CN103656740A - Brushite-calcium silicate/chitosan composite bone cement with rapid and controllable biodegrability - Google Patents
Brushite-calcium silicate/chitosan composite bone cement with rapid and controllable biodegrability Download PDFInfo
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- CN103656740A CN103656740A CN201310698336.5A CN201310698336A CN103656740A CN 103656740 A CN103656740 A CN 103656740A CN 201310698336 A CN201310698336 A CN 201310698336A CN 103656740 A CN103656740 A CN 103656740A
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Abstract
The invention relates to brushite-calcium silicate/chitosan composite bone cement with rapid and controllable biodegrability. The brushite-calcium silicate/chitosan composite bone cement comprises three parts of composite power I, composite powder II and a curing liquid which are stored separately, wherein the composite power I is formed by mixing MCPM (monocalcium phosphate monohydrate) and MgHPO4*3H2O; the composite powder II is formed by mixing calcium phosphate and calcium silicate with a molar ratio of calcium and silicon larger than 1:1, and calcium phosphate is a mixture of one or two of beta-TPC (tertiary calcium phosphate) and alpha-TCP; the curing liquid adopts a chitosan and citric acid solution; and the mass ratio of the composite power I to the composite power II is (0.3-1.5):1, and the ratio of the total mass of the composite power I and the composite power II to the volume of the curing liquid, namely the solid-to-liquid ratio is (1.5-2.7):1 g/ml. On the basis of that appropriate curing time and certain compressive strength are guaranteed, the brushite-calcium silicate/chitosan composite bone cement has continuous, rapid and controllable biodegrability.
Description
Technical field
The present invention relates to a kind of quick controlled degradation calcium phosphate composite bone cement, belong to medical hard tissue repairing material field.
Background technology
Calcium phosphate bone cement is mainly divided into two classes: hydroxyapatite bone cement and brushite bone cement.Although hydroxyapatite bone cement accounts for leading low level in clinical practice at present, the research deepening continuously is in recent years found: such bone cement is slow because of degradation rate, has greatly limited its bone and has rebuild ability.Brushite bone cement be at first in 1989 by Mirtchi and
by MCPM (Ca (H
2pO
4) H
2o) and β-TCP (Ca
3(PO
4)
2) mixed-powder adds that water makes, the brushite bone cement that this original formulation makes solidifies too fast, in 30s, solidifies, and another mechanical strength is not high, be only 1MPa; And meeting release hydrogen ions in the process of this kind of bone cement firming body degradation in vivo, cause local PH too low, tissue is produced to certain toxic and side effects, also have being scattered of a large amount of particulate matters, and the granule being scattered can damage other organs of human body after entering human recycle system; Except there is the tendency changing to hydroxyapatite in this its material internal, cause the defects such as degradation capability degeneration of material, greatly limited the application and research of such bone cement.
Summary of the invention
The present invention relates to a kind of quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement, this composite bone cement is guaranteeing, on the basis of suitable hardening time and certain comprcssive strength, to have controlled continuously and healthily degradation capability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
Quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it comprises composite granule one, composite granule two and consolidation liquid three parts, each several part is deposited separately, wherein: described composite granule one is by MCPM(Ca (H
2pO
4)
2h
2o) and MgHPO
43H
2the mixed system of O forms, and the mixed system of calcium silicates that described composite granule two is greater than 1:1 by calcium phosphate and calcium silicon mol ratio forms, and described calcium phosphate is β-TCP (Ca
3(PO
4)
2) and α-TCP (Ca
3(PO
4)
2) in one or both mixing, described consolidation liquid is the solution of chitosan and citric acid; Mass ratio between described composite granule one and composite granule two is 0.3-1.5:1, and described composite granule one and the gross mass of composite granule two and the volume ratio of consolidation liquid are that solid-to-liquid ratio is 1.5-2.7:1g/ml.
Press such scheme, in described composite granule one, each component is by mass percentage: MgHPO
43H
2o1-20%, surplus is MCPM(Ca (H
2pO
4)
2h
2o), in described composite granule two, each component is by mass percentage: calcium silicates 30-90%, and surplus is calcium phosphate, and in described consolidation liquid, the mass concentration of chitosan is 0.05-0.22g/ml, and the mass concentration of citric acid is 0.06-0.26g/ml.
