CN105311680A - Preparation method of calcium phosphate bone cement simultaneously releasing zinc ions and silicate ions - Google Patents
Preparation method of calcium phosphate bone cement simultaneously releasing zinc ions and silicate ions Download PDFInfo
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Abstract
The invention discloses a preparation method of calcium phosphate bone cement simultaneously releasing zinc ions and silicate ions. The preparation method comprises the following steps that (1) calcium phosphate bone cement powder, inorganic salt containing zinc ions and inorganic salt containing silicate ions are mixed evenly to obtain the calcium phosphate bone cement containing zinc and silicon elements, namely a solid phase; (2) the solid phase cement obtained through the step (1) and a liquid phase are blended, wherein the mass ratio of the liquid phase volume to the solid phase powder is 0.3-0.6 mL/g. The zinc ions and the silicate ions are simultaneously added into the calcium phosphate bone cement for the first time, the calcium phosphate bone cement has the advantages of having high mechanical strength and appropriate setting time and being capable of continuously releasing the zinc ions and silicate ions for a long time and controllable in release amount, and meanwhile the two different types of released functional ions can play roles of synergistically inhibiting bone absorption and promoting bone repair. Compared with traditional calcium phosphate bone cement, the calcium phosphate bone cement has more excellent bone defect repairing effect and wider clinical application prospect.
Description
Technical field
The present invention relates to bone defect healing field of medical materials, particularly a kind of preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion.
Background technology
Since Brown and Chow reported first calcium phosphate bone cement (CalciumPhosphateCement, CPC), CPC receives the extensive concern of researcher.CPC is made up of solid phase powder and liquid phase, is also in harmonious proportion by two-phase mixtures and evenly becomes paste, is filled into Cranial defect position afterwards by performing the operation or being implanted with injecting apparatus when Clinical practice.CPC solidifies under body temperature voluntarily, progressively degrades in vivo, guides New born formation, finally completes the reparation to Cranial defect.Because CPC has the performance that syringeability, random-shaping, original position isothermal self-curing performance etc. are different from other bone defect healing biomaterials, therefore CPC is a kind of Cranial defect filling renovation material with good potential applicability in clinical practice.Although CPC has good biocompatibility and bone conductibility, due to its shortcoming in induced osteogenesis performance, therefore the Bone Defect Repari effect of CPC is subject to certain impact.
The raising of CPC bone formation performance realizes with modification by ion-doping usually through somatomedin is composite modified.Somatomedin is expensive, and exists after being compound in CPC and prominently release phenomenon, only implants at material and has certain short ossification in early days, do not have the effect of long-term induced osteogenesis.The hydrated product of CPC is close to the main inorganic composition hydroxyapatite (hydroxyapatite, HA) of natural bone.There is various trace elements in natural bone HA, these trace element play an important role in the formation and growth course of congenital and posteriori osseous tissue.Research shows, carrys out modification CPC by ion doping, is a kind of method of effective raising calcium phosphate bone cement Bone Defect Repari effect.After in ion doping to CPC, material long-term stability can discharge functional ion in Bone Defect Repari process, improves the bone formation performance of CPC; And inorganic ions wide material sources, cheap, the burden alleviating patient that can be larger during Clinical practice.
The interpolation of bone cement medium trace element, makes material have the performance of various promotion Bone Defect Repari, as the performance, anti-microbial property etc. of the performance of induced osteogenesis, the performance of inducing into blood vessel, suppression bone resorption.Although these trace element content in bone cement is very low, it plays irreplaceable effect in the reparation of Cranial defect.The trace element added in CPC can dissolve and discharge from material, and be absorbed by the body utilization, participates in the formation of new bone, plays its biological action.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the invention is to a kind of preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion, technics comparing is simple, the calcium phosphate bone cement mechanical strength prepared is higher, can slow-release function ion, Ion release amount be controlled for a long time, and no cytotoxicity, along with the degraded of material after implanting, can simultaneously sustained release zinc ion and silicate ion, improve the Bone Defect Repari effect of calcium phosphate bone cement.
