CN105129756A - Method for preparing sub-nanometer hydroxyapatite ultrafine-needles through low-temperature mineralization - Google Patents
Method for preparing sub-nanometer hydroxyapatite ultrafine-needles through low-temperature mineralization Download PDFInfo
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- CN105129756A CN105129756A CN201510605232.4A CN201510605232A CN105129756A CN 105129756 A CN105129756 A CN 105129756A CN 201510605232 A CN201510605232 A CN 201510605232A CN 105129756 A CN105129756 A CN 105129756A
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Abstract
The invention provides a mineralization preparing method for sub-nanometer ultrafine-needles having characteristics of hydroxyapatite. The method comprises steps as follows: a calcium salt solution and a phosphate aqueous solution are added to a mixed solution of oleic acid, ethyl alcohol and water, mineralization is performed at the temperature of 0-30 DEG C, and the pure sub-nanometer ultrafine-needles having characteristics of hydroxyapatite are obtained. The ultrafine-needles prepared with the method have the good self-assembly characteristic, can be applied to preparation of coating materials, and can also be applied to preparation of degradable biological tissue repair materials.
Description
Technical field
The present invention relates to a kind of mineralising preparation method with the ultra-fine pin of Ya Na meter of hydroxyapatite characteristic.
Background technology
Hydroxyapatite (Ca
10(OH)
2(PO
4)
6, HAp) and be naturally mineralizing of a kind of apatite calcium, there is excellent biocompatibility and biological activity, nanoscale and organic polymer can be self-assembled into the sclerous tissues such as vertebrate skeletal and tooth.
Current biomineralization method is a kind of method of the gentleest acquisition hydroxyapatite, and prepared product is widely used in biological organization material.But the product general size prepared of aqueous phase system is comparatively large, and pattern is irregular, constructing matrix material for the later stage, to there is organic inorganic materials conjugation low, the problems such as assembling intensity difference.The nanometer hydroxyapatite degree of crystallinity utilizing collosol and gel, hydrothermal method, calcination method to prepare is high, but degradation cycle is long relatively.In addition, the sub-nanostructure of the ultra-fine ultra micro of nanometer hydroxyapatite obtains, processing condition relative complex by introducing the method for a certain dimension growth of heterogeneous ion restriction intended particle usually, and circulation ratio is poor.
Summary of the invention
The object of this invention is to provide a kind of mineralising preparation method with the ultra-fine sub-nanoneedle of hydroxyapatite characteristic.
Implementation procedure of the present invention is as follows:
A kind of method preparing the ultra-fine pin of Subnano-class hydroxyapatite, it is in the mixed system of oleic acid and ethanol, add calcium saline solution and aqueous phosphatic, the volume ratio of final oleic acid, ethanol, water is (1 ~ 5): (5 ~ 10): (5 ~ 20), leave standstill 1 ~ 14 day at 0 DEG C ~ 30 DEG C, the pure ultra-fine pin of Subnano-class hydroxyapatite can be obtained.
Above-mentioned calcium salt is nitrocalcite; Phosphoric acid salt is selected from sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate; Calcium salt and phosphatic mol ratio are 1:1.67.
Above-mentioned end product uses hexanaphthene and ethanol repetitive scrubbing for several times, and hexanaphthene is washing composition, and ethanol is for helping precipitation agent.
The sub-nano level superfine pin diameter of above-mentioned preparation is 0.5 ~ 0.8nm, and length is 20 ~ 120nm.
The application in coated material or Biocomposite material prepared by the ultra-fine pin of Subnano-class hydroxyapatite prepared by aforesaid method.
The present invention is based on the mechanism of crude substance mineralising, use for reference in organism and there is lyophobic dust in sclerous tissues's soil boy structure, changing biomass mineralization body is in the past aqueous phase system, in mineralising reaction system, introduce lyophobic dust form hydrophilic and hydrophobic mixed system, obtain the ultra-fine sub-nanoneedle with hydroxyapatite characteristic.
Advantage of the present invention and positively effect: the present invention is based on biomineralization method, consider that in organism, hydroxyapatite soil boy structure is not only hydrophilic fluid environment, and also there is hydrophobic lipid organic substance in this environment simultaneously, therefore simulate this environmental pattern, changing biomineralization system is in the past the category of hydrophilic environments, establish the mixed system of a kind of simple oleic acid, second alcohol and water, carry out low temperature mineralising synthesizing hydroxylapatite superfine nano pin.Preparation method's cheaper starting materials of the present invention is easy to get, and cost is low, and synthesis technique is simple and easy to realize, constant product quality, and technique is amplified easily and reproduction performance is good; Sub-nano level superfine needle set prepared by present method has good self-assembly characteristic, can be used for the preparation of mould material, also can be used for the packing material of matrix material; Ultra-fine pin low-crystalline makes its degradability promote, and can be used for preparing the biological tissue such as artificial bone, bone cement repair materials, and improves the controlled degradation of target material.