Press such scheme, described calcium silicates ((CaO)
x(SiO
2)
y) in calcium silicon mol ratio be that x/y is 1.5-4:1.
Press such scheme, described calcium silicates can prepare in accordance with the following methods: according to calcium silicon mol ratio in calcium silicates to be synthesized (x/y ratio), be the mol ratio of tetraethyl orthosilicate and four water-calcium nitrate, choose tetraethyl orthosilicate (TEOS) and four water-calcium nitrate, tetraethyl orthosilicate (TEOS) is joined in concentrated nitric acid solution and stirs 1-2 hour, then in 50-70 ℃, drip wherein four water-calcium nitrate (Ca (NO
3)
24H
2o) ethanol solution, stirring reaction 22-24h, dry except desolventizing, 900 ℃ of-1100 ℃ of roasting 2-3 hour, cooling, grind, obtain calcium silicate powder standby.
Press such scheme, described baking temperature 110-120 ℃, be 24-36h drying time.
Press such scheme, described quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement also comprises drug molecule component.The consumption of described drug molecule component is determined according to the character of medication and clinical needs.
Press such scheme, in described quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement, the particle diameter of calcium phosphate, calcium silicates and magnesium hydrogen phosphate is all less than 100 μ m.
Press such scheme, described consolidation liquid is chitosan to be joined in citric acid solution after citric acid is dissolved in water again, and ultrasonic dissolution obtains.
The using method of above-mentioned quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement is: composite granule one, composite granule two and consolidation liquid fully mixed to 0.5-1.5min by preset proportion and obtains injectable pulpous state composite bone cement and use, or through post processing: the firming body that obtains composite bone cement in mould after it solidifies is used again.
Beneficial effect of the present invention: quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement that the present invention obtains has on the basis of suitable hardening time and suitable comprcssive strength, there is degradation capability continuously and healthily, and by the ratio between adjusting MCPM and TCP, can realize the controllable adjustment of degradation rate, and it has certain cohesiveness can prevent being scattered of material, the anti-microbial property that separately it has chitosan concurrently, can be according to clinical needing random-shaping or for injectable treatment, meet the needs for bone, tooth defect repair.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the composite bone cement material that obtains of the embodiment of the present invention after solidifying 6 hours.By XRD spectra, can be found out: the thing phase composition of solidifying end-product is brushite (DCPD; CaHPO
42H
2o)), silico-calcium gel (C-S-H), TCP and a small amount of hydroxyapatite.
Fig. 2 is the scanning electron microscope (SEM) photograph after the composite bone cement material cured that obtains of the embodiment of the present invention 1.
Fig. 3 is the XRD figure spectrum of the calcium silicates that obtains of the embodiment of the present invention 1, a Ca in figure
2siO
4, b Ca
3siO
5.
The specific embodiment
Embodiment 1
Fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it is comprised of composite granule one, composite granule two and consolidation liquid three parts, and each component is deposited separately, wherein: described composite granule one is by MCPM1.2g, MgHPO
43H
2o 0.2g is mixed to get, and composite granule two is by β-TCP (Ca
3(PO
4)
2) 0.7g, α-TCP (Ca
3(PO
4)
2) 0.7g, calcium silicates ((CaO)
7(SiO
2)
3) the mixed system of 1.2g forms, consolidation liquid is chitosan and Fructus Citri Limoniae aqueous acid, in consolidation liquid, the mass concentration of citric acid is 0.06g/ml, and the mass concentration of chitosan is 0.05g/ml, and the gross mass of composite granule one and composite granule two is 1.5g/mL with the ratio of consolidation liquid volume.
The preparation of consolidation liquid: 2.4g citric acid is dissolved in 40ml deionized water, then 2g chitosan is slowly joined in the citric acid solution at the uniform velocity stirring, ultrasonic dissolution obtains consolidation liquid in 6 hours, and shady place saves backup.
