CN103285427B - Artificial bone material and preparation method thereof - Google Patents
Artificial bone material and preparation method thereof Download PDFInfo
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- CN103285427B CN103285427B CN201310149302.0A CN201310149302A CN103285427B CN 103285427 B CN103285427 B CN 103285427B CN 201310149302 A CN201310149302 A CN 201310149302A CN 103285427 B CN103285427 B CN 103285427B
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Abstract
The invention discloses a preparation method of an artificial bone material. The preparation method comprises providing raw materials including hydroxyapatite, collagen and nano-crystalline cellulose. The preparation method comprises: step (S1100). dropping a solution containing PO4<3-> of 0.05-0.5 mol/L into a collagen solution with a mass percent concentration of 0.1-1%, stirring to keep in reserve; step (S1200). preparing a nano-crystalline cellulose solution with a mass percent concentration of 0.5-10%, and mixing the nano-crystalline cellulose solution and the collagen PO4<3-> solution prepared by the step (S1100), stirring and homogenizing; step (S1300). adding a solution containing Ca<2+> of 0.2-0.8 mol/L into the collgen/ nano-crystalline cellulose composite solution prepared by the step (S1200), setting the mol ratio of Ca to P as 1.67, adjusting the pH to 7-9 with an alkaline solution and precipitating, freeze-drying the precipitation to obtain the artificial bone material.
Description
Technical field
The present invention relates to a kind of material, relate in particular to a kind of artificial bone and preparation method thereof.
Background technology
Osseous tissue is comprised of organic principle and inorganic constituents, and in adult bone, organic principle accounts for 1/3, and inorganic constituents accounts for 2/3.In organic principle, collagen accounts for 95% left and right, and inorganic constituents is mainly hydroxyapatite.Therefore can say, nature bone is comprised of hydroxyapatite and the collagen of low-crystallinity.
The hydroxyapatite of synthetic has good biocompatibility and biological activity, it is a kind of good hard tissue substituting material, and because the crystal grain of hydroxyapatite has skin effect and bulk effect, after implant into body, can reach perfect affine by hydrogen bond and tissue bonding, without immune rejection phenomenon and there is certain bone conduction performance, at tool aspect mechanics and biology, having an enormous advantage and application potential, is a kind of desirable tissue implanting material.Blemish in an otherwise perfect thing, the fragility of hydroxyapatite is large and toughness is low, can not be for the damaged reparation of position bone of bearing a heavy burden, and difficult degradation in vivo, limited its application in bone is repaired.Collagen has the good compatibility, reduced immunogenicity to osteocyte, and the medical material graft based on collagen is promoting to demonstrate good result aspect tissue repair and regeneration.But from current production technology and product, still there is the shortcomings such as mechanical strength is inadequate, porosity is low, hole traffic poor performance in prepared hydroxyapatite/collagen composite.
Therefore, hope can provide the artificial bone that a kind of mechanical strength is higher.
Artificial bone of the prior art is formed by hydroxyapatite and collagen composite.Although hydroxyapatite has good biocompatibility and biological activity, it is a kind of good hard tissue substituting material, and because the crystal grain of hydroxyapatite has skin effect and bulk effect, after implant into body, can reach perfect affine by hydrogen bond and tissue bonding, without immune rejection phenomenon and there is certain bone conduction performance, at tool aspect mechanics and biology, having an enormous advantage and application potential, is a kind of desirable tissue implanting material.Meanwhile, collagen has the good compatibility, reduced immunogenicity to osteocyte, and the medical material graft based on collagen is promoting to demonstrate good result aspect tissue repair and regeneration.But the fragility of hydroxyapatite is large and toughness is low, can not be for the damaged reparation of position bone of bearing a heavy burden, and difficult degradation in vivo, limited its application in bone is repaired.Collagen has the good compatibility, reduced immunogenicity to osteocyte, and the medical material graft based on collagen is promoting to demonstrate good result aspect tissue repair and regeneration.Therefore,, from current production technology and product, still there is the shortcomings such as mechanical strength is inadequate, porosity is low, hole traffic poor performance in prepared hydroxyapatite/collagen composite.
In order to overcome the above problems, the present invention adds nano-cellulose in the composite of hydroxyapatite and collagen formation to, is applied to artificial bone.
