CN101961509B - Silk fibroin/calcium phosphate bone cement composite material and preparation method thereof - Google Patents
Silk fibroin/calcium phosphate bone cement composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silk fibroin/calcium phosphate bone cement composite material and a preparation method thereof. In the preparation of the main component of tracalcium phosphate of calcium phosphate bone cement, the tracalcium phosphate is prepared in a mode of cooling by stages after calcining a tracalcium phosphate precursor which is synthesized by adopting a liquid-phase reaction method; composite powder is prepared by adding water-insoluble silk fibroin powder into the calcium phosphate bone cement; and the silk fibroin/calcium phosphate bone cement composite material with a similar structure to a bone is converted by blending the composite powder in a certain liquid-solid ratio to form paste. The silk fibroin/calcium phosphate bone cement composite material has high mechanical property and biocompatibility, is directly injected in a surgical site by using a syringe, and can be molded and cured accurately to serve as a filling material for bone repair; or the composite material can be implanted into a body to be used as an implant material for the bone repair after being self-cured in the in vitro environment. The technical scheme of the invention greatly improves preparation working conditions of the calcium phosphate bone cement, reduces preparation cost, and expands the medical application of silk fibroin.
Description
Technical field
The present invention relates to a kind of biomaterial for medical purpose and preparation method thereof, particularly a kind of is that matrix, silk fibroin powder are composite that strengthens body and preparation method thereof with the calcium phosphate bone cement.
Background technology
Calcium phosphate bone cement generally is made up of powder and consolidation liquid that two or more synthos mix, and both are in harmonious proportion evenly according to a certain percentage during use, can solidify voluntarily under room temperature or human body environment and accurate plastotype.Bone cement generation curing reaction end product is mainly the hydroxyapatite similar to the human body bone component, can conduct osteogenesis, progressively be organized and absorb and generation osteanagenesis effect, has excellent biological compatibility, at present in the advantage and the vast market prospect that have shown huge clinical practice aspect the bone injury reparation.But shortcomings such as still there is obvious deficiency in traditional calcium phosphate bone cement, and is big as fragility, and intensity is low are mainly used in nonweight-bearing bone defect, and this has seriously limited it in the more application of wide spectrum.Therefore, the mechanical property that how to improve calcium phosphate bone cement is to realize that it is applied to clinical and gives full play to the important foundation of its bone defect repair function.
At present, some scholars are devoted to how to improve the Mechanical Properties of calcium phosphate bone cement one after another both at home and abroad, because of different its performances of the composition of calcium phosphate bone cement also difference, combination property that there are some researches show tetracalcium phosphate is better, and the preparation condition of tetracalcium phosphate is harsh, must from the high temperature furnace more than 1400 ℃, take out chilling, not have its production marketing so far on the market.The method that tetracalcium phosphate is produced can be divided into two big classes, and a class is dry method (US Patent 5545254), another kind of be wet method (carry red lotus, Yan Yuhua, Wang Youfa etc. Study on Preparation of Tetracalcium Phosphate Powder. silicate circular, 2002, (4): 56-58).Adopt the synthetic calcium phosphate bone cement of dry method or wet method, a key factor that influences tetracalcium phosphate purity is exactly the type of cooling, research is in the past thought and must be taken out chilling in 1400 ℃ and above stove, could obtain the higher tetracalcium phosphate of purity, as at document " preparation of medical calcium phosphate bone cement and Performance Experiment " (Zheng Zhi, Xiang Qijun, .[J such as Liu Yong] biomedical engineering's magazine, 2006,23 (5): 1048-1051.), " Study on Preparation of Tetracalcium Phosphate Powder " (carries red lotus, Yan Yuhua, .[J such as Wang Youfa] the silicate circular, 2002, (4): 56-58.) and " preparation of calcium phosphate bone cement and performance " (Zhang Aijuan, the big .[J of Wang Wei] the Materials Science and Engineering journal, 2008,26 (5): report is all arranged 779-782), under 1400 ℃ and above temperature, take out sample, require all very high to stove and operation.
