CN1562385A - Method for preparing full natural material for renovating rigid tissue formed in vitro - Google Patents
Method for preparing full natural material for renovating rigid tissue formed in vitro Download PDFInfo
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- CN1562385A CN1562385A CN 200410014567 CN200410014567A CN1562385A CN 1562385 A CN1562385 A CN 1562385A CN 200410014567 CN200410014567 CN 200410014567 CN 200410014567 A CN200410014567 A CN 200410014567A CN 1562385 A CN1562385 A CN 1562385A
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Abstract
A hard tissue repairing material is prepared through calcining pork bone, holding temp for 2-20 hr, cooling pulverizing, adding it to water ultrasonic dispersing, dissolving chitosan in the aqueous solution of malic acid, adding it to hydroxy apatite suspension, stirring while ultrasonic dispersing, dropping the aqueous solution of inorganic alkali in it, stirring, regulating pH=more than 6.0, dropping the aqueous solution of cross-linking agent, cross-linking to obtain deposit, washing and drying.
Description
Technical field
The present invention relates to a kind of method for preparing hard tissue repairing material, relate in particular to the external molding hard tissue repairing material of a kind of All Pure Nature preparation method.
Background technology
Annual clinically by there being a large amount of patients damaged because of the sclerous tissues that wound, tumor and other diseases are caused, need a large amount of tissue substitute materials to repair, the reparation problem that histoorgan is damaged has become one of problem that generation is the most frequent, the most disruptive and expense is the highest in human health care's process, hard tissue repairing material also is one of repair materials of domestic and international clinical medicine demand maximum, and therefore novel hard tissue substituting material developing target market has a extensive future.
Biological activitys such as traditional metal material, ceramic material are low, be difficult to degraded, the back long-term effect that implants is undesirable, therefore utilize biocompatibility better, the natural biologic material that can degrade, exploitation more can adapt to the novel hard tissue repairing material of Human Physiology needs, has great importance for people's health and development and national economy, is the important directions of biomaterial research field from now on.
Skeleton is the inorganic/organic composite material that is formed by self assembly by nanometer hydroxyapatite and collagen.As the skeleton main inorganic composition, hydroxyapatite has excellent biological compatibility, and safety non-toxic can also conduct bone growth after implanting.1976, the blue or green wood of Japan synthesized hydroxyapatite respectively with U.S. Jarcho, the frontier of having started the research of hydroxylapatite biology medical material and having used; Tokyo medical university of tooth section began to be applied to the hydroxyapatite artificial dental root clinical in 1980.At present, the ceramic material of hydroxyapatite, metal coating layer material and become hard tissue repair materials such as most important clinically tooth, skeleton with organic composite.Yet the natural hydroxyapatite material (as animal bone) that is widespread in nature does not but obtain sufficient development and utilization so far.As everyone knows, biomaterial is more near human body, accepted by human body easily more.Natural biologic material is to have experienced evolution in 1 years, and the material that is formed by bioprocess is as the biogenic mineral bone, tooth, shell and structural protein collagen fiber, silkworm silk or the like, having some traditional synthetic material at aspects such as molecular composition, microstructures can't mimic characteristic.Natural hydroxyapatite is compared with artificial-synthetic hydroxyapatite's material owing to more approach the human skeleton composition on The Nomenclature Composition and Structure of Complexes, is expected to obtain higher biological activity.Therefore, the present invention selects natural hydroxyapatite from animal body as the basic material that conducts a research.
Because being applied to sclerous tissues's displacement, pure hydroxyapatite also has some weakness, as a little less than the bone inductive effect, big, the processing difficulties of fragility, granular pattern hydroxyapatite be not easy to be shaped etc., and from bionic angle, the hard tissue repair material for repairing also should comprise organic and inorganic constituents.Since the eighties, researcher has carried out multiple compound and modification to the artificial-synthetic hydroxyapatite both at home and abroad, compound, compound with natural biologic material of compound, the organic polymer biomaterial of research direction being and not being machine biomaterial, and compound with organism self material.In recent years, both at home and abroad begun one's study hydroxyapatite and chitosan composite of researcher prepared uniform hydroxylapatite/chitosan nano composite material as human coprecipitations such as Yamaguchi.
Chitosan is the natural biological polysaccharide, extensively is present in the animal shells such as shrimp, Eriocheir sinensis.Although chitosan is not the intravital composition of people, have good biocompatibility, surgical operation absorbable suture, medical dressing and the artificial skin made by chitosan have obtained clinical practice.People such as Muzzarelli find that chitosan and derivant thereof can stimulate the sclerous tissues especially recovery and the regeneration of osseous tissue, so the present invention is undertaken hydroxyapatite and chitosan compound to obtain ideal hard tissue repair material by chemical crosslinking.