Nano-cellulose is that cellulose is hydrolyzed with strong acid under certain condition, and resulting size is at the cellulose of Nano grade.Nano-cellulose is compared and is had superior character with general fibre element, can improve the biocompatibility of material, simultaneously because nanofiber has high strength, its Young's modulus can reach 100-143Gpa, nano-cellulose is added in the composite of hydroxyapatite and collagen formation, for artificial bone, can significantly improve the mechanical performance of artificial bone.
In addition, because nano-cellulose is to obtain by cellulose hydrolysis, and cellulose is that occurring in nature plant is by the synthetic material of photosynthesis, inexhaustible, so composition using nano-cellulose as artificial bone, can also reduce its manufacturing cost, meet medical profession and the patient demand to artificial bone.
Alternatively, preparation in accordance with the present invention, wherein, the described hydroxyapatite providing accounts for the 40-60% of raw material gross weight, and described collagen accounts for the 30-50% of raw material gross weight, and described nano-cellulose accounts for the 0.1-10% of raw material gross weight.When nano-cellulose accounts for the 0.1-10% of raw material gross weight, the mechanical performance of preparing resulting materials is optimum.
Alternatively, preparation in accordance with the present invention, wherein, comprises step:
Step S1100 prepares collagen PO
4 3-solution: described collagen is mixed with to the collagenic aqueous solution that mass percent concentration is 0.1-1%; Afterwards by the PO that contains of 0.05-0.5mol/l
4 3-solution splashes into collagenic aqueous solution, stirs;
Step S1200 prepares collagen/nano-cellulose composite solution: described nano-cellulose is mixed with to the nano-cellulose aqueous solution that mass percent concentration is 0.5-10%, collagen PO prepared by itself and step S1100
4 3-stirring after solution mixes, homogenizing;
Step S1300 prepares collagen/hydroxyapatite/nano-cellulose composite: by the Ca that contains of 0.2-0.8mol/l
2+solution splashes in collagen/nano-cellulose composite solution prepared by step S1200, and the mol ratio of Ca/P is set to 1.67, stirs, and with alkaline solution, regulates pH value precipitation, by precipitate lyophilization, makes artificial bone.Preferably, before precipitation, first still aging 24h, is used centrifugation, and so settling velocity is faster, and production efficiency is higher.
Alternatively, preparation in accordance with the present invention, wherein, described containing PO
4 3-solution is (NH
4)
2hPO
4, Na
2hPO
4and H
3pO
4in any one.
Alternatively, preparation in accordance with the present invention, wherein, described containing Ca
2+solution is CaCl
2, Ca(NO
3)
2and Ca(OH)
2in any one.
Alternatively, preparation in accordance with the present invention, wherein, the described alkaline solution that regulates pH value is any one in ammonia, sodium hydroxide and calcium hydroxide.Preferably, use calcium hydroxide as reagent, pH value that not only can regulator solution, can also introduce Ca thus
2+, so, described solution need not be introduced from the external world new solvent and adjust Ca/P mol ratio, has avoided introducing new impurity in described solution.
Alternatively, preparation in accordance with the present invention, wherein, described in step S1300, pH value is adjusted to 7-9.
Alternatively, preparation in accordance with the present invention, wherein, stirs 20-40 minute in step S1100, stir 1-2h in step S1300.In step S1100, contain PO
4 3-solution splashes into after the collagenic aqueous solution that mass percent concentration is 0.1-1%, stirs the even mixing that can guarantee solution for 20-40 minute, also can reduce preparation time, to enhance productivity.In step S1300, mixing time is 1-2h, can guarantee Ca
2+abundant dispersion.
Alternatively, the particle diameter of described nano-cellulose is 2-100nm.Particle diameter is that nano level cellulose has larger specific surface area, can be preferably with described raw material in other compositions compound better, thereby the porosity and the hole traffic that improve material.Preferably, the particle diameter of described hydroxyapatite is nanoscale.Particle diameter is that nano level hydroxyapatite has larger specific surface area, can be compound better with other compositions in described raw material, thus biocompatibility, biological activity and the bone conductibility of raising material.
According to an aspect of the present invention, provide a kind of artificial bone.In artificial bone provided by the invention, contain nano-cellulose, described nano-cellulose is to be prepared from by selective hydrolysis natural cellulosic feedstocks (as timber, Cotton Gossypii and Folium Agaves Sisalanae).Nano-cellulose is added in the composite of hydroxyapatite and collagen formation, for artificial bone, can significantly improve the mechanical performance of artificial bone.In addition, because nano-cellulose is to obtain by cellulose hydrolysis, and cellulose is that occurring in nature plant is by the synthetic material of photosynthesis, inexhaustible, so composition using nano-cellulose as artificial bone, its manufacturing cost be can also reduce, medical profession and the acquisition cost of patient to artificial bone reduced.
