CN101422632A - Preparation method of hydroxyapatite/sodium alginate nano composite material - Google Patents
Preparation method of hydroxyapatite/sodium alginate nano composite material Download PDFInfo
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- CN101422632A CN101422632A CNA2007101500264A CN200710150026A CN101422632A CN 101422632 A CN101422632 A CN 101422632A CN A2007101500264 A CNA2007101500264 A CN A2007101500264A CN 200710150026 A CN200710150026 A CN 200710150026A CN 101422632 A CN101422632 A CN 101422632A
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Abstract
The invention relates to a preparation method of a hydroxylapatite/sodium alginate nanometer composite material, which mixes calcium hydroxide and phosphoric acid water solution according to the chemical stoichiometric ratio of Ca/P in the hydroxylapatite and carries out the in-situ composite reaction with sodium alginate water gel, and a three dimensional net shaped structure similar to a natural bone is formed by adding calcium chloride to realize the intercrossing reaction with the sodium alginate. The method has the advantages that: the hydroxylapatite/sodium alginate nanometer composite material maintains the good biological compatibility, biological activity and bone conductibility of HA; the combination of the sodium alginate as an organic substrate with the HA can bestow the HA good processing and forming property, thus effectively inhabiting the moving of HA particles from the transplanting parts; and the sodium alginate has rich source and low price, and the preparation process can be operated at normal temperature and pressure, and has simple operation and low cost, and is an ideal bone repairing substitute materials of the new generation.
Description
(1) technical field
The present invention relates to bone and repair the preparation method of technical field of biomedical materials, particularly a kind of hydroxyapatite/sodium alginate nano composite material.
(2) background technology
Hydroxyapatite (Hydroxyapatite is called for short HA), its molecular formula is Ca
10(PO
4)
6(OH)
2, be the main inorganic composition that constitutes skeleton tissue and tooth.This material have excellent biological compatibility and, nontoxic and do not have immunological rejection, can form firm chemical bond with body osseous tissue on every side after implanting and combine, and can induce growing of new bone, be that a kind of ideal human body hard tissue is repaired substitution material.But single HA material mechanical performance is relatively poor, and is big as fragility, machine-shaping is difficult, the HA particle from transplantation site migration etc. takes place easily, and these shortcomings have limited its application in carrying position bone is replaced to a great extent.Therefore the composition of natural imitation bone and architectural feature and the bone renovating material of synthetic, become one of research focus of current biomedical material, wherein the HA/ natural biological polymer composite of Bionic Design can satisfy the clinical medicine requirement aspect biological reactivity and the mechanical property, and currently used natural polymer mainly contains ossein, gelatin, chitosan, alginate, fibroin, chondroitin sulfate etc.
Alginate are a kind of natural polyanionic polysaccharides that extract from brown Sargassum, belong to the linear polymeric class.Alginate have stronger cohesive, plasticity and efficient anastalsis, in physiological environment, have good hydrophilicity, biocompatibility and biological degradability, be widely used in medical fields such as wound covering, tooth section die, medicine transmission, cell fixation and organizational project.The compound fragility that can obviously improve HA of HA and alginate improves its toughness and machine-shaping property, can also suppress the migration of HA particle from transplantation site effectively.
People such as Maruyama are with HA powder and the direct blend of sodium alginate (J Biomed Mater Res1995,29:329～336), the composite that obtains has good bone conductibility, can form bone between implantation body and cortical bone and be connected, and not bring out any bad living precursor reactant; People such as Ribeiro adopt the drop extrusion molding to prepare the spherical composite particles (Biomaterials 2004,25:4363～4373) of HA/ sodium alginate of uniform size; It is the HA/ sodium alginate spheroidal particle (JBiomed Mater Res 2003,65:222～228) of 15 μ m that people such as Sivakumar adopt the dispersin polymerization technology to prepare average-size; Human phase separation methods such as Lin have prepared a series of sodium alginates/HA composite porous support material, and HA enters mechanical property and the cell adhesion (J Biomed Mater Res 2004,71:52～65) that has improved compound rest in the sodium alginate hydrogel.
