CN101757684A - Preparation and application of rod-like nanometer hydroxyapatite bone material - Google Patents
Preparation and application of rod-like nanometer hydroxyapatite bone material Download PDFInfo
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- CN101757684A CN101757684A CN200910113356A CN200910113356A CN101757684A CN 101757684 A CN101757684 A CN 101757684A CN 200910113356 A CN200910113356 A CN 200910113356A CN 200910113356 A CN200910113356 A CN 200910113356A CN 101757684 A CN101757684 A CN 101757684A
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Abstract
The invention relates to a preparation and an application of a rod-like nanometer hydroxyapatite bone material. The rod-like nanometer hydroxyapatite powder is formed by mixing the hartshorn of soluble calcium salt with the hartshorn of diammonium hydrogen phosphate, adding the mixture into a high-pressure reaction kettle, centrifugally separating, washing and drying. The acquired rod-like nanometer HA powder is injected into two moulds and is pressed into two base shapes at 15 to 20 MPa. The former is I-shaped and the latter is T-shaped. The height is 4.75mm; the top is of a round tray shape; the horizontal diameter of the tray is 3.0mm; the diameter of the pillaret is 1.17mm; the round tray bottom at the lower end is a cup-like concave side; the latter can be solid and hollow. The nanometer HA ceramic manual ossicle is formed by burning for 1 to 2 h at 900 to 1000 DEG C. The rod-like nanometer hydroxyapatite bone material of the invention has excellent biocompatibility, bone conductivity, plasticity and mechanical strength and is ideal bone repairing material for repairing the bone tissue.
Description
Technical field
The present invention relates to a kind of preparation and application thereof of rod-like nanometer hydroxyapatite bone material, belong to biologic inorganic material technology field.
Technical background
Hydroxyapatite (hydroxyapatite, chemical formula Ca (PO
4)
6(OH)
2, be called for short HA) very similar to the inorganic constituents of vertebrates bone, be most widely used a kind of biocompatibility pottery in the bone tissue engineer.Although hydroxyapatite and composite thereof have excellent biological compatibility, bone conductibility and plasticity, its bone inducing properties depends on the structure of finishing, processing technology improvement and the active component (as bone morphogenetic protein, osteoblast) of material to a great extent.
The nanotechnology that begin the eighties in 20th century has obtained breakthrough in the nineties, it has formed emerging frontier branch of science with combining of medical science---the nanometer medical treatment, the knowledge of promptly on molecular level, utilizing molecular tool and having grasped about human body, the medical diagnosis on disease of being engaged in, medical science, prevention, health care and improve health status etc.Because the particularity on the nanometer material structure, give the small-size effect and the surface/interface effect of nano material uniqueness, make it have significant difference with micro materials on performance, the excellent properties that nano material showed has tempting application prospect in field of tissue engineering technology.The HA nanoparticle of synthetic in medically application more and more widely can be used for the research of aspects such as pharmaceutical carrier and antitumor.Experimentation shows, the HA nanoparticle has in various degree inhibitory action to the growth of multiple cancerous cell such as hepatocarcinoma, gastric cancer, osteosarcoma.If nano-particle is pressed into biomaterial, this material also has targeting and extensibility to a certain degree preferably.
Nanometer HA pottery also can overcome pore and the crackle that exists in the conventional ceramic, makes material be difficult for causing transgranular fracture, and its intensity, hardness, toughness and plasticity also are improved simultaneously.One of main factor of decision nanometer HA ceramic machinery performance is the quality of HA powder quality.About the existing patent report of the preparation method of nanometer HA, for example the Chinese invention patent application number 02160058.9, and publication number CN1429538A discloses the preparation method of a kind of nanometer HA, this method is an additive with citric acid, polyacrylic acid or L-glutamic acid, by Ca (OH)
2With Ca (H
2PO
4)
2H
2The O reaction makes; Chinese invention patent application number 200710067822.1, publication number CN101032630A discloses the preparation method of a kind of hollow shape nanometer HA, this method is a template with cetyl trimethyl ammonium bromide (CTAB), under certain reaction temperature and ultrasound environments, calcium salt soln is added drop-wise in the solution that contains phosphate radical and CTAB, by the pH value of ammonia regulator solution, the gained suspension after filtration, washing, low-temperature vacuum drying obtain target product; Chinese invention patent application number 200710107226.1, publication number CN101058416A discloses a kind of preparation method of ordered nano HA polycrystal powder, under alkali condition, the dodecyl sodium sulfate ethanol water by containing lime nitrate and the ethanol water of Ammonium biphosphate or Ammonium biphosphate obtain target product through back flow reaction.