Calcium phosphate bone cement and various material are carried out compound, obtained some effects as chitosan, absorbable fibre, collagen etc.(Hockin H.K.Xu such as Hockin H.K.Xu, Michael D.Weir, Elena F.Burgueral, et al.Injectable and macroporous calcium phosphate cement scaffold.Biomaterials, 2006,27:4279-4287) adopt absorbable fibre to improve the calcium phosphate bone cement bending strength, though its bending strength is (3.2 ± 1.0) MPa when sample contains 5% fiber, but this numerical value still is smaller, and fiber is difficult for being dispersed in the calcium phosphate bone cement in addition.Chinese invention patent " preparation method of calcium phosphate cement/chitosan-gelatine compound rest " (CN101125223), though the material porosity of preparation is higher, compressive strength only is 1.52-1.82MPa.(Wang X. during document " utilizes phosphonized chitosan to improve the research of calcium phosphate bone cement performance ", Ma J., Wang Y., He B., [J] Polym.Sci., 2002,4:325-332) in, reported and utilized the soluble chitosan of different molecular weight, different deacetylation and different Phosphation substitution values to add in the calcium phosphate bone cement, can postpone the hardening time of bone cement a little.Document " collagen scaffold strengthens mechanics and the bone formation performance research of self-curable calcium phosphate bone cement " (Chen Dafu, Tian Wei, the brave .[J that just waited of row] Chinese orthopedics magazine, 2006,14 (18): research 1410-1412) is thought, collagen scaffold can improve the mechanical property of CPC, the raising of bending strength ratio CPC 64.2%; Result of study (Youji Miyamoto is also arranged, Kunio Ishikawa, Masaaki Takechi, et al.Basic properties of calcium phosphate cement containing atelocollagen in its liquid or powder phases.Biomaterials, 1998,19:707-715) show, adopt the setting time of collagen longer.
Existing nontoxic, the nonirritant of fibroin albumen that studies show that, have excellent biological compatibility, can promote the growth of human body cell, have biodegradability (David L.Kaplan.Silk-based biomaterials.Biomaterials, 2003,24:401-416).Just because of because fibroin albumen has these excellent biology performances, caused showing great attention to of people, launched the many-sided applied research of fibroin albumen, as silk fibroin protein is used for medicine controlled release carrier, anticoagulant material, functional cell culture matrix, biosensor, artificial ligament, artificial tendon, contact lens, artificial skin etc.Because contain many polar groups such as hydroxyl, carboxyl etc. on the fibroin macromole, the compatibility of these groups and polarity inorganic material is good, can be used for improving the mechanical property of synthos.Chinese invention patent (CN1736492) discloses a kind of fibroin hydroxyapatite composite material and preparation method thereof, though inventing resulting composite, this has the good mechanical performance, but need 110～130 ℃ temperature under dry solidification, do not have an injectivity, can not self-curing, can not solidify accurate forming in vivo, can only use as embedded material, influence the application of fibroin albumen in the scarce reparation of bone greatly; In addition, the mechanical property of its material is influenced at the hydroxyapatite distributing homogeneity by fibroin fiber, and fiber exists and is difficult for homodisperse shortcoming.