Technology contents
The invention provides a kind of can improve make the product mechanical property, production cost is low and the external molding hard tissue repairing material of the better All Pure Nature of bone repairing performance preparation method.
The present invention is a kind of external molding hard tissue repairing material of All Pure Nature preparation method that is used for hard tissue repair,
The first step: earlier fresh edible Os Sus domestica is boiled, muscle and the bone marrow and dry that adheres on it is removed in the cooling back, again exsiccant Os Sus domestica is placed 800-1050 ℃ of temperature lower calcination, behind insulation 2-20h under this temperature, be chilled to room temperature, collect the bone piece after calcining, then, pulverize the Os Sus domestica after calcining, be made into powder body, promptly get natural hydroxy apatite powder, ratio by natural hydroxy apatite powder and water is 1: (1-100), natural hydroxy apatite powder is added in the entry, ultra-sonic dispersion again after the stirring, the suspension of natural hydroxyapatite;
Second step: according to chitosan: malic acid: distilled water is 1: (1-10): mass ratio (1-100), chitosan is dissolved in solution in the water of the binary organic acid that contains 3～8 carbon atoms, get chitosan solution, then, according to chitosan: hydroxyapatite is the mass ratio of (1: 1)～(1: 4), the suspension that chitosan solution is added hydroxyapatite, stir and ultra-sonic dispersion, make its mix homogeneously, with mass percent concentration is that the aqueous solution of the inorganic base of 0.1%-40% is added drop-wise in the above-mentioned natural hydroxyapatite/chitosan mixture and stirs, when pH value rises to 6.0～14.0, stop dropping sodium solution, continue to stir 2h, then stop more than 6.0 stirring when pH value still remains on, otherwise dropping sodium solution is adjusted to them more than 6.0 again;
The 3rd step: under 1000-3000r/min speed, stir natural hydroxyapatite/chitosan mixture, according to chitosan: cross-linking agent is the mass ratio of (1: 1)～(5: 1), in natural hydroxyapatite/chitosan mixture, drip the aqueous solution of cross-linking agent, cross-linking agent is that the carbon atom number is below 8, the cross-linking agent that contains 2 active aldehyde radicals, treat to continue to stir 2-20 hour after cross-linking agent drips off, make it crosslinked, the natural hydroxyapatite/chitosan composite precipitation thing after crosslinked, this natural hydroxyapatite/chitosan composite precipitation thing is through washing, be external molding hard tissue repairing material after the drying.
The present invention can carry out precomminution with iron hammer to Os Sus domestica before the Os Sus domestica calcining, after the Os Sus domestica calcining, with ball mill Os Sus domestica is made powder body.
Compared with prior art, the present invention has following advantage:
1. good biocompatibility: we adopt the cell growth inhibition assay of recommending among the GB/T 16886-ISO 10993 (MTT colorimetry), the main component (natural hydroxyapatite and chitosan) and the cell compatibility of natural hydroxyapatite/chitosan composite sample to composite are estimated, and with inverted phase contrast microscope the influence of material lixiviating solution pair cell form are observed.Found that: be respectively 84%, 82% and 89.9% with natural hydroxyapatite, chitosan and the natural hydroxyapatite/chitosan composite lixiviating solution cultured cells rate of increase, the toxicity grading is 0 grade, and cellular morphology is similar to negative control group.The preliminary proof of cell in vitro test, composite has excellent biological compatibility;
2. the bone repairing performance is good: by natural hydroxyapatite material the adsorption test of three kinds of plasma proteins (Fibrinogen FiB, albumin A lb, immunoglobulin IgG) is found that natural hydroxyapatite to the adsorbance of three kinds of plasma proteins is: IgG＞FiB＞Alb.Relation according to the blood coagulation performance of the kind of adhesion protein and material: promptly fibrinogenic being adsorbed with is beneficial to blood coagulation, and albuminous absorption anticoagulant, greater than albuminous adsorbance, promptly natural hydroxyapatite has good blood coagulation performance to natural hydroxyapatite to fibrinogenic adsorbance; According to the organization of hematoma mechanism of union of fracture, the sludged blood that organization of hematoma forms includes multiple bone Induced substance, and good bone conduction effect is arranged, and helps the damaged reparation of skeleton, and therefore, our prepared material has bone repairing performance preferably;
3. mechanical property is good: with the composite quality densification that the inventive method makes, mechanical property obviously improves, and can keep in the bone repair process that calcium ion and phosphonium ion continue in the hydroxyapatite, steadily, discharge from glycan substrate lentamente;
4. multiple use: can be used for orthopaedics, tooth section, decorative sursery, neurocranial surgery and plastic surgery etc.