Above-mentioned preparation method all can successfully be prepared nanometer HA, but these methods need usually the certain surfactant of additive or other additive control size and, reaction will be removed these surfactants or other additive after finishing.The present invention mixes the ammonia spirit of soluble calcium salt with the ammonia spirit of diammonium phosphate, reactant mixture need not surfactant or other additive just can be evenly distributed, not have the rod-like nano HA of reunion under hydrothermal condition, and with the repressed one-tenth sintering formation of rod-like nano HA nano ceramics, this nano ceramics is nontoxic, has the favorable tissue compatibility, can be used as the main body of bone reparation, substitution material and the organizational project bone repair material of sclerous tissues, therefore have broad application prospects.
Summary of the invention
One of purpose of the present invention provides that a kind of preparation method is simple, cost is low, the preparation method of good reproducibility, workable rod-like nanometer hydroxyapatite bone material.
Another object of the present invention be above-mentioned generation bone material be applied in the clinical bone tissue restoration.
For achieving the above object, the technical solution adopted in the present invention comprises the steps:
The first step, press Ca: P=1.67: 1 mol ratio, take by weighing soluble calcium salt and diammonium phosphate, use the ammonia solvent of 0.1-0.2mol/L respectively, ammonia spirit with soluble calcium salt under stirring at normal temperature is added drop-wise in the ammonia spirit of diammonium phosphate, obtains white depositions after fully stirring.
Second step, the reactant mixture that obtains in the first step has been joined in the teflon-lined autoclave, taking out behind the constant temperature 18-24h under the 130-160 ℃ of condition, with reactant mixture centrifugalize, washing, drying, can obtain diameter is 20nm-30nm, and length is the rod-like nano HA powder body of 50nm-150nm.Fig. 1 is the XRD figure of hydro-thermal method products therefrom, with standard spectrogram contrast (JCPDS Card No 09-0432) as can be known this method can obtain the hydroxyapatite of pure phase.Fig. 2 is the TEM photo of products therefrom, and hydrothermal condition can make the bar-shaped hydroxyapatite of favorable dispersibility down as seen from the figure, and its diameter is 20nm-30nm, and length is 50nm-150nm.
The 3rd step poured into the rod-like nano HA powder body that obtains in 2 kinds of moulds, was pressed into two kinds of shapes the most basic under 15-20MPa, partial ossicular replacement prosthesis (PORP) and the complete counterfeit service of ossicular chain (TORP).The former is " I " type, and high 4.75 millimeters are not waited, and pushes up to be disc, and dish is horizontal, and little column diameter is 1.17 millimeters through being 3.0 millimeters, and following end disc ground is the cup-shaped concave surface, so that original head of stapes joins; The latter is T-shape, and post is high 4.75 millimeters, pushes up to be disc, and dish is horizontal in being 3.0 millimeters, and little column diameter is 1.17 millimeters, so that contact with stapes footplate.The latter divides two kinds again: solid and hollow.At 900-1000 ℃ of calcining 1-2h, form nanometer HA pottery artificial auditory ossicle (Fig. 3).
In the 4th step, 30 of healthy adult Cavia porcelluss (60 ear) are divided into 6 groups at random, 5 every group.Intraperitoneal injection of anesthesia, ear rear portion depilation, pathway behind the descending ear of aseptic condition separates and seeks auditory meatus,external,bony, and outer wall separates periosteum downwards to the belemnoid spline structure behind the auditory meatus,external,bony.Careful cleaning shows soft tissue, and electric drill is being the center with sclerotin in the middle of the belemnoid spline structure, and diameter is 15mm, does a bone lid, opens the bone lid and promptly enters otic capsule.Open gas room on the bilateral otic capsule, insert nanometer HA pottery ear bones piece in the left and right sides.The bone hole is closed with the bone cap seal, sews up the incision.After raising for 1～16 week, put to death 5 respectively at postoperative 4,8,16, broken end is got bilateral Cavia porcellus otic capsule (10), and row implant surface and contact edge general form are learned and the scanning electron microscope inspection.
The result: the animal about 2h after anesthesia that all performs the operation revives no obvious adverse reaction.The postoperative non-incision infects, and in 2 weeks of postoperative, the operative incision healing is good, and is good to audio response, and it is complete that endotoscpe is observed tympanum, do not have congested and perforation.
General form is learned good, and implant cavity does not have infections, oozes out, adhesion, fibrosis, smooth mucosal, complete, and implant does not have and repels to deviate from, and form is good, sharpness of border, good colour, structural integrity, no granulation formation.Each stage of postoperative listen bone material all to keep implanting the time the position, no cracked, do not have displacement, touch fixing, surrounding soft tissue is no abnormal.
