is the SEM figure of nanometer hydroxyapatite in embodiment one.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment one
A preparation method for nanometer hydroxyapatite, comprises the steps:
(1) sodium carbonate solution of natural mulberry silk massfraction 0.05% boils 30min and comes unstuck, and repeats 3 times and obtains pure mulberry silk fibroin fibers afterwards; This fibroin fiber is dissolved in the mixing solutions of formic acid/calcium chloride, wherein the mass ratio of fibroin fiber and calcium chloride is 1:0.5, room temperature magnetic agitation 3h, obtain the regenerated silk protein solution that massfraction is 5%, by regenerated silk protein solution film forming, dry, washing, dry again, obtain regenerated silk fibroin film;
(2) by (NH
4)
2hPO
4be prepared into (the NH of 0.5mol/L
4)
2hPO
4the aqueous solution, and be 11 by ammoniacal liquor regulator solution pH value; Regenerated silk fibroin film is put into the (NH of 0.5mol/L
4)
2hPO
4in the aqueous solution, room temperature ageing reaction 3h, filters, cleans 10min respectively with deionized water and dehydrated alcohol, then in 60 DEG C of dry 72h, obtains nano hydroxyapatite material.
The scanning electron microscope (SEM) photograph of above-mentioned obtained nanometer hydroxyapatite is see shown in accompanying drawing 1; As seen from the figure, hydroxyapatite is particulate state, and is of a size of 20 ~ 100nm.
Embodiment two
(1) sodium carbonate solution of natural mulberry silk massfraction 0.05% boils 30min and comes unstuck, and repeats 3 times and obtains pure mulberry silk fibroin fibers afterwards; This fibroin fiber is dissolved in the mixing solutions of formic acid/nitrocalcite, wherein the mass ratio of fibroin fiber and nitrocalcite is 1:1, room temperature magnetic agitation 3h, obtain the regenerated silk protein solution that massfraction is 20%, by regenerated silk protein solution film forming, dry, washing, dry again, obtain regenerated silk fibroin film;
(2) by H
3pO
4be prepared into the H of 0.1mol/L
3pO
4the aqueous solution, and be 7 by ammoniacal liquor regulator solution pH value; Regenerated silk fibroin film is put into the H of 0.1mol/L
3pO
4in the aqueous solution, room temperature still aging reaction 120h, filters, cleans 10min respectively with deionized water and dehydrated alcohol, then in 120 DEG C of dry 1h, obtains nano hydroxyapatite material.
Embodiment three
(1) natural tussah silk massfraction be 0.5% sodium carbonate solution boil 30min and come unstuck, repeat 3 times and obtain pure mulberry silk fibroin fibers afterwards; By this fibroin fiber solution in the mixing solutions of hexafluoroisopropanol/calcium chloride, wherein the mass ratio of fibroin fiber and calcium chloride is 20:1, room temperature magnetic agitation 6h, obtain the regenerated silk protein solution that massfraction is 0.2%, by regenerated silk protein solution film forming, dry, washing, dry again, obtain regenerated silk fibroin film;
(2) by (NH
4)
2hPO
4be prepared into (the NH of 0.2mol/L
4)
2hPO
4the aqueous solution, and be 6 by hydrochloric acid conditioning solution pH value; Regenerated silk fibroin film is inserted the (NH of 0.2mol/L
4)
2hPO
4in the aqueous solution, room temperature still aging reaction 24h, filters, cleans 10min respectively with deionized water and dehydrated alcohol, then in 90 DEG C of dry 20h, obtains hydroxyapatite material.
Embodiment four
(1) natural mulberry silk massfraction be 0.5% sodium carbonate solution boil 30min and come unstuck, repeat 3 times and obtain pure mulberry silk fibroin fibers afterwards; By this fibroin fiber solution in the mixing solutions of hexafluoroisopropanol/calcium hydroxide, wherein the mass ratio of fibroin fiber and calcium hydroxide is 1:2, room temperature magnetic agitation 6h, obtain the regenerated silk protein solution that massfraction is 20.0%, by regenerated silk protein solution film forming, dry, washing, dry again, obtain regenerated silk fibroin film;
(2) by Na
3pO
4be prepared into saturated Na
3pO
4the aqueous solution, and be 8 by hydrochloric acid conditioning solution pH value; Regenerated silk fibroin film is inserted saturated Na
3pO
4in the aqueous solution, room temperature still aging reaction 72h, filters, cleans 10min respectively with deionized water and dehydrated alcohol, then in 50 DEG C of dry 40h, obtains hydroxyapatite material.