Accompanying drawing explanation
Fig. 1 is the TEM figure of ultra-fine Subnano-class pin prepared by embodiment 1;
Fig. 2 is the EDS figure of ultra-fine sub-nanoneedle prepared by embodiment 1;
Fig. 3 is the infrared spectrogram of ultra-fine sub-nanoneedle prepared by embodiment 1;
Fig. 4 is the TEM figure of ultra-fine sub-nanoneedle prepared by embodiment 2;
Fig. 5 is the TEM figure of hydroxyapatite prepared by embodiment 5;
Fig. 6 is the TEM figure of the self-assembly of the ultra-fine sub-nanoneedle of hydroxyapatite prepared by embodiment 6;
Fig. 7 is the TEM figure of the self-assembly of the ultra-fine sub-nanoneedle of hydroxyapatite prepared by embodiment 6;
Fig. 8 is the SEM figure of the ultra-fine sub-nanoneedle biologic bracket material of hydroxyapatite prepared by embodiment 6.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method; Material used, reagent etc., if no special instructions, all can obtain from commercial channels.
embodiment 1the preparation of the ultra-fine pin of Subnano-class hydroxyapatite
In the beaker of 50mL, add 2mL oleic acid, 10mL ethanol, and then add the sodium radio-phosphate,P-32 solution 8mL of nitrocalcite 8mL and 0.15M of 0.25M, stir, sealing of hole film seals beaker mouth, in 25 DEG C of thermostat containers, leave standstill 7d.After reaction terminates, centrifugal collecting precipitation, and obtain end product for several times by hexanaphthene and washing with alcohol.
The product reacted by transmission electron microscope detection display is sub-nano level superfine pin, diameter about 0.5 ~ 0.8nm and be about 100nm, as shown in Figure 1; The ultra-fine pin of visible gained Ya Na meter is analyzed elementary composition identical with hydroxyapatite, as shown in Figure 2 through EDS; The infrared spectrogram of product meets the diffuse reflectance infrared spectroscopy of hydroxyapatite, as shown in Figure 3.
embodiment 2the preparation of the ultra-fine pin of Subnano-class hydroxyapatite
In the beaker of 50mL, add 2mL oleic acid, 10mL ethanol, and then add the ammonium phosphate solution 8mL of nitrocalcite 8mL and 0.15M of 0.25M, stir, sealing of hole film seals beaker mouth, in 4 DEG C of refrigerators, leave standstill 7d.After reaction terminates, centrifugal collecting precipitation, and obtain end product for several times by hexanaphthene and washing with alcohol.Detecting product by transmission electron microscope is sub-nano level superfine pin, and diameter is 0.5 ~ 0.8nm about, is about 25nm, as shown in Figure 4.
embodiment 3the preparation of the ultra-fine pin of Subnano-class hydroxyapatite
In the beaker of 50mL, add 4mL oleic acid, 10mL ethanol, and then add the sodium hydrogen phosphate solution 10mL of nitrocalcite 10mL and 0.15M of 0.25M, stir, sealing of hole film seals beaker mouth, in 4 DEG C of refrigerators, leave standstill 14d.After reaction terminates, centrifugal collecting precipitation, and obtain end product for several times by hexanaphthene and washing with alcohol.Detecting product by transmission electron microscope is sub-nano level superfine pin, and diameter is 0.5 ~ 0.8nm about, is about 60nm.
embodiment 4the preparation of the ultra-fine pin of Subnano-class hydroxyapatite
In the beaker of 250mL, add 20mL oleic acid, 40mL ethanol, and then add the sodium radio-phosphate,P-32 solution 30mL of nitrocalcite 30mL and 0.15M of 0.25M, stir, sealing of hole film seals beaker mouth, in 10 DEG C of thermostat containers, leave standstill 14d.After reaction terminates, centrifugal collecting precipitation, and obtain end product for several times by hexanaphthene and washing with alcohol.Detecting product by transmission electron microscope is sub-nano level superfine pin, and diameter is 0.5 ~ 0.8nm about, is about 80nm.
embodiment 5comparison example
Similar with example 1, difference is that mineralising system does not introduce hydrophobicity oleic acid, and introduces other wetting ability organic molecule.
In the beaker of 50mL, add the PEG10000 of 0.5g, 10mL ethanol, and then add the sodium radio-phosphate,P-32 solution 8mL of nitrocalcite 8mL and 0.15M of 0.25M, stir, sealing of hole film seals beaker mouth, in 25 DEG C of thermostat containers, leave standstill 7d.After reaction terminates, centrifugal collecting precipitation, and obtain end product for several times with ethanol and water washing.Detecting product by transmission electron microscope is irregular and rod, as shown in Figure 5.
embodiment 6the regulation and control of the self-assembly of the ultra-fine pin of sub-nanometer and film application
The ultra-fine pin of Ya Na meter prepared by example 1 is scattered in the mixed solution of hexanaphthene and ethanol makes stock liquid, carries out the dip-coating of matrix thing, can be wrapped by last layer phosphatic rock self-assembled film to improve the physico-chemical property of substrate material as prevented water logging lubricant nature corrosion etc.The assembling microstructure TEM being two kinds of self assembly method as Fig. 6 (alcohol dispersion liquid) and Fig. 7 (ethanol adds hexanaphthene dispersion liquid) schemes.