Utilize polar group such as carboxyl on the good biocompatibility of fibroin albumen and the fibroin macromole, hydroxyls etc. discharge biocompatibility and the mechanical property that calcium ion is combined to improve bone cement in synthos, before the present invention makes, the fibroin albumen that the research fibroin albumen/calcium phosphate bone cement adopts all is that impalpable structure is main water-soluble fibroin, at document " preparation of CPC/SF composite " (Xie Ruijuan, Deng Qiming, Zhan Hong continent .[J] textile journal, 2009,30 (10): 5-9.), " InfIuences of siIk fibroin on the compressive strength and injectability of calcium phosphate cement " (Chen Xiao-qing, Yang Hui-lin, Gan MIn-feng, Xie Rui-juan, Chen Liang, Zhu Xue-song, Wang Gen-lin, GuYong.[J] Chinese Tissue Engineering Study and clinical rehabilitation, 2008,12 (45): 8985-8988.) (do Man Feng with " fibroin albumen is to the influence of injectable calcium phosphate bone cement cell compatibility ", Yang Huilin, Gu Yanzheng, Chen Xiaoqing, Wang Genlin, Chen Liang, Zhu Xuesong, the beautiful .[J of Xie Rui] Chinese Tissue Engineering Study and clinical rehabilitation, 2009,73 (3): visible report 427-431.), this no fixed structure is that main water-soluble fibroin albumen can be dissolved in the liquid phase when curing reaction, cause finally retaining in the firming body fibroin albumen seldom; And the viscosity resistance of this kind fibroin albumen is big, thus can only add the fibroin albumen of a small amount of (less than 3%), otherwise can influence its injectivity.
Summary of the invention
The purpose of this invention is to provide a kind of fibroin albumen/calcium phosphate cement composite material with good mechanical performance, biocompatibility and suitable setting time and preparation method thereof.
Realize that the object of the invention technical scheme is: a kind of fibroin albumen/calcium phosphate cement composite material, the component of its firming body comprises calcium phosphate bone cement and water-insoluble silk fibroin powder, by weight percentage, water-insoluble silk fibroin powder is 0.5～30%, and all the other are calcium phosphate bone cement.
The preparation method of above-mentioned fibroin albumen/calcium phosphate cement composite material may further comprise the steps:
(1) will adopt the synthetic tetracalcium phosphate precursor of liquid phase reactor method after calcining under 1450～1500 ℃ the temperature conditions, insulation, logical nitrogen or air are quickly cooled to 1280～1320 ℃ in the stove, take out the back and in air, be cooled to 100～105 ℃, put into dry environment again and be cooled to room temperature, obtain tetracalcium phosphate;
(2) press the ratio requirement of bone cement, tetracalcium phosphate is mixed levigate with synthos, obtain calcium phosphate bone cement;
(3) the water-soluble fibroin egg albumen powder that will adopt spray drying method for preparation to obtain places alcoholic solution to handle, and dry back obtains water-insoluble silk fibroin powder under 50～80 ℃ of temperature again;
(4) water-insoluble silk fibroin powder is joined in the calcium phosphate bone cement in 0.5～30% ratio, mix through the ball mill ball milling, make fibroin albumen/calcium phosphate bone cement composite granule;
(4) ratio in liquid-solid ratio 0.30～0.98ml/g joins consolidation liquid in fibroin albumen/calcium phosphate bone cement composite granule, reconciles into uniform pastel, solidify to form fibroin albumen/calcium phosphate cement composite material firming body.
Compared with prior art, the present invention has the following advantages:
1, the tetracalcium phosphate that synthesizes of the present invention adopts the method for segmentation cooling to make tetracalcium phosphate, the method of segmentation cooling is: the phase I is in the time of 1450～1500 ℃, logical nitrogen or air are quickly cooled to 1280～1320 ℃ in the stove, second stage is put into dry environment and is cooled to room temperature after about 1300 ℃ taking-up is cooled to 100～105 ℃ in air from stove; Do not need from the high temperature furnace more than 1450 ℃, to take out chilling, improve the preparation work condition widely, reduced preparation cost;
2, the present invention adopts water-insoluble silk fibroin powder to join in the solid phosphoric acid calcium salt powder body, the easy mix homogeneously of fibroin albumen and synthos, both mix the composite granule that the back is formed, but under the effect of consolidation liquid in room temperature or simulation body fluid environment self-curing, arbitrarily plastotype, do not need as the fibroin hydroxyapatite composite material will be under 110～130 ℃ temperature dry solidification, and injectable, also can directly be solidified into artificial bone.Comprcssive strength 15～24.8MPa can improve 26.8% than pure phosphoric acid calcium bone cement maximum, and setting time is suitable, is 12～20min.Owing to do not use poisonous chemical reagent in preparation process, the fibroin albumen/calcium phosphate cement composite material that makes by technical solution of the present invention is nontoxic, harmless to human body, and has excellent biological compatibility, is a kind of Green Product.Fibroin albumen, the source is abundant, produces conveniently, and equipment and the technology of preparation of product are simple, low, the high efficiency of cost.Therefore, has vast market prospect.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of a kind of tetracalcium phosphate of providing of the embodiment of the invention;
Fig. 2 is the component analysis figure of a kind of tetracalcium phosphate of providing of the embodiment of the invention.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described.