5. production cost is low: the raw material source is abundant, cheap at home for the method for extracting natural hydroxyapatite from Os Sus domestica that the present invention proposes; Production technology is simple, does not need special equipment, and is with low cost.The expense of raw materials that the Sol-Gel method is produced the 500g product is 85 yuan, and adopts technology of the present invention, and the products material expense of producing 500g only needs 10 yuan; On the production operation expense, every production 500g product, Sol-Gel method technology will consume electric power 5000 degree than technology of the present invention more.
6. production capacity height: Sol-Gel method commonly used will spend the time in a week with the reactor of 3L just can produce the hydroxyapatite of 20g, and adopts technology of the present invention just can produce the product of 500g in one day;
7. environmental protection, do not have " three wastes " discharging: the method for synthetic is produced hydroxyapatite can produce the phosphorated waste water of a large amount of richnesses, and the bio-medical material that the method for extracting natural hydroxyapatite from Os Sus domestica that the present invention proposes can become clinical a large amount of needs to the animal bone of being used as refuse in the past in the slaughterhouse, tooth.
Description of drawings
Fig. 1 is that the present invention extracts natural hydroxyapatite technological operation step legend.
Fig. 2 is preparation were established figure of the present invention.
Embodiment
Embodiment 1 the present invention is a kind of external molding hard tissue repairing material of All Pure Nature preparation method that is used for hard tissue repair:
The first step: earlier fresh edible Os Sus domestica is boiled, muscle and the bone marrow and dry that adheres on it is removed in the cooling back, again exsiccant Os Sus domestica is placed 800-1050 ℃ of temperature lower calcination, behind insulation 2-20h under this temperature, be chilled to room temperature, collect the bone piece after calcining, then, pulverize the Os Sus domestica after calcining, be made into powder body, promptly get natural hydroxy apatite powder, ratio by natural hydroxy apatite powder and water is 1: (1-100), natural hydroxy apatite powder is added in the entry, ultra-sonic dispersion again after the stirring, natural hydroxyapatite suspension;
Second step: according to chitosan: malic acid: distilled water 1: (1-10): ratio (1-100), chitosan is dissolved in the aqueous solution of the binary organic acid that contains 3～8 carbon atoms, for example: be dissolvable in water malic acid, 1,3-propanedicarboxylic acid or adipic acid, get chitosan solution, then, according to chitosan: hydroxyapatite is the ratio of (1: 1)～(1: 4), the suspension of hydroxyapatite will be added in the chitosan solution, stir and ultra-sonic dispersion, make its mix homogeneously, with mass percent concentration is that the aqueous solution of the inorganic base (as sodium hydroxide) of 0.1%-40% is added drop-wise in the above-mentioned natural hydroxyapatite/chitosan mixture and stirs, when pH value rises to 6.0～14.0, stop dropping sodium solution, continue to stir, then stop more than 6.0 stirring when pH value still remains on, otherwise dropping sodium solution again is adjusted to them more than 6.0;
The 3rd step: under 1000-3000r/min speed, stir natural hydroxyapatite/chitosan mixture, according to chitosan: cross-linking agent is the mass ratio of (1: 1)～(5: 1), in natural hydroxyapatite/chitosan mixture, drip the aqueous solution of cross-linking agent, cross-linking agent is that the carbon atom number is below 8, the cross-linking agent that contains 2 active aldehyde radicals, for example: cross-linking agent can adopt glutaraldehyde, butanedial or hexandial, treat to continue to stir 2-20 hour after cross-linking agent drips off, make it crosslinked, the natural hydroxyapatite/chitosan composite precipitation thing after crosslinked, this natural hydroxyapatite/chitosan composite precipitation thing is through washing, be external molding hard tissue repairing material after the drying.Present embodiment carries out precomminution with iron hammer to Os Sus domestica before the Os Sus domestica calcining, after the Os Sus domestica calcining, with ball mill Os Sus domestica is made powder body.
Embodiment 2 at first extracts natural hydroxyapatite from the healthy eating Os Sus domestica, then natural hydroxyapatite and chitosan are carried out compoundly, obtains natural hard tissue repair material, and concrete operations are as follows:
1. the cleaning of Os Sus domestica: fresh porker is boiled, and muscle and bone marrow that the cooling back is adhered to the removal of bamboo chopsticks after processing is clean, place the baking oven finish-drying.