The preparation of calcium silicate powder: 25.7ml tetraethyl orthosilicate (TEOS) is joined in 20ml concentrated nitric acid solution and stirred one hour.Meanwhile, by 63.92g four water-calcium nitrate (Ca (NO
3)
24H
2o) be dissolved into and in the dehydrated alcohol of 85.63ml, join to obtain the ethanol solution of four water-calcium nitrate.Then under 60 ℃ of conditions, four water-calcium nitrate solution is slowly added drop-wise in tetraethyl orthosilicate solution, stirring reaction 24 hours, under 120 ℃ of conditions, evaporate dried overnight after 900 ℃ of roastings 2 hours, cooling rear grinding, screening, obtain calcium silicates ((CaO)
7(SiO
2)
3) powder body, be kept in exsiccator standby.The XRD spectra of described calcium carbonate powder is shown in Fig. 3, and in figure, a is Ca
2siO
4characteristic diffraction peak, b is Ca
3siO
5characteristic diffraction peak.
Using method: after above-mentioned composite granule one and composite granule two machineries are mixed, add wherein the consolidation liquid of respective amount, after rapid stirring 0.5-1.5 minute, obtain injectable fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement.This capable of injecting bone cement can solidify about 25 minutes, under 37 ℃ of tepidarium conditions, solidify comprcssive strength two days later and can reach 2MPa, be injected into internal diameter and be and in 6mm, the high column type grinding tool for 2mm, treat that it solidifies 10 days degradable 15wt% left and right in the phosphate buffer that firming body of obtaining is 7 at pH.The XRD figure spectrum that this capable of injecting bone cement solidifies after 6h is shown in Fig. 1, as seen from Figure 1: the main thing phase composition of solidifying end-product is brushite (DCPD; CaHPO
42H
2o)), silico-calcium gel (C-S-H), TCP and hydroxyapatite.SEM figure is shown in Fig. 2.Above-mentioned bone cement is solidified to firming body after one hour and insert in the phosphate buffer that 37 ℃, PH are 7 and shake 24 hours, mass loss is less than 1% of its initial mass, and under similarity condition, the mass loss of brushite bone cement can reach 23% of its initial mass.
Embodiment 2
Fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it is comprised of composite granule one, composite granule two and consolidation liquid three parts, and each component is deposited separately, wherein: described composite granule one is by MCPM1.2g, MgHPO
43H
2o 0.2g is mixed to get, and composite granule two is by β-TCP (Ca
3(PO
4)
2) 0.2g, α-TCP (Ca
3(PO
4)
2) 1.2g, calcium silicates ((CaO)
7(SiO
2)
3) the mixed system of 1.2g forms, consolidation liquid is the solution of chitosan and citric acid, in consolidation liquid, the mass concentration of citric acid is 0.175g/ml, and the mass concentration of chitosan is 0.14g/ml, and the ratio of composite granule one and the gross mass of composite granule two and the volume of consolidation liquid is 2.0g/ml.
The configuration of consolidation liquid: 7g citric acid is dissolved in 40ml deionized water, then 5.6g chitosan is slowly joined in the citric acid solution at the uniform velocity stirring, ultrasonic dissolution obtains consolidation liquid in 6 hours, and shady place saves backup.
The preparation of calcium silicate powder is with embodiment 1.
Using method: after above-mentioned composite granule one and composite granule two machineries are mixed, add wherein respective amount consolidation liquid, rapid stirring 0.5-1.5 minute, injects grinding tool, treats that it solidifies can obtain the packing material with fast degradation ability for bone defect repair.Bone cement can solidify about 5 minutes, under 37 ℃ of tepidarium conditions, solidify comprcssive strength two days later and can reach 10MPa, be injected into internal diameter and be and in 6mm, the high column type grinding tool for 2mm, treat that it solidifies 10 days degradable 15wt% left and right in the phosphate buffer that firming body of obtaining is 7 at pH.Above-mentioned bone cement is solidified to firming body after one hour and insert in the phosphate buffer that 37 ℃, PH are 7 and shake 24 hours, mass loss is less than 1% of its initial mass.