Embodiment one
The preparation process of fibroin albumen/calcium phosphate cement composite material that present embodiment provides is as follows:
(1) preparation of tetracalcium phosphate
With (NH
4)
2HPO
4Solution is 1.67 ratio in Ca/P (calcium/phosphorus) mol ratio, is added drop-wise to Ca (NO
3)
24H
2In the O solution, pH value remains on more than 9 in the dropping process, dropwises, and continues stirring reaction 3h, staticly settles 24h, is 2.0 ratio in whole system Ca/P mol ratio, drips Ca (NO simultaneously in above-mentioned suspension
3)
24H
2O solution and (NH
4)
2CO
3Solution after dripping, continues to filter behind the ageing reaction 24h, and filter cake is put into dry 12h in 110 ℃ of baking ovens.To place high temperature furnace by the synthetic tetracalcium phosphate precursor of above-mentioned liquid phase reactor method, speed with 360 ℃/h is warming up to 1500 ℃, behind the insulation 8h, advance nitrogen and be cooled fast to 1300 ℃ of taking-ups, after in air, being cooled to 105 ℃, put into dry environment and be cooled to room temperature, obtain tetracalcium phosphate, grind the back and cross 250 order molecular sieves.
Referring to accompanying drawing 1, it is the x-ray diffraction pattern of the sample that provides of present embodiment; Can see that by Fig. 1 institute's test sample product are tetracalcium phosphate.
Referring to accompanying drawing 2, it is that the tetracalcium phosphate that present embodiment provides adopts the component analysis figure that obtains after the high score software processes, and (A) is the standard C a of card 00-025-1137 among the figure
4O (PO
4)
2Diffraction maximum position figure, (B) the diffraction maximum position figure of the sample that provides for present embodiment; Can see diffraction maximum position and standard C a in the sample by Fig. 2
4O (PO
4)
2The diffraction maximum unanimity.
(2) preparation of fibroin albumen
After the silkworm silk that will give up is sloughed sericin, be dissolved in the ternary solution of calcium chloride, ethanol and deionized water, obtain silk fibroin solution through diafiltration, use spray drying device to be dried under 130 ℃ in inlet temperature, obtain the water-soluble fibroin egg albumen powder; Again this silk fibroin powder is passed through volumetric concentration 75% Ethanol Treatment 3 hours, after drying under 80 ℃ of temperature conditions, obtain non-water-soluble silk fibroin powder again.
(3) preparation of calcium phosphate bone cement solid phase
Tetracalcium phosphate and calcium hydrogen phosphate that step (1) is obtained were mixed into the calcium phosphate bone cement powder in 1: 1 in molar ratio, again with 0.8g set by step (2) silk fibroin powder of obtaining join in the 19.2g calcium phosphate bone cement powder, putting into the ball mill ball milling mixes, non-water-soluble silk fibroin powder is evenly dispersed in the calcium phosphate bone cement powder, makes fibroin albumen/calcium phosphate bone cement composite granule solid phase.
(4) preparation of calcium phosphate bone cement firming body
Consolidation liquid is added in the solid phase of step (3) acquisition in liquid-solid ratio 0.39ml/g ratio, after the modulation evenly the bone cement pastel is injected mould molding, be 37 ℃ in temperature, relative humidity is the demoulding behind the maintenance 4h in 100% the environment, sample is immersed in 37 ℃ the simulation body fluid to soak 20h again.Namely get calcium phosphate cement composite material (being numbered 1#), its performance is referring to table one.