2. the calcining of Os Sus domestica: exsiccant Os Sus domestica is smashed, divide and install in the ceramic crucible, place in the electric furnace, shut fire door, design temperature is opened the on and off switch of electric furnace between 800-1050 ℃, after being raised to design temperature, temperature is incubated 2-20h again, by the time after fire box temperature drops to room temperature, take out crucible, collect the bone piece after calcining.
3. the pulverizing of forging bone piece: the bone piece after will calcining is pulverized with pulverizer, uses the ball mill ball milling then, makes natural hydroxy apatite powder;
4. with analytical balance weighing a certain amount of natural hydroxy apatite powder, add an amount of distilled water, ultra-sonic dispersion again after the stirring is placed standby;
5. with analytical balance weighing certain amount of chitosan, add an amount of distilled water, stir and the adding malic acid, chitosan is dissolved fully;
6. add the suspension of hydroxyapatite in above-mentioned chitosan solution, make chitosan: the ratio of hydroxyapatite is in 1: 1 to 1: 4 scope, and high-speed stirred and ultra-sonic dispersion make its mix homogeneously;
7. be configured to the sodium hydroxide solution of 0.1%-40%, it is added drop-wise in the above-mentioned natural hydroxyapatite/chitosan mixture, when pH value rises to 6.0～14.0, can form a large amount of precipitations, stop dropping sodium solution this moment, continue to stir, then stop more than 6.0 stirring when pH value still remains on, otherwise be adjusted to more than 6.0 with a spot of sodium hydroxide solution;
8. according to chitosan: cross-linking agent (as glutaraldehyde) is that the ratio of (1: 1)～(5: 1) slowly drips glutaraldehyde solution under the state of high-speed stirred, continue after dripping off to stir 2-20 hour, make it full cross-linked, can get the natural hydroxyapatite/chitosan composite precipitation after crosslinked;
Above-mentioned precipitation is overanxious 9., use the distilled water cyclic washing, with the centrifugal after drying of composite precipitation, be external molding hard tissue repairing material.
The healthy Os Sus domestica of embodiment 3 present embodiment utilizations prepares natural hydroxyapatite material through high-temperature calcination, prepare micron-sized powder through pulverizing and mechanical ball milling again, disperse the back to add in the dissolved malic acid solution of chitosan with distilled water, through stirring and ultra-sonic dispersion, make finely dispersed natural hydroxyapatite/chitosan mixed liquor again; Under the situation of high-speed stirred in mixed liquor the sodium hydroxide solution of Dropwise 5 %, regulate pH value to 8.0, drip a certain amount of glutaraldehyde solution again, after full cross-linked, make homodisperse natural hydroxyapatite/chitosan composite precipitation, to precipitate cyclic washing with distilled water, be neutral up to cleaning mixture, again through centrifugal, drying and moulding in mould can make the composite of good mechanical performance.After tested, the pH value of composite impregnation liquid is stabilized in 7.2, scanning electron microscopic observation shows this composite quality densification, biphase combining closely, cell in vitro experimental results show that this composite has the good cell compatibility, certain dilatancy is arranged after implanting, can combine closely good mechanical performance with bone is damaged.
Claims (2)
1, a kind of external molding hard tissue repairing material of All Pure Nature preparation method that is used for hard tissue repair is characterized in that:
The first step: earlier fresh edible Os Sus domestica is boiled, muscle and the bone marrow and dry that adheres on it is removed in the cooling back, again exsiccant Os Sus domestica is placed 800-1050 ℃ of temperature lower calcination, behind insulation 2-20h under this temperature, be chilled to room temperature, collect the bone piece after calcining, then, pulverize the Os Sus domestica after calcining, be made into powder body, promptly get natural hydroxy apatite powder, mass ratio by natural hydroxy apatite powder and water is 1: (1-100), natural hydroxy apatite powder is added in the entry, ultra-sonic dispersion again after the stirring, natural hydroxyapatite suspension;
Second step: according to chitosan: organic acid: distilled water is 1: (1-10): mass ratio (1-100), chitosan is dissolved in the aqueous solution of the binary organic acid that contains 3～8 carbon atoms, get chitosan solution, then according to chitosan: hydroxyapatite is the mass ratio of (1: 1)～(1: 4), the suspension that chitosan solution is added hydroxyapatite, stir and ultra-sonic dispersion, make its mix homogeneously, with mass percent concentration is that the aqueous solution of the inorganic base of 0.1%-40% is added drop-wise in the above-mentioned natural hydroxyapatite/chitosan mixture and stirs, when pH value rises to 6.0～14.0, stop dropping sodium solution, continue to stir and make it even, then stop more than 6.0 stirring when pH value still remains on, otherwise dropping sodium solution is again regulated it more than PH to 6.0;
The 3rd step: under 1000-3000r/min speed, stir natural hydroxyapatite/chitosan mixture, according to chitosan: cross-linking agent is the mass ratio of (1: 1)～(5: 1), in natural hydroxyapatite/chitosan mixture, drip the aqueous solution of cross-linking agent, cross-linking agent is that the carbon atom number is below 8, the cross-linking agent that contains 2 active aldehyde radicals, treat to continue to stir 2-20 hour after cross-linking agent drips off, make it crosslinked, the natural hydroxyapatite/chitosan composite precipitation thing after crosslinked, this natural hydroxyapatite/chitosan composite precipitation thing is through washing, be external molding hard tissue repairing material after the drying.