Embodiment 3
Fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it is comprised of composite granule one, composite granule two and consolidation liquid three parts, and each component is deposited separately, wherein: described composite granule one is by MCPM2.09g, MgHPO
43H
2o 0.2g is mixed to get, and composite granule two is by β-TCP (Ca
3(PO
4)
2) the mixed system of 0.51g, dicalcium silicate 1.2g forms, consolidation liquid is the solution of chitosan and citric acid, in consolidation liquid, the mass concentration of citric acid is 0.175g/ml, and the mass concentration of chitosan is 0.14g/ml, and the gross mass of composite granule one and composite granule two is 2.0g/mL with the ratio of consolidation liquid volume.
The preparation of consolidation liquid is with embodiment 2.
Using method: after above-mentioned composite granule one and composite granule two machineries are mixed, the consolidation liquid that adds wherein respective amount, rapid stirring 0.5-1.5 minute, injects grinding tool, treats that it solidifies can obtain the packing material with fast degradation ability for bone defect repair.This composite bone cement can solidify about 4 minutes, solidify comprcssive strength two days later and can reach 10MPa, be injected into internal diameter and be and in 6mm, the high column type grinding tool for 2mm, treat that it solidifies 10 days degradable 25wt% left and right in the phosphate buffer that firming body of obtaining is 7 at pH.
Embodiment 4
Fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it is comprised of composite granule one, composite granule two and consolidation liquid three parts, and each component is deposited separately, wherein: described composite granule one is by MCPM2.09g, MgHPO
43H
2o 0.2g is mixed to get, and composite granule two is by β-TCP (Ca
3(PO
4)
2) 0.51g, calcium silicates ((CaO)
6(SiO
2)
4) the mixed system of 1.2g forms, consolidation liquid is the solution of chitosan and citric acid, in consolidation liquid, the mass concentration of citric acid is 0.175g/ml, and the mass concentration of chitosan is 0.14g/ml, and the gross mass of composite granule one and composite granule two is 2.0g/mL with the ratio of consolidation liquid volume.
The preparation of consolidation liquid is with embodiment 2.
Calcium silicates ((CaO)
6(SiO
2)
4) preparation of powder body: 34.2ml tetraethyl orthosilicate (TEOS) is joined in 26.7ml concentrated nitric acid solution and stirred 1 hour.Meanwhile, by 54.8g four water-calcium nitrate (Ca (NO
3)
24H
2o) be dissolved into and in dehydrated alcohol, join to obtain the ethanol solution of four water-calcium nitrate.Then under 60 ℃ of conditions, four water-calcium nitrate solution is slowly added drop-wise in tetraethyl orthosilicate solution, stirring reaction 24 hours evaporates and spends the night under 120 ℃ of conditions.After dry, 900 ℃ of roastings 2 hours, cooling rear grinding, screened, and obtains calcium silicates ((CaO)
6(SiO
2)
4) powder body, be kept in exsiccator standby.
Using method: after above-mentioned composite granule one and composite granule two machineries are mixed, the consolidation liquid that adds wherein respective amount, rapid stirring 0.5-1.5 minute, injects grinding tool, treats that it solidifies can obtain the packing material with fast degradation ability for bone defect repair.This bone cement can solidify about 6 minutes, solidify comprcssive strength two days later and can reach 10MPa, be injected into internal diameter and be and in 6mm, the high column type grinding tool for 2mm, treat that it solidifies 10 days degradable 25wt% left and right in the phosphate buffer that firming body of obtaining is 7 at pH.
Embodiment 5
Carry the compound capable of injecting bone cement of curcumin fast degradation biological activity brushite-calcium silicates/chitosan: it is partly comprised of composite granule one, composite granule two, consolidation liquid, in consolidation liquid, be loaded with curcumin, each component is deposited separately, wherein: described composite granule one is by MCPM1.2g, and MgHPO
43H
2o 0.2g is mixed to get, and composite granule two is by β-TCP (Ca
3(PO
4)
2) 0.4g, α-TCP (Ca
3(PO
4)
2) 1.0g, calcium silicates ((CaO)
7(SiO
2)
3) the mixed system of 1.2g forms, consolidation liquid is the solution of chitosan and citric acid, in consolidation liquid, the mass concentration of citric acid is 0.2g/ml, the mass concentration of chitosan is 0.14g/ml, the concentration of curcumin is 0.0015g/ml, and the gross mass of composite granule one and composite granule two is 1.5g/mL with the ratio of consolidation liquid volume.