Above-mentioned these preparation methoies are HA microgranule and sodium alginate mechanical mixture by a certain percentage basically, the composite that obtains like this, the HA microgranule is difficult to reach homodisperse in sodium alginate substrate, chemical bonding effect for want of between the two and a little less than causing inorganic and organic facies interface binding power, be difficult to form the multilevel hierarchy similar to natural bone, its mechanical property does not reach the requirement of human loaded bone.Therefore, realize nanoparticle homodisperse in organic polymer substrate, thereby formed, structure, to give birth to body activity and mechanical property be the research emphasis in present bone tissue engineer field near the HA base Biocomposite material of natural bone.
(3) summary of the invention
The objective of the invention is problem at above-mentioned existence, a kind of method for preparing hydroxyapatite/sodium alginate nano composite material is provided, realize nanoparticle homodisperse in organic polymer substrate, thereby formed, structure, give birth to body activity and mechanical property hydroxyapatite/sodium alginate nano composite material near natural bone.
Technical scheme of the present invention:
A kind of preparation method of hydroxyapatite/sodium alginate nano composite material, it is characterized in that: the stoichiometric proportion of calcium hydroxide and phosphate aqueous solution being pressed Ca/P in the hydroxyapatite is mixed, and carry out the original position compound reaction with the sodium alginate hydrogel that mixes, utilize the regulating and controlling effect of sodium alginate organic formwork to crystalline nucleation of HA and growth, reduce the particulate spontaneous reunion degree of nanometer HA, in organic substrate, reach the homodisperse of nanoscale to guarantee HA; Realize and the cross-linking reaction of sodium alginate that by adding calcium chloride inorganic to strengthen-the organic interface adhesion, promotion HA and sodium alginate organic substrate form firm chemical bond, form the tridimensional network similar to nature bone.
Concrete preparation process is as follows:
1) be 4～8% calcium hydroxide suspension with weight percent concentration with weight percent concentration be that 3～4% sodium alginate hydrogel mixes and stirs;
2) under above-mentioned mixed liquor stirring, the dropping weight percent concentration is 6～9% phosphoric acid solution, and continuous stirring was reacted 5～6 hours under room temperature, normal pressure;
3) adding concentration then is 0.01～1.0mol/L calcium chloride solution, does not stop to stir at least 30 minutes to carry out cross-linking reaction;
4) gelatinous mixture after crosslinked was at room temperature left standstill heavyization 20～24 hours;
5) the precipitate deionized water rinsing that centrifugalize is obtained repeats 3 times at least;
6) the oven dry back grind into powder in temperature is 50～80 ℃ vacuum drying oven of the precipitate after will washing gets final product.
Advantage of the present invention is: the hydroxyapatite/sodium alginate nano composite material of the present invention's preparation, and its main component is hydroxyapatite (HA), has kept the inherent excellent biological compatibility of HA, biological activity and bone conductibility; Sodium alginate is compound as organic substrate and HA's, has improved the biodegradation absorption function of HA, gives HA good machine-shaping property, can effectively suppress the migration of HA particle from transplantation site; The sodium alginate source is abundant and cheap, preparation technology implements under room temperature, condition of normal pressure, thus easy to operate, so hydroxyapatite/sodium alginate nano composite material not only has good biological characteristics and plastotype, and cost is low, is that ideal bone of new generation is repaired substitution material.
(4) specific embodiment
Embodiment:
1) take by weighing the 5.16g calcium hydroxide, add deionized water 65g, the preparation weight percent concentration is 7.4% calcium hydroxide suspension; Take by weighing 4.82g 85wt% phosphoric acid, add deionized water 50ml, the preparation weight percent concentration is 7.6% phosphoric acid solution;
2) take by weighing the 3.00g sodium alginate, add the 77g deionized water, magnetic agitation 1h is mixed with weight percent concentration and is 3.8% sodium alginate hydrogel;
3) the sodium alginate hydrogel of under electronic stirring condition (2) being prepared dropwise joins the Ca (OH) of (1) preparation
2In the suspension;
4) phosphoric acid solution of under electronic stirring condition (1) being prepared slowly is added drop-wise in the mixed liquor of (3) gained, and the continuous stirring reaction is 6 hours under room temperature, normal pressure;
5) dropwise adding concentration in the mixture that (4) obtain is that 0.1mol/L calcium chloride solution 10ml is crosslinked with sodium alginate wherein, continues to stir 30 fens;
6) mixture that (5) are obtained at room temperature leaves standstill 24h, deionized water rinsing is also used in centrifugalize then, so hocket 3 times, precipitation put under 50 ℃ of drying baker take out behind the vacuum drying 48h, use the agate mortar grind into powder, can obtain hydroxyapatite/sodium alginate nano composite material of the present invention, wherein the mass ratio of hydroxyapatite and sodium alginate is 70:30.