2, the external molding hard tissue repairing material of All Pure Nature according to claim 1 preparation method is characterized in that with iron hammer Os Sus domestica being carried out precomminution before the Os Sus domestica calcining, after the Os Sus domestica calcining, with ball mill Os Sus domestica is made powder body.
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Cited By (7)
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| CN100465137C (en) * | 2007-01-10 | 2009-03-04 | 南京大学 | Regulation and control agent in use for treating soil polluted by heavy metals |
| CN101401965B (en) * | 2008-11-17 | 2013-09-11 | 昆明理工大学 | Synthesis of composite bone restoration bioactive material |
| CN103948964A (en) * | 2014-04-04 | 2014-07-30 | 北京大学口腔医院 | Preparation method of bone grafting material coated with adiponectin |
| CN105713400A (en) * | 2016-03-31 | 2016-06-29 | 青岛百瑞吉生物工程有限公司 | Preparation method of TiO2 biomedical film |
| CN106075600A (en) * | 2016-06-25 | 2016-11-09 | 张静 | A kind of preparation method of medical degradable calcium phosphate coating magnesium alloy |
| KR20220095641A (en) * | 2020-12-30 | 2022-07-07 | 한국화학연구원 | Manufacturing method of nanopore type eco-friendly hydroxyapatite with flame retardant, deodorant and toxic substance adsorption performance |
| CN116161955A (en) * | 2022-12-19 | 2023-05-26 | 南京航空航天大学 | Normal-temperature one-step extrusion 3D printing forming preparation method of high-strength hydroxyapatite bone tissue engineering scaffold |
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2004
- 2004-04-06 CN CN 200410014567 patent/CN1251768C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465137C (en) * | 2007-01-10 | 2009-03-04 | 南京大学 | Regulation and control agent in use for treating soil polluted by heavy metals |
| CN101401965B (en) * | 2008-11-17 | 2013-09-11 | 昆明理工大学 | Synthesis of composite bone restoration bioactive material |
| CN103948964A (en) * | 2014-04-04 | 2014-07-30 | 北京大学口腔医院 | Preparation method of bone grafting material coated with adiponectin |
| CN103948964B (en) * | 2014-04-04 | 2015-08-05 | 北京大学口腔医院 | A kind of preparation method of bone-grafting material of adiponectin bag quilt |
| CN105713400A (en) * | 2016-03-31 | 2016-06-29 | 青岛百瑞吉生物工程有限公司 | Preparation method of TiO2 biomedical film |
| CN106075600A (en) * | 2016-06-25 | 2016-11-09 | 张静 | A kind of preparation method of medical degradable calcium phosphate coating magnesium alloy |
| KR20220095641A (en) * | 2020-12-30 | 2022-07-07 | 한국화학연구원 | Manufacturing method of nanopore type eco-friendly hydroxyapatite with flame retardant, deodorant and toxic substance adsorption performance |
| KR102608854B1 (en) | 2020-12-30 | 2023-11-30 | 한국화학연구원 | Manufacturing method of nanopore type eco-friendly hydroxyapatite with flame retardant, deodorant and toxic substance adsorption performance |
| CN116161955A (en) * | 2022-12-19 | 2023-05-26 | 南京航空航天大学 | Normal-temperature one-step extrusion 3D printing forming preparation method of high-strength hydroxyapatite bone tissue engineering scaffold |
| CN116161955B (en) * | 2022-12-19 | 2024-05-03 | 南京航空航天大学 | Normal-temperature one-step extrusion 3D printing forming preparation method of high-strength hydroxyapatite bone tissue engineering scaffold |
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