Visible ceramic surface lining of 4 weeks of postoperative thin layer fibrous connective tissue, and see have fibrous tissue to stretch into the ceramic mesh from the surface, implanting pottery combines closely with osseous tissue, and there is the small amount of bone tissue form at its edge, newborn osseous tissue and pottery are direct synostosis, and no fiber tunica is separated (Fig. 4).Postoperative 8 all freshman bone tissues showed increased, and stretch into ceramic material inside, become the island shape to substitute embedded material (Fig. 5) gradually.16 weeks of postoperative are new life's bone trabecula (Fig. 6) as seen.
The Cavia porcellus otic capsule is implanted into nanometer HA pottery artificial auditory ossicle, and implant cavity does not have infections, oozes out, adhesion, fibrosis, and mucosa is smooth, complete, and implant does not have repulsion to be deviate from, and form is good, sharpness of border, good colour, structural integrity.16 weeks of scanning electron microscope postoperative have a large amount of fibrous tissue to hold, and no inflammatory cell has new bone formation.After nanoporous HA implants, soft or hard is at the interface organized in the hole of all growing into, be formed the state of fibrous tissue and freshman bone tissue's cross coupled, this interface can keep normal metabolism relation, and has the bonded characteristics of physiological.
Pass through the foregoing description, one kind of rod-like nano HA is nontoxic, nonirritant, have the biomaterial of good organization's compatibility, can induce new bone formation at the bone wound surface, osseous tissue is directly grows into, middle no transition zone, and increase dark more that new bone tissue climbs in time in material, and the osseous tissue of newly growing into is woven into net mutually, improved the bond strength of material itself and material and osseous tissue interface, newborn bone trabecula also can require reconstruction gradually according to mechanics.Therefore, this material is a kind of comparatively ideal ear bones prosthesis.
The present invention, realized two purposes of design invention, and compared with prior art had following major advantage and beneficial effect:
1. preparation method is simple, and is easy to operate, need not surfactant and other additive, and the soluble calcium salt and the diammonium phosphate of employing are cheap and easy to get.
2. even by the resulting rod-like nano HA of the inventive method particle size distribution, no agglomeration,
3. the nanometer HA pottery of compacting sintering has higher intensity, and characteristics such as favorable mechanical bearing capacity, plasticity is strong, histocompatibility is good are arranged, during the reconstruction that can be used for sclerous tissues's defective at many positions is repaired,
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is further described.
Fig. 1 sends out rod-like nano HA bone synthetic for the X-ray powder diffraction figure of material for the present invention utilizes hydro-thermal;
Fig. 2 sends out rod-like nano HA bone synthetic for the transmission electron microscope photo (TEM) of material for the present invention utilizes hydro-thermal;
Fig. 3 is the enlarged photograph of nanometer HA bone of the present invention for material
Fig. 4 is the surface sweeping electromicroscopic photograph (SEM) in 4 weeks of postoperative;
Fig. 5 is the surface sweeping electromicroscopic photograph (SEM) in 8 weeks of postoperative;
Fig. 6 is the surface sweeping electromicroscopic photograph (SEM) in 16 weeks of postoperative;
Claims (4)
1. rod-like nanometer hydroxyapatite bone material, it is characterized in that: the diameter of described rod-like nano hydroxyapatite is 20nm-30nm, length is 50nm-150nm.
2. the preparation method of according to claim a kind of rod-like nano hydroxyapatite, its feature comprises the steps:
(1) presses Ca: P=1.67: 1 mol ratio, take by weighing soluble calcium salt and diammonium phosphate, use the ammonia solvent of 0.1-0.2mol/L respectively, the ammonia spirit with soluble calcium salt under stirring at normal temperature is added drop-wise in the ammonia spirit of diammonium phosphate, obtains white depositions after fully stirring;
(2) reactant mixture that obtains in the previous step has been joined in the teflon-lined autoclave,,, can obtain rod-like nano HA powder body reactant mixture centrifugalize, washing, drying taking out behind the constant temperature 18-24h under the 130-160 ℃ of condition.
3. the application of rod-like nano hydroxyapatite in bone tissue restoration is characterized in that rod-like nano hydroxy-apatite compacting sintering is become nano ceramics.
