CN102861356A - Bone repairing material and preparation method thereof - Google Patents

Bone repairing material and preparation method thereof Download PDF

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Publication number
CN102861356A
CN102861356A CN2012103995686A CN201210399568A CN102861356A CN 102861356 A CN102861356 A CN 102861356A CN 2012103995686 A CN2012103995686 A CN 2012103995686A CN 201210399568 A CN201210399568 A CN 201210399568A CN 102861356 A CN102861356 A CN 102861356A
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China
Prior art keywords
gelatin
phosphoric acid
solution
gelatin solution
renovating material
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CN2012103995686A
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Chinese (zh)
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刘斌
姚义俊
沈国柱
吴红艳
苏义
盛群
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Nanjing University of Information Science and Technology
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Nanjing University of Information Science and Technology
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Priority to CN2012103995686A priority Critical patent/CN102861356A/en
Publication of CN102861356A publication Critical patent/CN102861356A/en
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Abstract

The invention discloses a bone repairing material and a preparation method thereof. According to the bone repairing material, calcium hydroxide and a phosphoric acid are used as raw materials, a gelatin solution is used as a reaction mother liquor, a white suspension is formed in a self-assembly mode by a neutralization method, the centrifugal separation is performed to generate precipitation, and the precipitation is subjected to freeze drying and ground to obtain the bone repairing material. The obtained bone repairing material has good biocompatibility and biological activity.