With prepared hydroxyapatite/sodium alginate nano composite material, observe by transmission electron microscope, transmission electron microscope photo shows: HA is that 20～50nm is long, the wide rhabdolith of 5～10nm, and they are distributed in the organic substrate along c axle oriented growth and self assembly gathering cluster; Observe by scanning electron microscope, stereoscan photograph shows: hydroxyapatite/sodium alginate presents continuously, microstructure uniformly, wherein the HA nanoparticle is assembled in the cluster embedding sodium alginate substrate that forms, sodium alginate organic substrate and HA nanoparticle merge fully, in composite, made up comparatively ideal tridimensional network, comparatively approaching with the multi-polar structure of natural bone.
Claims (1)
- A kind of preparation method of hydroxyapatite/sodium alginate nano composite material, it is characterized in that: the stoichiometric proportion of calcium hydroxide and phosphate aqueous solution being pressed Ca/P in the hydroxyapatite is mixed, and carry out the original position compound reaction with the sodium alginate hydrogel that mixes, utilize the regulating and controlling effect of sodium alginate organic formwork to crystalline nucleation of HA and growth, reduce the particulate spontaneous reunion degree of nanometer HA, to guarantee that HA reaches the homodisperse of nanoscale in organic substrate, calcium chloride is realized and the cross-linking reaction of sodium alginate by adding, inorganic to strengthen-the organic interface adhesion, promote HA and sodium alginate organic substrate to form firm chemical bond, form the nano composite material with generation of the tridimensional network similar to nature bone; Concrete preparation process is as follows:1) be that 4～8% calcium hydroxide suspension mixes with the sodium alginate hydrogel of weight percent concentration 3～4% and stirs with weight percent concentration;2) under above-mentioned mixed liquor stirring, the dropping weight percent concentration is 6～9% phosphoric acid solution, and continuous stirring was reacted 5～6 hours under room temperature, normal pressure;3) adding concentration then is 0.01～1.0mol/L calcium chloride solution, does not stop to stir at least 30 minutes to carry out cross-linking reaction;4) gelatinous mixture after crosslinked was at room temperature left standstill heavyization 20～24 hours;5) the precipitate deionized water rinsing that centrifugalize is obtained repeats 3 times at least;6) the oven dry back grind into powder in temperature is 50～80 ℃ vacuum drying oven of the precipitate after will washing gets final product.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905036A (en) * | 2009-06-04 | 2010-12-08 | 佳木斯大学 | Novel hydroxyapatite/SiOC biological ceramic composite material and preparation method thereof |
| WO2011035573A1 (en) * | 2009-09-28 | 2011-03-31 | 暨南大学 | Nanometer hydroxyapatite / natural polymer composite material, preparation method and use thereof |
| CN102247820A (en) * | 2011-07-06 | 2011-11-23 | 大连工业大学 | Fibrillar heavy metal ion adsorbent as well as preparation method and application thereof |
| CN103083728A (en) * | 2013-01-25 | 2013-05-08 | 四川大学 | Hydroxylapatite-polyphenol composite nanometer material and preparation method thereof |
| CN104117341A (en) * | 2014-08-15 | 2014-10-29 | 武汉理工大学 | Nano-hydroxyapatite/sodium alginate composite material, preparation method and application of nano-hydroxyapatite/sodium alginate composite material |
| CN104548211A (en) * | 2014-12-19 | 2015-04-29 | 戴立军 | Orthopedics or dental filling material, dental implant and degradable artificial bone |
| CN104958766A (en) * | 2015-06-03 | 2015-10-07 | 四川大学 | Sodium alginate-hydroxyapatite hybridization nano particle and preparing method thereof |