Embodiment two
Technical scheme by embodiment one prepares non-water-soluble silk fibroin powder.
With (NH
4)
2HPO
4Solution is 1: 1.6 ratio in the Ca/P mol ratio, is added drop-wise to Ca (NO
3)
24H
2In the O solution, pH value remains on more than 9 in the dropping process, dropwises, and continues stirring reaction 3h, staticly settles 22h, is 2.0 ratio in whole system Ca/P mol ratio, drips Ca (NO simultaneously in above-mentioned suspension
3)
24H
2O solution and (NH
4)
2CO
3Solution, after dripping, continue to filter behind the ageing reaction 22h, filter cake is put into dry 12h is placed in the high temperature furnace in 110 ℃ of baking ovens, be warming up to 1500 ℃ with the speed of 360 ℃/h, behind the insulation 8h, advance nitrogen and be cooled fast to 1300 ℃ of taking-ups, in air, be cooled to 100 ℃ after, put into dry environment and be cooled to room temperature, obtain tetracalcium phosphate, grind the back and cross 250 order molecular sieves.
The 1.5g silk fibroin powder is joined in 13.5g tetracalcium phosphate and the calcium hydrogen phosphate system, put into the ball mill ball milling and mix, silk fibroin powder is evenly dispersed in the calcium phosphate bone cement powder, obtain solid phase.
In liquid-solid ratio 0.57ml/g ratio consolidation liquid is joined in the solid phase, after the modulation evenly the bone cement paste is injected mould molding, and place it in maintenance 48h in the normal temperature environment, and namely getting calcium phosphate cement composite material (being numbered 2#), its performance is referring to table one.
Embodiment three
Technical scheme by embodiment one prepares non-water-soluble silk fibroin powder.
With (NH
4)
2HPO
4Solution is 1: 1 ratio in the Ca/P mol ratio, is added drop-wise to Ca (NO
3)
24H
2In the O solution, pH value remains on more than 9 in the dropping process, dropwises, and continues stirring reaction 3h, staticly settles 20h, is 2.0 ratio in whole system Ca/P mol ratio, drips Ca (NO simultaneously in above-mentioned suspension
3)
24H
2O solution and (NH
4)
2CO
3Solution, after dripping, continue to filter behind the ageing reaction 24h, filter cake is put into dry 12h is placed in the high temperature furnace in 110 ℃ of baking ovens, be warming up to 1500 ℃ with the speed of 360 ℃/h, behind the insulation 8h, advance nitrogen and be cooled fast to 1300 ℃ of taking-ups, in air, be cooled to 102 ℃ after, put into dry environment and be cooled to room temperature, obtain tetracalcium phosphate, grind the back and cross 250 order molecular sieves.
0.96g fibroin silk fibroin powder is attached in tetracalcium phosphate that 11.04g is housed, the calcium hydrogen phosphate system, put into the ball mill ball milling and mix, silk fibroin powder is evenly dispersed in the calcium phosphate bone cement powder, make the solid phase of calcium phosphate cement composite material.
In liquid-solid ratio 0.51ml/g ratio consolidation liquid is joined in the solid phase, after the modulation evenly the bone cement pastel is injected mould molding, and to place it in temperature be 37 ℃, relative humidity is the demoulding behind the maintenance 4h in 100% the curing environment, sample after the demoulding be immersed in 37 ℃ simulation body fluid in 20h, namely get calcium phosphate cement composite material (being numbered 3#), its performance is referring to table one.
Embodiment four
Technical scheme by embodiment one prepares non-water-soluble silk fibroin powder.