Because artificial bone provided by the invention has stronger mechanical performance, high porosity, hole traffic and good biocompatibility, the 3D that therefore this material can be applied to field of tissue engineering technology prints.
A technical bottleneck of field of tissue engineering technology lacks the artificial scaffolds of a kind of " tailor-made " exactly, can not make support to measure according to the difference of patient body structure or situation.It is to utilize three-dimensional CAD data that 3D prints, and by rapid shaping machine, material stacking is become to the technology of entity prototype, and it can be automatically, fast, directly, accurately design philosophy is changed into prototype.3D printing technique has been broken through the technical bottleneck of field of tissue engineering technology.Artificial bone provided by the invention is applied to 3D and prints, can produce more quickly and accurately the material that more approaches nature bone.Simultaneously because the fusing point of collagen is low, when artificial bone provided by the invention is printed for 3D, print temperature is lower, energy loss is low, good moldability, and can be according to not being all it and making to measure of patient's condition, for organizational project pore size and hole traffic Properties Control provide a kind of solution.
Summary of the invention
For this reason, the present invention proposes a kind of novel artificial bone material and preparation method thereof of at least a portion that can address the above problem.
According to an aspect of the present invention, provide a kind of preparation method of artificial bone, this preparation method comprises: supply raw materials, described raw material comprises hydroxyapatite, collagen and nano-cellulose.
Accompanying drawing explanation
By reading below detailed description of the preferred embodiment, various other advantage and benefits will become cheer and bright for those of ordinary skills.Accompanying drawing is only for the object of preferred implementation is shown, and do not think limitation of the present invention.
Fig. 1 shows according to the preparation method of the artificial bone of one embodiment of the present invention.
The specific embodiment
The invention provides many applicable creative concepts, this creativeness concept can be reflected in a large number of in concrete context.The specific embodiment of describing in following embodiments of the present invention is only as the exemplary illustration of the specific embodiment of the present invention, and do not form limitation of the scope of the invention.
First enter step S1100 and prepare collagen PO
4 3-solution: by the PO that contains of 0.05-0.5mol/l
4 3-solution splashes in the collagenic aqueous solution that mass percent concentration is 0.1-1%, stirs standby after 20-40 minute.Then enter step S1200 and prepare collagen/nano-cellulose composite solution: the preparation mass percent concentration nano-cellulose aqueous solution that is 0.5-10%, collagen PO prepared by itself and step S1100
4 3-stirring after solution mixes, homogenizing; Finally enter step S1300 and prepare collagen/hydroxyapatite/nano-cellulose composite: 0.2-0.8mol/l is contained to Ca
2+solution splashes in collagen/nano-cellulose composite solution prepared by step S1200, and Ca/P mol ratio is set to 1.67, stirs 1-2h, and with alkaline solution, regulating its pH is 7-9, still aging 24h, and centrifugation, by precipitate lyophilization, makes artificial bone.Described containing PO
4 3-solution is (NH
4)
2hPO
4, Na
2hPO
4and H
3pO
4in any one.Described containing Ca
2+solution is CaCl
2, Ca(NO
3)
2and Ca(OH)
2in any one.For the alkaline solution that regulates pH, be any one of ammonia, sodium hydroxide and calcium hydroxide.
Below in conjunction with accompanying drawing and concrete embodiment, the invention will be further described.
Embodiment 1
Fig. 1 shows according to the preparation method of the artificial bone of one embodiment of the present invention, as shown in the figure:
First enter step S1100 and prepare collagen PO
4 3-solution: the collagenic aqueous solution 450ml that compound concentration is 0.1%, by the H of 0.1mol/l
3pO
4solution 30ml splashes in collagenic aqueous solution, stirs 20 minutes.Then enter step S1200 and prepare collagen/nano-cellulose composite solution: the nano-cellulose aqueous solution 1ml that compound concentration is 5%, the collagen PO preparing with step S1100
4 3-solution blending stirs, afterwards by high pressure homogenizer homogenizing.Finally enter step S1300 and prepare collagen/hydroxyapatite/nano-cellulose composite: the CaCl that compound concentration is 0.2mol/l
2solution 25ml, splashes in collagen/nano-cellulose homogenizing fluid, and Ca/P mol ratio is set to 1.67, stirs 1.5h, to guarantee Ca
2+abundant dispersion; With ammonia regulator solution pH, be 8.5, still aging 24h, centrifugation, by precipitate lyophilization, makes artificial bone.