Description

A kind of bone renovating material and preparation method thereof
Technical field
The invention belongs to the bio-medical material technical field, be specifically related to a kind of nano double calcium phosphate phase/gelatin bone renovating material and preparation method thereof.
Background technology
The development of bone renovating material is the direction that the large quantities of scientists of biomedical engineering field make great efforts always.What the bone renovating material effect that reality is used in the operation now was best is from body bone and allograph bone.But from body bone limited amount, and the danger that allograph bone has immunologic rejection and catches.People developed by metal, pottery, macromolecule with and the multiple bone renovating material made of composite.But these materials respectively have deficiency, in clinical, do not have any can with compare favourably from body bone or allograph bone.
Consider that biological superiority from body bone and allograph bone is that mainly their structure and composition and natural bone are identical.From the composition of material, hydroxyapatite (Ca 5(PO 4) 3(OH), HA) mutually and collagen be undoubtedly the best composition of complex.Because HA has similar chemical constitution to the mineralogical composition of natural bone, have good biological activity and osteoinductive; Collagen then is a kind of bioactive natural polymer that has, and has the ligand of being combined with recipient cell, and susceptibility and natural plasticity that cell triggers protein degradation are good.But as bone renovating material, all there is the defective on the performance in they.At first synthetic HA generally believes it is nondegradable, even nanoscale can accelerate the degraded of HA, but its degradation rate is still very low.And all be to use the HA of high temperature sintering as mineral constituent in great majority research, can not bring into play the good biological property of HA.Secondly collagen exists the source limited mainly from human body or animal, and the problems such as propagation of immunogenicity and pathogen make it be difficult to obtain follow-up development.From combination, present composite is a kind of simple physical mixture between calcium phosphate and the polymer mainly take mechanical mixture as main, does not have atom or intermolecular combination between the two, and synthetic material is defeated and dispersed easily under the body fluid environment.
Summary of the invention
To the objective of the invention is the defective that exists in the prior art in order solving, a kind of have good biocompatibility and very high bioactive nano double calcium phosphate phase/gelatin bone renovating material and preparation method thereof to be provided.
In order to achieve the above object, the invention provides a kind of bone renovating material, take gelatin solution as mother solution, by feed hydrogen calcium oxide and phosphatase reaction preparation; The concentration of gelatin solution is 1.0 * 10 -3-1.0 * 10 -2G/ml; The addition of phosphoric acid is take gelatin weight as benchmark, and every gram gelatin adds 0.01-0.1mol; The mol ratio of calcium hydroxide and phosphoric acid is 1.55-1.65.
The present invention also provides the preparation method of above-mentioned bone renovating material, may further comprise the steps:
A, under 80 ~ 90 ℃, gelatin (analytical pure) is dissolved in deionized water, the configuration solubility be 1.0 * 10 -3~ 1.0 * 10 -2The gelatin solution of g/ml is cooled to room temperature;
Under b, the stirring, in gelatin solution, slowly drip phosphoric acid, make in every gram gelatin to contain 0.01 ~ 0.1molPO 4 3-
C. after step b phosphoric acid is added dropwise to complete, under stirring, slowly drip and the calcium hydroxide aqueous solution of gelatin solution with volume, the calcium hydroxide of adding and the mol ratio of phosphoric acid are 1.55 ~ 1.65; Stirring reaction 4 ~ 6 hours obtains white suspension;
D. above-mentioned suspension is left standstill 24 ~ 48 hours, centrifugal, get the precipitation lyophilization after, grind and namely to get described bone renovating material dry powder.
Wherein 80 ~ 90 ℃ temperature is controlled by water-bath among the step a; The whipping process of step b and c is finished by magnetic stirring apparatus.
The present invention has the following advantages compared to existing technology:
(1) the present invention is with calcium hydroxide (Ca (OH) 2) and phosphoric acid (H 3PO 4) for the biphasic calcium phosphate of raw material preparation, have good biological activity and osteoinductive, and controlled degradation property.The simultaneous reactions cost of material is low, and byproduct of reaction only is water, need not follow-up precipitate be washed repeatedly, filter, and preparation technology is simple, environmental protection.
(2) adopt gelatin solution as reaction mother liquor, utilize its good cytoactive and no antigen, can avoid the collagen problem, the problem includes: immunogenicity and the problems such as propagation of pathogen as timbering material.Gelatin can form one deck organic protective film on its surface in the biphasic calcium phosphate forming process on the one hand, has suppressed the undue growth of biphasic calcium phosphate crystal grain, makes its crystal grain remain on nanoscale; The backbone of gelatin is so that the biphasic calcium phosphate crystal grain that generates is combined with gelatin closely on the other hand, and arrangement has certain rule.The composite that obtains thus is not only similar to natural bone on composition, and certain imitative bone is also arranged on the structure.
(3) material for preparing of the present invention has good biocompatibility and biological activity, can be used as bone renovating material.
Description of drawings
