CN103656740B - 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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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 controlled degradation calcium phosphate composite bone cement fast, 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 current clinical practice, the research that deepens continuously in recent years finds: such bone cement because of degradation rate slow, greatly limit its bone remoulding ability.Brushite bone cement be at first in 1989 by Mirtchi and
by MCPM (Ca (H
2pO
4) H
2and β-TCP (Ca O)
3(PO
4)
2) mixed-powder adds water obtained, the obtained brushite bone cement solidification of this original formulation is too fast, and solidify in 30s, another mechanical strength is not high, is 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, certain toxic and side effects is produced to tissue, also has being scattered of a large amount of particulate matters, and the granule be scattered can damage other organs of human body after entering human recycle system; Except this its material internal exists the tendency changed to hydroxyapatite, cause the defects such as the degradation capability degeneration of material, greatly limit the application and research of such bone cement.
Summary of the invention
The present invention relates to a kind of controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement fast, this composite bone cement, on the basis ensureing suitable hardening time and certain comprcssive strength, has degradation capability controlled continuously and healthily.
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 part, and each several part is deposited separately, wherein: described composite granule one is by MCPM(Ca (H
2pO
4)
2h
2and MgHPO O)
43H
2the O system of mixing forms, and the calcium silicates system of mixing 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 and solid-to-liquid ratio are 1.5-2.7:1g/ml.
By 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.
By such scheme, described calcium silicates ((CaO)
x(SiO
2)
y) in calcium silicon mol ratio and x/y be 1.5-4:1.
By 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) the i.e. 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 drip four water-calcium nitrate (Ca (NO wherein in 50-70 DEG C
3)
24H
2o) ethanol solution, stirring reaction 22-24h, dry except desolventizing, 900 DEG C-1100 DEG C roasting 2-3 hour, cooling, grinding, obtains calcium silicate powder for subsequent use.
By such scheme, described baking temperature 110-120 DEG C, drying time is 24-36h.
By 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.
By 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 μm.
By such scheme, described consolidation liquid is dissolved into by citric acid after in water to join in citric acid solution by chitosan 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 are fully mixed 0.5-1.5min in setting ratio and obtains injectable pulpous state composite bone cement and use, or through post processing: the firming body obtaining composite bone cement in a mold after its solidification uses 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 the controllable adjustment by regulating the ratio between MCPM and TCP can realize degradation rate, and it has certain cohesiveness can prevent being scattered of material, anti-microbial property that separately it has chitosan concurrently, can random-shaping be needed according to clinical or for injectable treatment, meet the needs for bone, tooth defect repair.
Accompanying drawing explanation
Fig. 1 is that the composite bone cement material that the embodiment of the present invention obtains is composed in the XRD figure of solidification after 6 hours.Can be found out by XRD spectra: the thing phase composition of solidification 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 the embodiment of the present invention 1 obtains, a Ca in figure
2siO
4, b Ca
3siO
5.
Detailed description of the invention
Embodiment 1
Fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it is made up of composite granule one, composite granule two and consolidation liquid three part, 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 1.2g system of mixing 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 and the ratio of consolidation liquid volume are 1.5g/mL.
The preparation of consolidation liquid: be dissolved into by 2.4g citric acid in 40ml deionized water, then slowly joins 2g chitosan in the citric acid solution at the uniform velocity stirred, and 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 stir one hour.Meanwhile, by 63.92g four water-calcium nitrate (Ca (NO
3)
24H
2o) be dissolved in the dehydrated alcohol of 85.63ml and join to obtain the ethanol solution of four water-calcium nitrate.Then under 60 DEG C of conditions, four water-calcium nitrate solution is slowly added drop-wise in tetraethyl orthosilicate solution, stirring reaction 24 hours, 900 DEG C of roastings 2 hours evaporate dried overnight under 120 DEG C of conditions after, grinding after cooling, screening, obtains calcium silicates ((CaO)
7(SiO
2)
3) powder body, be kept in exsiccator for subsequent use.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 the mixing of composite granule two machinery, add the consolidation liquid of respective amount wherein, after rapid stirring 0.5-1.5 minute, obtain injectable fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement.This injecting bone cement can solidification in about 25 minutes, under 37 DEG C of tepidarium conditions, solidify comprcssive strength two days later can reach 2MPa, being injected into and treating that it solidifies the firming body obtained in the column type grinding tool that internal diameter is 6mm, height is 2mm is 10 days degradable about 15wt% in the phosphate buffer of 7 at pH.XRD figure spectrum after this injecting bone cement solidification 6h is shown in Fig. 1, as seen from Figure 1: the dominant phase composition of solidification end-product is brushite (DCPD; CaHPO
42H
2o)), silico-calcium gel (C-S-H), TCP and hydroxyapatite.SEM figure is shown in Fig. 2.Firming body after above-mentioned bone cement is solidified one hour insert 37 DEG C, PH be in the phosphate buffer of 7 shake 24 hours, mass loss is less than 1% of its initial mass, and under similarity condition, the mass loss of brushite bone cement then can reach 23% of its initial mass.
Embodiment 2
Fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it is made up of composite granule one, composite granule two and consolidation liquid three part, 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 1.2g system of mixing 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 the volume of consolidation liquid.