Embodiment 2
Fig. 1 shows according to the preparation method of the artificial bone of one embodiment of the present invention, as shown in the figure:
First enter step S1100 and prepare collagen PO
4 3-solution: the collagenic aqueous solution 1ml that compound concentration is 10%, by (the NH of 0.5mol/l
4)
2hPO
4solution 7ml splashes in collagenic aqueous solution, stirs 30 minutes.Then enter step S1200 and prepare collagen/nano-cellulose composite solution: the nano-cellulose aqueous solution 20ml that compound concentration is 0.5%, collagen PO prepared by itself and step S1100
4 3-solution blending stirs, afterwards by high pressure homogenizer homogenizing.Finally enter step S1300 and prepare collagen/hydroxyapatite/nano-cellulose composite: the Ca(OH that compound concentration is 0.6mol/l)
2solution 10ml, splashes in collagen/nano-cellulose homogenizing fluid, and with sodium hydroxide, being neutralized to pH is that 8, Ca/P mol ratio is set to 1.67, stirs 2h, still aging 18h, and centrifugation, by precipitate vacuum drying, makes artificial bone.
Embodiment 3
Fig. 1 shows according to the preparation method of the artificial bone of one embodiment of the present invention, as shown in the figure:
First enter step S1100 and prepare collagen PO
4 3-solution: the collagenic aqueous solution 41ml that compound concentration is 1%, by the Na of 0.3mol/l
2hPO
4solution 14ml splashes in collagenic aqueous solution, stirs 30 minutes.Then enter step S1200 and prepare collagen/nano-cellulose composite solution: the nano-cellulose aqueous solution 2ml that compound concentration is 0.5%, collagen PO prepared by itself and step S1100
4 3-solution blending stirs, afterwards by high pressure homogenizer homogenizing.Finally enter step S1300 and prepare collagen/hydroxyapatite/nano-cellulose composite: the Ca(NO that compound concentration is 0.8mol/l
3)
2solution 7ml, splashes in collagen/nano-cellulose homogenizing fluid, and Ca/P mol ratio is set to 1.67, stirs 2h, to guarantee Ca
2+abundant dispersion; With ammonia regulator solution pH, be 7.4, still aging 20h, centrifugation, by precipitate lyophilization, makes artificial bone.
Generally speaking, composite nano fiber element on the basis that the present invention is prepared at hydroxyapatite/collagen, this preparation method is simple, resulting hydroxyapatite/collagen/nano-cellulose composite good biocompatibility, mechanical strength is high, while printing artificial bone for 3D, print temperature is lower, energy loss is low, good moldability, and can also for it, make suitable artificial bone to measure according to patient's different situations.
Hydroxyapatite/collagen/nano-cellulose the composite obtaining for abundant identity basis preparation method of the present invention has good performance, has chosen the material that embodiment 1, embodiment 2 and embodiment 3 prepare, and has carried out bending property test.
According to GB1040-79, respectively by hydroapatite particles, and hydroxyapatite/collagen/nano-cellulose composite material granular that embodiment 1, embodiment 2 and embodiment 3 obtain is made bending strength test sample.
By Instron1341 Material Testing Machine, sample is carried out to bending property test, sample testing environment is: loading velocity 10mm/ minute, and room temperature: 25 ℃, humidity: 65%,
Computing formula:
σ wherein
f-bending strength, MPa; P-breaking load, N; The span of L-sample, mm; B-specimen width, mm; H-sample thickness, mm.
Concrete test result is as shown in the table:
| Project | Blank | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Bending strength/Mpa | 37 | 49 | 41 | 44 |
According to the data of upper table, can find out, add nano-cellulose to carry out after modification artificial bone, the hydroxyapatite/collagen/nano-cellulose composite hot strength obtaining is all improved, thereby can effectively improve the mechanical strength of artificial bone.