4. according to claim 3, the preparation method of hydroxyapatite nano pottery comprises the steps:
Artificial auditory ossicle plastotype: the rod-like nano HA powder body that obtains is poured in 2 kinds of moulds, under 15-20MPa, be pressed into two kinds of shapes the most basic, partial ossicular replacement prosthesis (PORP) and the complete counterfeit service of ossicular chain (TORP).The former is " I " type, and high 4.75 millimeters are not waited, and pushes up to be disc, and dish is horizontal, and little column diameter is 1.17 millimeters through being 3.0 millimeters, and following end disc ground is the cup-shaped concave surface, so that original head of stapes joins; The latter is T-shape, and post is high 4.75 millimeters, pushes up to be disc, and dish is horizontal in being 3.0 millimeters, and little column diameter is 1.17 millimeters, so that contact with stapes footplate.The latter divides two kinds again: solid and hollow.At 900-1000 ℃ of calcining 1-2h, form nanometer HA pottery artificial auditory ossicle.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431986A (en) * | 2011-10-08 | 2012-05-02 | 山东大学 | Method for preparing hydroxyapatite nano fiber |
| CN102616762A (en) * | 2011-02-01 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN103342555A (en) * | 2013-07-05 | 2013-10-09 | 北京北达燕园微构分析测试中心有限公司 | Strontium magnesium-doped nano-hydroxyapatite and preparation method thereof |
| CN103539093A (en) * | 2013-09-16 | 2014-01-29 | 浙江理工大学 | Rapid preparation method of rod-like nano-hydroxyapatite |
| CN106115642A (en) * | 2016-06-24 | 2016-11-16 | 山东大学 | A kind of large scale hydroxyapatite porous microsphere material and preparation method thereof |
| CN106672933A (en) * | 2016-12-02 | 2017-05-17 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite super-long nanowire-based macro-scale ordered structure material and preparation method thereof |
| CN110512249A (en) * | 2018-05-22 | 2019-11-29 | 南京理工大学 | The preparation method of titanium carbonitride and carboxy apatite composite coating |
| CN112978695A (en) * | 2021-03-16 | 2021-06-18 | 华东理工大学 | Preparation method of bionic hydroxyapatite nanoparticles with high osteogenic activity |
| CN113797395A (en) * | 2021-09-17 | 2021-12-17 | 北京爱康宜诚医疗器材有限公司 | Nano hydroxyapatite/block copolymer composite material and preparation method thereof |
| CN113968577A (en) * | 2021-11-30 | 2022-01-25 | 西安理工大学 | Method for preparing hydroxyapatite nanorod by using egg white template |
-
2009
- 2009-06-05 CN CN200910113356A patent/CN101757684A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616762A (en) * | 2011-02-01 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN102616762B (en) * | 2011-02-01 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN102431986A (en) * | 2011-10-08 | 2012-05-02 | 山东大学 | Method for preparing hydroxyapatite nano fiber |
| CN103342555A (en) * | 2013-07-05 | 2013-10-09 | 北京北达燕园微构分析测试中心有限公司 | Strontium magnesium-doped nano-hydroxyapatite and preparation method thereof |
| CN103539093A (en) * | 2013-09-16 | 2014-01-29 | 浙江理工大学 | Rapid preparation method of rod-like nano-hydroxyapatite |
| CN103539093B (en) * | 2013-09-16 | 2015-03-11 | 浙江理工大学 | Rapid preparation method of rod-like nano-hydroxyapatite |
| CN106115642B (en) * | 2016-06-24 | 2018-04-24 | 山东大学 | A kind of large scale hydroxyapatite porous microsphere material and preparation method thereof |
| CN106115642A (en) * | 2016-06-24 | 2016-11-16 | 山东大学 | A kind of large scale hydroxyapatite porous microsphere material and preparation method thereof |
| CN106672933A (en) * | 2016-12-02 | 2017-05-17 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite super-long nanowire-based macro-scale ordered structure material and preparation method thereof |
| CN106672933B (en) * | 2016-12-02 | 2019-01-08 | 中国科学院上海硅酸盐研究所 | The preparation method of hydroxyapatite overlong nanowire macro-scale ordered structural material |
| CN110512249A (en) * | 2018-05-22 | 2019-11-29 | 南京理工大学 | The preparation method of titanium carbonitride and carboxy apatite composite coating |
| CN110512249B (en) * | 2018-05-22 | 2021-04-27 | 南京理工大学 | Preparation method of titanium carbonitride and hydroxyapatite composite coating |
| CN112978695A (en) * | 2021-03-16 | 2021-06-18 | 华东理工大学 | Preparation method of bionic hydroxyapatite nanoparticles with high osteogenic activity |
| CN113797395A (en) * | 2021-09-17 | 2021-12-17 | 北京爱康宜诚医疗器材有限公司 | Nano hydroxyapatite/block copolymer composite material and preparation method thereof |
| CN113797395B (en) * | 2021-09-17 | 2023-02-21 | 北京爱康宜诚医疗器材有限公司 | Nano hydroxyapatite/block copolymer composite material and preparation method thereof |
| CN113968577A (en) * | 2021-11-30 | 2022-01-25 | 西安理工大学 | Method for preparing hydroxyapatite nanorod by using egg white template |
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Application publication date: 20100630 |