embodiment 7biological tissue's repair materials application of the ultra-fine pin of sub-nanometer
The first step, the hydrophilic and hydrophobic conversion of ultra-fine wire surface.Appropriate ultra-fine pin prepared by Example 1 is scattered in the hexanaphthene of 2ml, and joins and be dissolved with in the 10ml aqueous solution of 20mgPluronicF127, and then adds 6ml tetrahydrofuran (THF), after concussion mixing, obtains muddy suspension.Then removed the organic solvent in mixed solution by decompression rotary evaporation, then after washing unnecessary PluronicF127 with water, obtain wetting ability europium doped hydroxyapatite monocrystalline fluorescent nano particles;
Second step, is dissolved in 2g Human-like Collagen in 20g apirogen water, obtained 13.6% (w/v) HLC aqueous solution.Be that 1:4 (w/w) takes 8g and to wet ultra-fine pin by albumen and the ratio of ultra-fine pin, ultrasonic several minutes, make it become homogenate shape, then add appropriate above-mentioned protein solution wherein, concuss mixes.Above-mentioned obtained thick solution is proceeded in mould rapidly, and after the freezing lower freezing 4h of the Ultralow Temperature Freezer being placed in-80 DEG C, vacuum lyophilization 48h.After adopting the genipin solution of 0.1% to be cross-linked freeze-drying timbering material 48h at 37 DEG C, with apirogen water washing by soaking 1 day several times, and then put into Ultralow Temperature Freezer maintenance 4h, take out and to be put in vacuum freeze drier after dry 48h again, obtain degradable porous artificial bone supporting material finally, as shown in Figure 8.
Claims (5)
1. prepare the method for the ultra-fine pin of Subnano-class hydroxyapatite for one kind, it is characterized in that: in the mixed system of oleic acid and ethanol, add calcium saline solution and aqueous phosphatic, the volume ratio of final oleic acid, ethanol, water is (1 ~ 5): (5 ~ 10): (5 ~ 20), leave standstill 1 ~ 14 day at 0 DEG C ~ 30 DEG C, the pure ultra-fine pin of Subnano-class hydroxyapatite can be obtained.
2. method according to claim 1, is characterized in that: calcium salt is nitrocalcite; Phosphoric acid salt is selected from sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate; Calcium salt and phosphatic mol ratio are 1:1.67.
3. method according to claim 1, is characterized in that: use the end product that hexanaphthene and ethanol repetitive scrubbing obtain for several times, hexanaphthene is washing composition, and ethanol is for helping precipitation agent.
4. method according to claim 1, is characterized in that: the sub-nano level superfine pin diameter of preparation is 0.5 ~ 0.8nm, and length is 20 ~ 120nm.
5. the application in coated material or Biocomposite material prepared by the ultra-fine pin of Subnano-class hydroxyapatite that prepared by method described in claim 1.
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| CN110775953A (en) * | 2019-11-27 | 2020-02-11 | 中山市科信生物技术有限公司 | Method for synthesizing thermodynamically stable hydroxyapatite with microscopic kinetic reaction limitation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783217A (en) * | 1995-11-07 | 1998-07-21 | Etex Corporation | Low temperature calcium phosphate apatite and a method of its manufacture |
| CN101297978A (en) * | 2008-06-17 | 2008-11-05 | 东南大学 | Preparation method of hydroxyapatite nano pole |
| CN101723341A (en) * | 2009-11-06 | 2010-06-09 | 上海师范大学 | Preparation method of hydroxylapatite nano fibers or nano wires |
| CN102491300A (en) * | 2011-11-16 | 2012-06-13 | 陕西巨子生物技术有限公司 | Preparation method of amphiphilic monodisperse hydroxyapatite monocrystal nanorod |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783217A (en) * | 1995-11-07 | 1998-07-21 | Etex Corporation | Low temperature calcium phosphate apatite and a method of its manufacture |
| CN101297978A (en) * | 2008-06-17 | 2008-11-05 | 东南大学 | Preparation method of hydroxyapatite nano pole |
| CN101723341A (en) * | 2009-11-06 | 2010-06-09 | 上海师范大学 | Preparation method of hydroxylapatite nano fibers or nano wires |
| CN102491300A (en) * | 2011-11-16 | 2012-06-13 | 陕西巨子生物技术有限公司 | Preparation method of amphiphilic monodisperse hydroxyapatite monocrystal nanorod |
Non-Patent Citations (1)
| Title |
|---|
| JUNFENG HUI等: "Control synthesis and self-assembly of calcium apatite at low temperatures", 《CERAMICS INTERNATIONAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110775953A (en) * | 2019-11-27 | 2020-02-11 | 中山市科信生物技术有限公司 | Method for synthesizing thermodynamically stable hydroxyapatite with microscopic kinetic reaction limitation |
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