It should be noted, the present invention will be described rather than limit the invention for above-described embodiment, and those skilled in the art can design alternative embodiment in the situation that do not depart from the scope of claims.In the claims, any reference marks between bracket should be configured to limitations on claims.Word " comprises " not to be got rid of existence and is not listed as element or step in the claims.Being positioned at word " " before element or " one " does not get rid of and has a plurality of such elements.The use of word first, second and C grade does not represent any order.Can be title by these word explanations.
Claims (8)
1. a preparation method for artificial bone, this preparation method comprises: supply raw materials, described raw material comprises hydroxyapatite, collagen and nano-cellulose,
Wherein, the described hydroxyapatite providing accounts for the 40-60% of raw material gross weight, and described collagen accounts for the 30-50% of raw material gross weight, and described nano-cellulose accounts for the 0.1-10% of raw material gross weight;
Described preparation method, comprises step:
Step (S1100) is prepared collagen PO
4 3-solution: described collagen is mixed with to the collagenic aqueous solution that mass percent concentration is 0.1-1%; Afterwards by the PO that contains of 0.05-0.5mol/l
4 3-solution splashes into collagenic aqueous solution, stirs;
Step (S1200) is prepared collagen/nano-cellulose composite solution: described nano-cellulose is mixed with to the nano-cellulose aqueous solution that mass percent concentration is 0.5-10%, collagen PO prepared by itself and step (S1100)
4 3-after mixing, solution stirs, passes through high pressure homogenizer homogenizing;
Step (S1300) is prepared collagen/hydroxyapatite/nano-cellulose composite: by the Ca that contains of 0.2-0.8mol/l
2+solution splashes in collagen/nano-cellulose composite solution prepared by step (S1200), and the mol ratio of Ca/P is set to 1.67, stirs, and with alkaline solution, regulates pH value precipitation, by precipitate lyophilization, makes artificial bone.
2. preparation method according to claim 1, wherein, described containing PO
4 3-solution is (NH
4)
2hPO
4, Na
2hPO
4and H
3pO
4in any one.
3. preparation method according to claim 1, wherein, described containing Ca
2+solution is CaCl
2, Ca (NO
3)
2and Ca (OH)
2in any one.
4. preparation method according to claim 1, wherein, the described alkaline solution that regulates pH value is any one in ammonia, sodium hydroxide and calcium hydroxide.
5. preparation method according to claim 1, wherein, described in step (S1300), pH value is adjusted to 7-9.
6. preparation method according to claim 1, wherein, stirs 20-40 minute in step (S1100), stirs 1-2h in step (S1300).
7. preparation method according to claim 1, wherein, the particle diameter of the described nano-cellulose providing is 2-100nm.
8. according to artificial bone that in claim 1-7, any one preparation method obtains.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642251A (en) * | 2013-12-12 | 2014-03-19 | 石家庄铁道大学 | Artificial bone material for B-ultrasonic detection and preparation method thereof |
| EP3532117B1 (en) | 2016-10-28 | 2023-08-02 | CELLINK Bioprinting AB | Preparation and applications of 3d bioprinting bioinks for repair of bone defects, based on cellulose nanofibrils hydrogels with natural or synthetic calcium phosphate particles |
| WO2018078130A1 (en) * | 2016-10-28 | 2018-05-03 | Paul Gatenholm | Preparation and applications of 3d bioprinting bioinks for repair of bone defects, based on cellulose nanofibrils hydrogels with natural or synthetic calcium phosphate particles |
| CN108419194B (en) * | 2017-02-10 | 2021-04-30 | 华邦电子股份有限公司 | Bone conduction hearing aid and bone conduction loudspeaker |
| WO2019002912A1 (en) * | 2017-06-27 | 2019-01-03 | ETH Zürich | Nanocomposite materials comprising cationic nanoparticles and anionic polymers useful in methods for 3d printing thereof |
| CN108478874B (en) * | 2018-04-25 | 2020-11-27 | 信阳师范学院 | Preparation method of hydroxyethyl chitosan nano composite bone scaffold material |
| CN109078220A (en) * | 2018-08-27 | 2018-12-25 | 白晋 | A kind of compound formulation comprising autologous collagen albumen and its application |
| CN110157170B (en) * | 2019-06-05 | 2021-07-20 | 东华大学 | Polylactic acid/nano-cellulose/hydroxyapatite composite material and preparation thereof |
| CN111643729B (en) * | 2020-06-28 | 2022-04-26 | 四川大学华西医院 | Drug-loaded bone scaffold material and preparation method thereof, and functional hybrid bone scaffold and preparation method thereof |
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