Object of the present invention is achieved through the following technical solutions:
Discharge a preparation method for the calcium phosphate bone cement of zinc ion and silicate ion simultaneously, comprise the following steps:
(1) by calcium phoshate bone cement powder, the inorganic salt containing zinc ion, the inorganic salt mix homogeneously containing silicate ion, the calcium phosphate bone cement simultaneously containing zinc element and element silicon is obtained, i.e. solid phase; The described inorganic salt containing zinc ion in calcium phosphate bone cement in volume be 2.5 ~ 10wt.%; The described inorganic salt containing silicate ion in calcium phosphate bone cement in volume be 2.5 ~ 10wt.%;
(2) solid phase mud step (1) obtained and liquid phase are in harmonious proportion, and liquid phase volume and solid phase powder mass ratio are 0.3 ~ 0.6mL/g; The phosphate solution that described liquid phase is deionized water, normal saline, blood, pH are 7.0 ~ 7.4, pH are the one in the citrate solution of 7.0 ~ 7.4.
The described inorganic salt containing zinc ion is the inorganic salt simultaneously containing zinc ion and silicate ion; The described inorganic salt containing silicate ion is the inorganic salt simultaneously containing zinc ion and silicate ion.
The described inorganic salt simultaneously containing zinc ion and silicate ion in calcium phosphate bone cement in volume be 5 ~ 20wt.%.
The described inorganic salt containing zinc ion is the one in zinc carbonate, zinc phosphate, zinc oxide, zinc doping calcium phosphate, zinc doping hydroxyapatite.
The described inorganic salt containing silicate ion is the one in magnesium silicate, strontium silicate, potassium silicate, silicon doping calcium phosphate, silicon doping hydroxyapatite; Or be the solid solution of the silicate of monocalcium silicate, dicalcium silicate, tricalcium silicate or calcium silicates and other ions; Other ions described are magnesium ion or strontium ion.
The described inorganic salt simultaneously containing zinc ion and silicate ion is the one in zinc silicate, zinc doping monocalcium silicate, zinc doping dicalcium silicate, zinc doping tricalcium silicate, zinc doping magnesium silicate, zinc doping strontium silicate, hardystonite.
Described calcium phoshate bone cement powder is " tetracalcium phosphate+dicalcium phosphate dehydrate " system bone cement, " dalcium biphosphate+type alpha tricalcium phosphate+calcium carbonate " system bone cement, " unformed calcium phosphate+dicalcium phosphate dehydrate " system bone cement, " tetracalcium phosphate+type alpha tricalcium phosphate+dicalcium phosphate dehydrate " system bone cement, " tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " system bone cement, any one in " partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement or " type alpha tricalcium phosphate+dicalcium phosphate dehydrate+calcium carbonate " system bone cement.
Described phosphate solution is dibastic sodium phosphate solution or phosphoric acid hydrogen potassium solution.
Described citrate solution is lemon acid sodium solution or potassium citrate solution.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, the inorganic salt simultaneously containing zinc ion and silicate ion adds in traditional calcium phosphate bone cement by the present invention first, utilizes the biological function of the ion discharged, improves the bone formation performance of bone cement.Compared with the additive promoting skeletonization with bioactie agent etc., the inorganic additive wide material sources containing functional ion, cheap and easy to get, and chemical stability is good, can continue slow releasing from material, has the effect of long-term promotion skeletonization.
2, the calcium phosphate bone cement that simultaneously can discharge zinc ion and silicate ion prepared by the present invention, add the inorganic salt containing zinc ion and silicate ion in traditional calcium phosphate bone cement after, appreciable impact can not be caused on the composition of the syringeability of bone cement, setting time and hydrated product.The addition of inorganic salt within the specific limits, can improve the mechanical strength of bone cement significantly.
3, the calcium phosphate bone cement that simultaneously can discharge zinc ion and silicate ion prepared by the present invention, confirms through Ion release experiment test, and along with the continuous degraded of material, zinc ion and silicate ion can the slow releasing of long-time stable.
4, the calcium phosphate bone cement that simultaneously can discharge zinc ion and silicate ion prepared by the present invention, by changing the addition of the inorganic salt containing zinc ion and silicate ion in bone cement, the object controlling Ion release amount can be reached, make its stripping quantity within the bio-safety scope of this ion.The calcium phosphate bone cement containing zinc ion and silicate ion prepared by the present invention, within the scope of the stripping quantity of limited zinc ion and silicate ion, can not produce the cytotoxicity being greater than 1 grade.
5, prepared by the present invention can the calcium phosphate bone cement of simultaneously sustained release zinc ion and silicate ion, because it has suitable zinc ion and the stripping quantity of silicate ion, significantly can promote propagation and the differentiation of mesenchymal stem cells MSCs in vitro under environment, there is under environment the significant effect promoting skeletonization in vivo.