The configuration of consolidation liquid: be dissolved into by 7g citric acid in 40ml deionized water, then slowly joins 5.6g chitosan in the citric acid solution at the uniform velocity stirred, and 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 the mixing of composite granule two machinery, add wherein respective amount consolidation liquid, rapid stirring 0.5-1.5 minute, injects grinding tool, treats that its solidification can obtain the packing material with fast degradation ability for bone defect healing.Bone cement can solidification in about 5 minutes, under 37 DEG C of tepidarium conditions, solidify comprcssive strength two days later can reach 10MPa, being injected into and treating that it solidifies the firming body obtained in the column type grinding tool that internal diameter is 6mm, height is 2mm is 10 days degradable about 15wt% in the phosphate buffer of 7 at pH.Firming body after above-mentioned bone cement is solidified one hour insert 37 DEG C, PH be in the phosphate buffer of 7 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 made up of composite granule one, composite granule two and consolidation liquid three part, 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, the dicalcium silicate 1.2g system of mixing form, consolidation liquid is the solution of chitosan and citric acid, in consolidation liquid, the mass concentration of citric acid is 0.175g/ml, the mass concentration of chitosan is 0.14g/ml, and the gross mass of composite granule one and composite granule two and the ratio of consolidation liquid volume are 2.0g/mL.
The preparation of consolidation liquid is with embodiment 2.
Using method: after above-mentioned composite granule one and the mixing of composite granule two machinery, add the consolidation liquid of respective amount wherein, rapid stirring 0.5-1.5 minute, injects grinding tool, treats that its solidification can obtain the packing material with fast degradation ability for bone defect healing.This composite bone cement can solidification in about 4 minutes, solidify comprcssive strength two days later and can reach 10MPa, being injected into and treating that it solidifies the firming body obtained in the column type grinding tool that internal diameter is 6mm, height is 2mm is 10 days degradable about 25wt% in the phosphate buffer of 7 at pH.
Embodiment 4
Fast degradation biological activity brushite-calcium silicates/chitosan composite bone cement, it is made up of composite granule one, composite granule two and consolidation liquid three part, 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 1.2g system of mixing 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 and the ratio of consolidation liquid volume are 2.0g/mL.
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 stir 1 hour.Meanwhile, by 54.8g four water-calcium nitrate (Ca (NO
3)
24H
2o) be dissolved in dehydrated alcohol and join to obtain the ethanol solution of four water-calcium nitrate.Then under 60 DEG C of conditions, four water-calcium nitrate solution is slowly added drop-wise in tetraethyl orthosilicate solution, stirring reaction 24 hours, evaporates under 120 DEG C of conditions and spend the night.900 DEG C of roastings 2 hours after drying, grinding after cooling, screening, obtains calcium silicates ((CaO)
6(SiO
2)
4) powder body, be kept in exsiccator for subsequent use.
Using method: after above-mentioned composite granule one and the mixing of composite granule two machinery, add the consolidation liquid of respective amount wherein, rapid stirring 0.5-1.5 minute, injects grinding tool, treats that its solidification can obtain the packing material with fast degradation ability for bone defect healing.This bone cement can solidification in about 6 minutes, solidify comprcssive strength two days later and can reach 10MPa, being injected into and treating that it solidifies the firming body obtained in the column type grinding tool that internal diameter is 6mm, height is 2mm is 10 days degradable about 25wt% in the phosphate buffer of 7 at pH.
Embodiment 5
Carry curcumin fast degradation biological activity brushite-calcium silicates/chitosan compound injecting bone cement: it is made up of composite granule one, composite granule two, consolidation liquid part, curcumin is loaded with in consolidation liquid, 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) 0.4g, α-TCP (Ca
3(PO
4)
2) 1.0g, calcium silicates ((CaO)
7(SiO
2)
3) the 1.2g system of mixing 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 and the ratio of consolidation liquid volume are 1.5g/mL.
The preparation of consolidation liquid: be dissolved in 40ml deionized water by 8g citric acid and 0.06g curcumin, at ambient temperature, slowly joined by 5.6g chitosan in the citric acid solution at the uniform velocity stirred, 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 the mixing of composite granule two machinery, add the consolidation liquid of respective amount wherein, 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 solidification in about 4 minutes, under 37 DEG C of tepidarium conditions, solidify comprcssive strength two days later can reach 10MPa, being injected into and treating that it solidifies the firming body obtained in the column type grinding tool that internal diameter is 6mm, height is 2mm can be 10 days degradable about 15wt% in the phosphate buffer of 7 at pH.
Claims (5)
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 part, each several part is deposited separately, wherein: described composite granule one is by MCPM(Ca (H
2pO
4)
2h
2and MgHPO O)
43H
2the O system of mixing forms, and the calcium silicates system of mixing 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 the gross mass of described composite granule one and composite granule two and the volume ratio of consolidation liquid are 1.5-2.7:1g/ml; Described calcium silicates (CaO)
x(SiO
2)
yin calcium silicon mol ratio x/y be 1.5-4:1, 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) the i.e. 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 drip four water-calcium nitrate (Ca (NO wherein in 50-70 DEG C
3)
24H
2o) ethanol solution, stirring reaction 22-24h, dry except desolventizing, 900 DEG C-1100 DEG C roasting 2-3 hour, cooling, grinding, obtains calcium silicate powder for subsequent use.
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
2o 1-20%, 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: it also comprises drug molecule component.
4. 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 μm.
5. the using method of quick controlled degradation biological activity brushite-calcium silicates/chitosan composite bone cement according to claim 1, it is characterized in that: composite granule one, composite granule two and consolidation liquid are fully mixed 0.5-1.5min in setting ratio and obtains injectable pulpous state composite bone cement and use, or through post processing: the firming body obtaining composite bone cement in a mold after its solidification uses again.
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| CN104857568B (en) * | 2015-05-29 | 2017-06-23 | 河南科技大学 | A kind of calcium orthophosphate base bone cement with anti-microbial 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 |
| CN111514372B (en) * | 2020-04-17 | 2022-04-22 | 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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