With (NH
4)
2HPO
4Solution is 1: 1.7 ratio in the Ca/P mol ratio, is added drop-wise to Ca (NO
3)
24H
2In the O solution, pH value remains on more than 9 in the dropping process, dropwises, and continues stirring reaction 3h, staticly settles 24h, is 2.0 ratio in whole system Ca/P mol ratio, drips Ca (NO simultaneously in above-mentioned suspension
3)
24H
2O solution and (NH
4)
2CO
3Solution, after dripping, continue to filter behind the ageing reaction 20h, filter cake is put into dry 12h is placed in the high temperature furnace in 110 ℃ of baking ovens, be warming up to 1500 ℃ with the speed of 360 ℃/h, behind the insulation 8h, advance nitrogen and be cooled fast to 1300 ℃ of taking-ups, in air, be cooled to 105 ℃ after, put into dry environment and be cooled to room temperature, obtain tetracalcium phosphate, grind the back and cross 250 order molecular sieves.
At first with 0.45g set by step (1) silk fibroin powder of obtaining join 29.55g tetracalcium phosphate, calcium hydrogen phosphate and, in the type alpha tricalcium phosphate system, putting into the ball mill ball milling mixes, silk fibroin powder is evenly dispersed in the calcium phosphate bone cement powder, obtains solid phase material.
In liquid-solid ratio 0.35ml/g ratio consolidation liquid is added in the solid phase material that step (2) obtains, after the modulation evenly the bone cement paste is injected mould molding, and to place it in temperature be 37 ℃, relative humidity is the demoulding behind the maintenance 4h in 100% the curing environment, sample after the demoulding is immersed in 20h in 37 ℃ the deionized water, namely get the calcium phosphate bone cement material, be numbered 4#, its performance is referring to table one.
The performance of table one calcium phosphate bone cement
| Sample | Comprcssive strength (MPa) | Setting time (min) |
| 1# | 23.4 | 15 |
| 2# | 16.8 | 17 |
| 3# | 17.7 | 16 |
| 4# | 18.9 | 17 |
Claims (1)
1. the preparation method of a fibroin albumen/calcium phosphate cement composite material is characterized in that: may further comprise the steps:
(1) will adopt the synthetic tetracalcium phosphate precursor of liquid phase reactor method after calcining under 1450～1500 ℃ the temperature conditions, insulation, logical nitrogen or air are quickly cooled to 1280～1320 ℃ in the stove, take out the back and in air, be cooled to 100～105 ℃, put into dry environment again and be cooled to room temperature, obtain tetracalcium phosphate;
(2) press the ratio requirement of bone cement, tetracalcium phosphate is mixed levigate with synthos, obtain calcium phosphate bone cement;
(3) the water-soluble fibroin egg albumen powder that will adopt spray drying method for preparation to obtain places alcoholic solution to handle, and dry back obtains water-insoluble silk fibroin powder under 50～80 ℃ of temperature again;
(4) water-insoluble silk fibroin powder is joined in the calcium phosphate bone cement in 0.5～30% ratio, mix through the ball mill ball milling, make fibroin albumen/calcium phosphate bone cement composite granule;
(5) ratio in liquid-solid ratio 0.30～0.98 ml/g joins consolidation liquid in fibroin albumen/calcium phosphate bone cement composite granule, reconciles into uniform pastel, solidify to form fibroin albumen/calcium phosphate cement composite material firming body.
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| CN102552985B (en) * | 2012-01-20 | 2014-03-19 | 苏州大学 | Silk fibroin/calcium phosphate bone cement-based porous composite material and preparation method thereof |
| CN104043149A (en) * | 2014-06-20 | 2014-09-17 | 苏州大学 | Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof |
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| CN101502669A (en) * | 2009-03-05 | 2009-08-12 | 苏州大学 | Silk fibroin porous three-dimensional material and preparation method thereof |
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2010
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| CN1475533A (en) * | 2003-05-13 | 2004-02-18 | 北京理工大学 | Insoluble silk fibroin film and preparation of silk fibroin pipe |
| CN1560136A (en) * | 2004-03-04 | 2005-01-05 | 苏州大学 | Manufacture process of nano fibroin partical |
| CN101502669A (en) * | 2009-03-05 | 2009-08-12 | 苏州大学 | Silk fibroin porous three-dimensional material and preparation method thereof |
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