Embodiment five
(1) natural mulberry silk massfraction be 0.5% sodium carbonate solution boil 30min and come unstuck, repeat 3 times and obtain pure mulberry silk fibroin fibers afterwards; By this fibroin fiber solution in hexafluoroisopropanol/Ca (OC
2h
5)
2mixing solutions in, wherein fibroin fiber and Ca (OC
2h
5)
2mass ratio be 1:9, room temperature magnetic agitation 6h, obtains the regenerated silk protein solution that massfraction is 60.0%, by regenerated silk protein solution film forming, dry, washing, drier, obtains regenerated silk fibroin film;
(2) by K
2hPO
4be prepared into the K of 0.05mol/L
2hPO
4the aqueous solution, and be 10 by hydrochloric acid conditioning solution pH value; Regenerated silk fibroin film is inserted the K of 0.05mol/L
2hPO
4in the aqueous solution, the still aging reaction of room temperature 10 days, filters, cleans 10min respectively with deionized water and dehydrated alcohol, then in 100 DEG C of dry 10h, obtains hydroxyapatite material.
Claims (7)
1. a preparation method for nanometer hydroxyapatite, is characterized in that, comprises the steps:
The preparation of (a) fibroin protein film: silk through coming unstuck, drying obtains fibroin fiber, fibroin fiber obtains silk fibroin protein solution through dissolving, then through super-dry, washing, dry again, is prepared into regenerated silk fibroin film;
The dissolution mechanism of described fibroin fiber is for dissolving fibroin fiber with formic acid/calcium salt mixing solutions or hexafluoroisopropanol/calcium salt mixing solutions; The mass ratio of fibroin fiber and calcium salt is 99:1 ~ 10:90;
The preparation of (b) hydroxyapatite: phosphoric acid salt is mixed with the aqueous phosphatic that concentration is 0.05mol/L ~ saturated, and regulate aqueous phosphatic pH value to be 4 ~ 11, then regenerated silk fibroin film prepared by step (a) is put into aqueous phosphatic, through still aging, filtration, washing, alcohol wash, drying, obtain nanometer hydroxyapatite.
2. the preparation method of nanometer hydroxyapatite according to claim 1, is characterized in that: described calcium salt is selected from CaCl
2, Ca (OH)
2, Ca (NO
3)
2, Ca (OC
2h
5)
2in one or more.
3. the preparation method of nanometer hydroxyapatite according to claim 1, is characterized in that: in described step (a), the mass concentration of silk fibroin protein solution is 0.1% ~ 60%.
4. the preparation method of nanometer hydroxyapatite according to claim 1, is characterized in that: in described step (b), phosphoric acid salt is selected from (NH
4)
2hPO
4, H
3pO
4, Na
3pO
4, NaH
2pO
4, K
2hPO
4in one or more.
5. the preparation method of nanometer hydroxyapatite according to claim 1, is characterized in that: the reagent regulating aqueous phosphatic pH value in described step (b) is ammoniacal liquor or hydrochloric acid.
6. the preparation method of nanometer hydroxyapatite according to claim 1, is characterized in that: in described step (b), the still aging time is 0.5 ~ 30 day, and drying temperature is 20 ~ 120 DEG C, and time of drying is 1 ~ 72h.
7. the preparation method of nanometer hydroxyapatite according to claim 1, is characterized in that: in described step (b), the particle diameter of the hydroxyapatite of preparation is 10 ~ 500nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104211037B (en) * | 2014-08-07 | 2016-06-01 | 华中农业大学 | Phosvitin and polypeptide thereof is utilized to catalyze and synthesize the method for biomimetic material hydroxyapatite |
| CN106115644B (en) * | 2016-06-24 | 2017-12-01 | 张文凯 | A kind of preparation method of hydroxyapatite structure |
| CN106853961B (en) * | 2016-12-02 | 2019-04-16 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite nano line, nano wire assembling reticular structure and preparation method thereof |
| CN111603607B (en) * | 2020-05-21 | 2021-01-05 | 武汉理工大学 | Fibroin-calcium hydrogen phosphate compound obtained by induction with fibroin as template and preparation method thereof |
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