Fig. 1 is the XRD figure spectrum of the bone renovating material of preparation among the embodiment 1;
Fig. 2 is the XRD figure spectrum after the bone renovating material of preparation among the embodiment 1 is removed gelatin.
The specific embodiment
Below in conjunction with specific embodiment bone renovating material of the present invention is elaborated.
Embodiment 1
Material therefor is analytical pure Ca (OH) 2, analytical pure H 3PO 4(content 〉=85%, density 1.689g/ml), the chemical pure gelatin.
A. under 85 ℃ of water bath condition, gelatin is dissolved in deionized water, configuration solubility is 5.0 * 10 -3The gelatin solution 100ml of g/ml is cooled to room temperature;
B. in gelatin solution, slowly drip phosphatase 11 .7ml, use simultaneously magnetic stirrer during dropping;
C. the amount that slowly drips while stirring the aqueous solution 100ml(calcium hydroxide of calcium hydroxide in the solution of above-mentioned second step is 2.96g); After being added dropwise to complete, magnetic stirrer 5 hours obtains white suspension;
D. above-mentioned suspension was left standstill 36 hours, remove supernatant, centrifugalize goes out precipitation, puts into the freezer dryer drying, makes dry powder after the grinding.
Adopt X ray powder diffracting technology (XRD) that the crystalline phase of sample is characterized, as shown in Figure 1.The diffraction maximum that some inorganic phases wherein occurred, the existence of organic principle gelatin in the higher diffraction maximum substrate explanation product.In order further to determine the composition of inorganic phase, we carry out X-ray diffraction analysis after adopting hydro-thermal method that gelatin, oven dry are removed in the sample washing, as shown in Figure 2.Calcium phosphate (Ca in diffraction maximum and the PDF card 3(PO 4) 2) standard diagram (#702065) and hydroxyapatite (Ca 5(PO 4) 3(OH)) standard diagram (#090432) is consistent, does not detect obvious dephasign peak, contains calcium phosphate (Ca in the interpret sample 3(PO 4) 2) and hydroxyapatite (Ca 5(PO 4) 3(OH)) two phase constituents.According to the peak width of 5 diffraction maximums wherein, the average grain size with Scherrer formula estimation sample is about 87nm.Above presentation of results the technical solution used in the present invention can successfully obtain nanoscale biphasic calcium phosphate/gelatin powder body.
Embodiment 2
Material therefor is analytical pure Ca (OH) 2, analytical pure H 3PO 4(content 〉=85%, density 1.689g/ml), the chemical pure gelatin.
A. under 90 ℃ of water bath condition, gelatin is dissolved in deionized water, configuration solubility is 1.0 * 10 -2The gelatin solution 100ml of g/ml is cooled to room temperature;
B. in gelatin solution, slowly drip phosphoric acid 6.8ml, use simultaneously magnetic stirrer during dropping;
C. the amount that slowly drips while stirring the aqueous solution 100ml(calcium hydroxide of calcium hydroxide in the solution of above-mentioned second step is 12.2g); After being added dropwise to complete, magnetic stirrer 6 hours obtains white suspension;
D. above-mentioned suspension was left standstill 48 hours, remove supernatant, centrifugalize goes out precipitation, puts into the freezer dryer drying, makes dry powder after the grinding.
Embodiment 3
Material therefor is analytical pure Ca (OH) 2, analytical pure H 3PO 4(content 〉=85%, density 1.689g/ml), the chemical pure gelatin.
A. under 80 ℃ of water bath condition, gelatin is dissolved in deionized water, configuration solubility is 1.0 * 10 -3The gelatin solution 100ml of g/ml is cooled to room temperature;
B. in gelatin solution, slowly drip phosphoric acid 0.068ml, use simultaneously magnetic stirrer during dropping;
C. the amount that slowly drips while stirring the aqueous solution 100ml(calcium hydroxide of calcium hydroxide in the solution of above-mentioned second step is 0.11g); After being added dropwise to complete, magnetic stirrer 4 hours obtains white suspension;
D. above-mentioned suspension was left standstill 24 hours, remove supernatant, centrifugalize goes out precipitation, puts into the freezer dryer drying, makes dry powder after the grinding.
Embodiment 4
Material therefor is analytical pure Ca (OH) 2, analytical pure H 3PO 4(content 〉=85%, density 1.689g/ml), the chemical pure gelatin.
A. under 80 ℃ of water bath condition, gelatin is dissolved in deionized water, configuration solubility is 1.0 * 10 -3The gelatin solution 100ml of g/ml is cooled to room temperature;
B. in gelatin solution, slowly drip phosphoric acid 0.68ml, use simultaneously magnetic stirrer during dropping;
C. the amount that slowly drips while stirring the aqueous solution 100ml(calcium hydroxide of calcium hydroxide in the solution of above-mentioned second step is 1.22g); After being added dropwise to complete, magnetic stirrer 5 hours obtains white suspension;
D. above-mentioned suspension was left standstill 36 hours, remove supernatant, centrifugalize goes out precipitation, puts into the freezer dryer drying, makes dry powder after the grinding.
Embodiment 5
Material therefor is analytical pure Ca (OH) 2, analytical pure H 3PO 4(content 〉=85%, density 1.689g/ml), the chemical pure gelatin.
A. under 80 ℃ of water bath condition, gelatin is dissolved in deionized water, configuration solubility is 1.0 * 10 -2The gelatin solution 100ml of g/ml is cooled to room temperature;
B. in gelatin solution, slowly drip phosphoric acid 0.68ml, use simultaneously magnetic stirrer during dropping;
C. the amount that slowly drips while stirring the aqueous solution 100ml(calcium hydroxide of calcium hydroxide in the solution of above-mentioned second step is 1.15g); After being added dropwise to complete, magnetic stirrer 5 hours obtains white suspension;
D. above-mentioned suspension was left standstill 36 hours, remove supernatant, centrifugalize goes out precipitation, puts into the freezer dryer drying, makes dry powder after the grinding.