Accompanying drawing explanation
The setting time of the calcium phosphate bone cement of release zinc ion and silicate ion while that Fig. 1 being embodiment 1 preparation.
The comprcssive strength of the calcium phosphate bone cement of release zinc ion and silicate ion while that Fig. 2 being embodiment 1 preparation.
Fig. 3 is the proliferative conditions that mesenchymal stem cells MSCs discharges on the calcium phosphate bone cement of zinc ion and silicate ion while prepared by embodiment 1.
Fig. 4 is the expression that mesenchymal stem cells MSCs discharges the type i collagen on the calcium phosphate bone cement of zinc ion and silicate ion while prepared by embodiment 1.
Fig. 5 is the expression that mesenchymal stem cells MSCs discharges the alkali phosphatase on the calcium phosphate bone cement of zinc ion and silicate ion while prepared by embodiment 1.
Fig. 6 is the expression that mesenchymal stem cells MSCs discharges the Runx-2 on the calcium phosphate bone cement of zinc ion and silicate ion while prepared by embodiment 1.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Select zinc silicate as the inorganic additives containing zinc ion and silicate ion simultaneously, added in " partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement, implementation step comprises:
(11) microwave hydrothermal method is adopted to prepare zinc silicate powder body.Zinc acetate and ethyl orthosilicate are dissolved in successively in deionized water, the mol ratio of zinc and silicon is 2:1, adjusts solution ph to 7 with ammonia.Along with the carrying out of chemical reaction, solution becomes uniform white emulsion gradually.By this white emulsion microwave hydrothermal 1 hour under 160 DEG C of conditions, dry with under deionized water wash white precipitate 80 DEG C of conditions after hydro-thermal completes, obtain required zinc silicate powder body.
(12) take the zinc silicate powder body 0.1g prepared by step (11), take " partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement powder body 0.9g, by its mix homogeneously.According to the ratio of liquid-solid ratio 0.35mL/g, deionized water is joined prepared by the present embodiment containing in the bone cement powder body of zinc silicate, and reconcile into paste.
(13) be respectively charged in injectable apparatus by the paste prepared by step (12), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.35mL/g, deionized water is joined in this comparative example, and reconcile into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " bone cement containing zinc silicate prepared by the present embodiment, confirms to have suitable hardening time (28min) and higher comprcssive strength (67MPa) (Fig. 1 ~ Fig. 2) through physicochemical property test.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 54.6%, residue Si constituent content is 36.2% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 4.62 μMs, the stripping quantity of Si first day is 0.97mM, does not all exceed the highest limit value.Confirm through In vitro cell experiment, compared with contrast sample, the present embodiment bone cement significantly can promote propagation (Fig. 3) and the Osteoblast Differentiation (Fig. 4 ~ 6) of mesenchymal stem cells MSCs.
Embodiment 2
Select zinc doping monocalcium silicate as the inorganic additives containing zinc ion and silicate ion, added in " dalcium biphosphate+type alpha tricalcium phosphate+calcium carbonate " system bone cement, implementation step comprises:
(11) high-temperature solid phase reaction method is adopted to prepare zinc doping monocalcium silicate.Take zinc oxide and the calcium silicates of certain mass, wherein the mol ratio of zinc and calcium is 1:19.After mix homogeneously, calcine at 1000 DEG C, be incubated 4 hours, finally obtain testing required zinc doping monocalcium silicate.
(12) take the zinc doping monocalcium silicate powder body 0.2g prepared by step (11), take " dalcium biphosphate+type alpha tricalcium phosphate+calcium carbonate " system bone cement powder body 0.8g, by its mix homogeneously.Choosing 0.25mol/L disodium phosphate soln is distiller liquor, according to the ratio of liquid-solid ratio 0.6mL/g join prepared by the present embodiment containing in the bone cement powder body of zinc doping monocalcium silicate, and reconcile into paste.
(13) be respectively charged in injectable apparatus by the paste prepared by step (12), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " dalcium biphosphate+type alpha tricalcium phosphate+calcium carbonate " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.6mL/g, 0.25mol/L disodium phosphate soln is joined in this comparative example, and reconciles into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" dalcium biphosphate+type alpha tricalcium phosphate+calcium carbonate " system bone cement containing zinc doping monocalcium silicate prepared by the present embodiment, syringeability, setting time and mechanical strength meet the demand of clinical practice.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 34.8%, residue Si constituent content is 18.5% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 0.58 μM, the stripping quantity of Si first day is 1.36mM, does not all exceed the highest limit value.Compared with contrast sample, in the present embodiment bone cement, the stripping of zinc ion and silicate ion significantly improves the bone formation performance of bone cement.