| CN108030957A (en) * | 2017-12-29 | 2018-05-15 | 成都新柯力化工科技有限公司 | A kind of gel rubber material and preparation method and application for 3D printing artificial cartilage |
| CN108785741A (en) * | 2018-06-22 | 2018-11-13 | 苏州市贝克生物科技有限公司 | Bone defect graphene packing material |
| CN109758615A (en) * | 2019-02-13 | 2019-05-17 | 四川大学 | A kind of two-sided composite hydrogel and preparation method thereof |
| CN111195372A (en) * | 2020-01-16 | 2020-05-26 | 北京诺康达医药科技股份有限公司 | Porous bone repair material and preparation method thereof |
| 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 |
| CN111388751A (en) * | 2020-03-03 | 2020-07-10 | 上海亚朋生物技术有限公司 | Composite bone cement and preparation method and application thereof |
| CN112646228A (en) * | 2020-12-21 | 2021-04-13 | 嘉兴学院 | Tannin crosslinked chitosan/gelatin liquid-absorbing hemostatic antibacterial sponge and preparation method thereof |
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2007
- 2007-11-01 CN CNA2007101500264A patent/CN101422632A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905036A (en) * | 2009-06-04 | 2010-12-08 | 佳木斯大学 | Novel hydroxyapatite/SiOC biological ceramic composite material and preparation method thereof |
| WO2011035573A1 (en) * | 2009-09-28 | 2011-03-31 | 暨南大学 | Nanometer hydroxyapatite / natural polymer composite material, preparation method and use thereof |
| CN102247820A (en) * | 2011-07-06 | 2011-11-23 | 大连工业大学 | Fibrillar heavy metal ion adsorbent as well as preparation method and application thereof |
| CN102247820B (en) * | 2011-07-06 | 2013-04-03 | 大连工业大学 | Fibrillar heavy metal ion adsorbent as well as preparation method and application thereof |
| CN103083728A (en) * | 2013-01-25 | 2013-05-08 | 四川大学 | Hydroxylapatite-polyphenol composite nanometer material and preparation method thereof |
| CN103083728B (en) * | 2013-01-25 | 2014-11-26 | 四川大学 | Hydroxylapatite-polyphenol composite nanometer material and preparation method thereof |
| CN104117341A (en) * | 2014-08-15 | 2014-10-29 | 武汉理工大学 | Nano-hydroxyapatite/sodium alginate composite material, preparation method and application of nano-hydroxyapatite/sodium alginate composite material |
| CN104117341B (en) * | 2014-08-15 | 2016-06-01 | 武汉理工大学 | Nanometer hydroxyapatite/sodium alginate matrix material and its preparation method and application |
| CN104548211A (en) * | 2014-12-19 | 2015-04-29 | 戴立军 | Orthopedics or dental filling material, dental implant and degradable artificial bone |
| CN104958766B (en) * | 2015-06-03 | 2018-05-25 | 四川大学 | Sodium alginate-hydroxyapatite hybridized nano-particle and preparation method thereof |
| CN104958766A (en) * | 2015-06-03 | 2015-10-07 | 四川大学 | Sodium alginate-hydroxyapatite hybridization nano particle and preparing method thereof |
| CN108030957A (en) * | 2017-12-29 | 2018-05-15 | 成都新柯力化工科技有限公司 | A kind of gel rubber material and preparation method and application for 3D printing artificial cartilage |
| CN108785741A (en) * | 2018-06-22 | 2018-11-13 | 苏州市贝克生物科技有限公司 | Bone defect graphene packing material |
| 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 |
| CN109758615A (en) * | 2019-02-13 | 2019-05-17 | 四川大学 | A kind of two-sided composite hydrogel and preparation method thereof |
| CN109758615B (en) * | 2019-02-13 | 2021-05-25 | 四川大学 | Double-sided composite hydrogel and preparation method thereof |
| CN111195372A (en) * | 2020-01-16 | 2020-05-26 | 北京诺康达医药科技股份有限公司 | Porous bone repair material and preparation method thereof |
| CN111195372B (en) * | 2020-01-16 | 2021-07-23 | 北京诺康达医药科技股份有限公司 | Porous bone repair material and preparation method thereof |
| CN111388751A (en) * | 2020-03-03 | 2020-07-10 | 上海亚朋生物技术有限公司 | Composite bone cement and preparation method and application thereof |
| CN112646228A (en) * | 2020-12-21 | 2021-04-13 | 嘉兴学院 | Tannin crosslinked chitosan/gelatin liquid-absorbing hemostatic antibacterial sponge and preparation method thereof |
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