Claims (2)

1. bone renovating material is characterized in that: described bone renovating material is take gelatin solution as mother solution, by feed hydrogen calcium oxide and phosphatase reaction preparation; The concentration of described gelatin solution is 1.0 * 10 -3-1.0 * 10 -2G/ml; The addition of described phosphoric acid is take gelatin weight as benchmark, and every gram gelatin adds 0.01-0.1mol; The mol ratio of described calcium hydroxide and phosphoric acid is 1.55-1.65.
2. the preparation method of the described bone renovating material of claim 1 is characterized in that: may further comprise the steps:
A, under 80 ~ 90 ℃, gelatin is dissolved in deionized water, the configuration gelatin solution, be cooled to room temperature;
Under b, the stirring, in gelatin solution, slowly drip phosphoric acid;
C. after step b phosphoric acid is added dropwise to complete, under stirring, slowly drip and the calcium hydroxide aqueous solution of gelatin solution with volume; After being added dropwise to complete, stirring reaction 4 ~ 6 hours obtains white suspension;
D. above-mentioned suspension is left standstill 24 ~ 48 hours, centrifugal, get the precipitation lyophilization after, grind and namely to get described bone renovating material dry powder.
CN2012103995686A 2012-10-19 2012-10-19 Bone repairing material and preparation method thereof Pending CN102861356A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103588187A (en) * 2013-11-14 2014-02-19 安徽淮化股份有限公司 Preparation method of nano bioactive material
CN103588186A (en) * 2013-11-14 2014-02-19 安徽淮化股份有限公司 Preparation method of nano-hydroxyapatite
CN107096071A (en) * 2017-04-20 2017-08-29 常州创索新材料科技有限公司 A kind of preparation method of bone renovating material
CN113521391A (en) * 2021-05-28 2021-10-22 西安交通大学医学院第二附属医院 CHA gelatin support

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0999248A1 (en) * 1998-11-03 2000-05-10 Eastman Kodak Company Enzyme method of manufacturing gelatin
CN1562389A (en) * 2004-03-19 2005-01-12 清华大学 Mineralized fibrion/macromolecule composite porous material and preparation method
CN1919359A (en) * 2006-01-05 2007-02-28 天津市威曼生物材料有限公司 Collagen base bionic bone matrix
WO2008022859A2 (en) * 2006-08-24 2008-02-28 Henkel Ag & Co. Kgaa Composition containing 1 to 99 percent by weight of poorly water-soluble calcium salts and/or the composite materials thereof
CN101239202A (en) * 2008-03-12 2008-08-13 天津大学 Nano sheet hydroxyapatite and glutin composite material and preparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0999248A1 (en) * 1998-11-03 2000-05-10 Eastman Kodak Company Enzyme method of manufacturing gelatin
CN1562389A (en) * 2004-03-19 2005-01-12 清华大学 Mineralized fibrion/macromolecule composite porous material and preparation method
CN1919359A (en) * 2006-01-05 2007-02-28 天津市威曼生物材料有限公司 Collagen base bionic bone matrix
WO2008022859A2 (en) * 2006-08-24 2008-02-28 Henkel Ag & Co. Kgaa Composition containing 1 to 99 percent by weight of poorly water-soluble calcium salts and/or the composite materials thereof
CN101239202A (en) * 2008-03-12 2008-08-13 天津大学 Nano sheet hydroxyapatite and glutin composite material and preparation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103588187A (en) * 2013-11-14 2014-02-19 安徽淮化股份有限公司 Preparation method of nano bioactive material
CN103588186A (en) * 2013-11-14 2014-02-19 安徽淮化股份有限公司 Preparation method of nano-hydroxyapatite
CN107096071A (en) * 2017-04-20 2017-08-29 常州创索新材料科技有限公司 A kind of preparation method of bone renovating material
CN113521391A (en) * 2021-05-28 2021-10-22 西安交通大学医学院第二附属医院 CHA gelatin support

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Application publication date: 20130109