The preparation of consolidation liquid: 8g citric acid and 0.06g curcumin are dissolved in 40ml deionized water, at ambient temperature, 5.6g chitosan are slowly joined in the citric acid solution at the uniform velocity stirring, ultrasonic dissolution 6 hours, obtains consolidation liquid, saves backup at shady place.
The preparation of calcium silicate powder is with embodiment 1.
Using method: after above-mentioned composite granule one and composite granule two machineries are mixed, the consolidation liquid that adds wherein respective amount, after rapid stirring 0.5-1.5 minute, obtain carrying curcumin injectable fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement.This medicine carrying bone cement can solidify about 4 minutes, under 37 ℃ of tepidarium conditions, solidify comprcssive strength two days later and can reach 10MPa, be injected into internal diameter and be in 6mm, the high column type grinding tool for 2mm, treat its solidify firming body of obtaining can the phosphate buffer that be 7 at pH in 10 days degradable 15wt% left and right.
Claims (6)
1. quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it is characterized in that: it comprises composite granule one, composite granule two and consolidation liquid three parts, each several part is deposited separately, wherein: described composite granule one is by MCPM(Ca (H
2pO
4)
2h
2o) and MgHPO
43H
2the mixed system of O forms, and the mixed system of calcium silicates that described composite granule two is greater than 1:1 by calcium phosphate and calcium silicon mol ratio forms, and described calcium phosphate is β-TCP (Ca
3(PO
4)
2) and α-TCP (Ca
3(PO
4)
2) in one or both mixing, described consolidation liquid is the solution of chitosan and citric acid; Mass ratio between described composite granule one and composite granule two is 0.3-1.5:1, and described composite granule one and the gross mass of composite granule two and the volume ratio of consolidation liquid are 1.5-2.7:1g/ml.
2. quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement according to claim 1, is characterized in that: in described composite granule one, each component is by mass percentage: MgHPO
43H
2o1-20%, surplus is MCPM, and in described composite granule two, each component is by mass percentage: calcium silicates 30-90%, and surplus is calcium phosphate, in described consolidation liquid, the mass concentration of chitosan is 0.05-0.22g/ml, and the mass concentration of citric acid is 0.06-0.26g/ml.
3. quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement according to claim 1, is characterized in that: the calcium silicon mol ratio in described calcium silicates is 1.5-4:1.
4. quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement according to claim 1, is characterized in that: it also comprises drug molecule component.
5. quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement according to claim 1, is characterized in that: the particle diameter of described calcium phosphate, calcium silicates and magnesium hydrogen phosphate is all less than 100 μ m.
6. the using method of quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement claimed in claim 1, it is characterized in that: composite granule one, composite granule two and consolidation liquid are fully mixed to 0.5-1.5min by preset proportion and obtain injectable pulpous state composite bone cement and use, or through post processing: the firming body that obtains composite bone cement in mould after it solidifies is used again.
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Cited By (3)
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|---|---|---|---|---|
| CN104857568A (en) * | 2015-05-29 | 2015-08-26 | 河南科技大学 | Calcium phosphate-based bone cement with antibacterial property and preparation method thereof |
| RU2725767C1 (en) * | 2019-11-07 | 2020-07-06 | федеральное государственное бюджетное образовательное учреждение высшего образования "Омский государственный университет им. Ф.М. Достоевского" | Method for producing brushite granules in a chitosan matrix |
| CN111514372A (en) * | 2020-04-17 | 2020-08-11 | 上海交通大学医学院附属第九人民医院 | CaCO3MgO nano composite and application thereof in bone repair |
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| CN111514372A (en) * | 2020-04-17 | 2020-08-11 | 上海交通大学医学院附属第九人民医院 | CaCO3MgO nano composite and application thereof in bone repair |
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| Publication number | Publication date |
|---|---|
| CN103656740B (en) | 2015-06-24 |
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