Embodiment 3
Select zinc phosphate and dicalcium silicate as the inorganic additives containing zinc ion and silicate ion, added in " unformed calcium phosphate+dicalcium phosphate dehydrate " system bone cement, implementation step comprises:
(11) take dicalcium silicate 0.05g, take zinc phosphate 0.05g, take " unformed calcium phosphate+dicalcium phosphate dehydrate " system bone cement powder body 0.9g, by its mix homogeneously.Choosing 0.1mol/L potassium citrate solution is distiller liquor, liquid phase to be joined in the bone cement powder body of phosphoric acid zinc prepared by the present embodiment and dicalcium silicate, and reconcile into paste according to the ratio of liquid-solid ratio 0.4mL/g.
(12) be respectively charged in injectable apparatus by the paste prepared by step (11), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " unformed calcium phosphate+dicalcium phosphate dehydrate " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.4mL/g, 0.1mol/L potassium citrate solution is joined in this comparative example, and reconciles into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" unformed calcium phosphate+dicalcium phosphate dehydrate " system bone cement of phosphoric acid zinc prepared by the present embodiment and dicalcium silicate, syringeability, setting time and mechanical strength meet the demand of clinical practice.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 67.7%, residue Si constituent content is 20.8% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 0.26 μM, the stripping quantity of Si first day is 0.89mM, does not all exceed the highest limit value.Compared with comparative example, in the present embodiment bone cement, the stripping of zinc ion and silicate ion significantly improves the Bone Defect Repari effect of bone cement.
Embodiment 4
Select zinc silicate and magnesium silicate as the inorganic additives containing zinc ion and silicate ion, added in " partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement, implementation step comprises:
(11) take magnesium silicate 0.05g, take zinc carbonate 0.1g, take " partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement powder body 0.85g, by its mix homogeneously.Choosing 0.05mol/L dipotassium hydrogen phosphate solution is distiller liquor, liquid phase is joined in the bone cement powder body of magnesium silicate prepared by the present embodiment, and reconcile into paste according to the ratio of liquid-solid ratio 0.3mL/g.
(12) be respectively charged in injectable apparatus by the paste prepared by step (11), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.3mL/g, 0.05mol/L dipotassium hydrogen phosphate solution is joined in this comparative example, and reconciles into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement containing zinc silicate and magnesium silicate prepared by the present embodiment, syringeability, setting time and mechanical strength meet the demand of clinical practice.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 55.9%, residue Si constituent content is 40.6% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 4.37 μMs, the stripping quantity of Si first day is 1.28mM, does not all exceed the highest limit value.Compared with contrast sample, in the present embodiment bone cement, the stripping of zinc ion and silicate ion significantly improves the bone formation performance of bone cement.
Embodiment 5
Select zinc carbonate and strontium silicate as the inorganic additives containing zinc ion and silicate ion, added in " tetracalcium phosphate+type alpha tricalcium phosphate+dicalcium phosphate dehydrate " system bone cement, implementation step comprises:
(11) high-temperature solid phase reaction method is adopted to prepare strontium silicate powder body.Taking ethanol as medium, is silicon dioxide and the strontium carbonate powder ball milling mixing 2h of 2:1 by mol ratio, after 60 DEG C of oven dry, the powder body of drying is put into high temperature furnace, high-temperature calcination 4h at 1400 DEG C, thus obtains high-purity strontium silicate powder body.
(12) take strontium silicate 0.05g, take zinc carbonate 0.05g, take " tetracalcium phosphate+type alpha tricalcium phosphate+dicalcium phosphate dehydrate " system bone cement powder body 0.9g, by its mix homogeneously.Choosing 0.25mol/L sodium hydrogen phosphate/phosphate sodium dihydrogen buffer solution is distiller liquor, according to the ratio of liquid-solid ratio 0.5mL/g join prepared by the present embodiment containing in the bone cement powder body of zinc carbonate and strontium silicate, and reconcile into paste.
(13) be respectively charged in injectable apparatus by the paste prepared by step (12), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " tetracalcium phosphate+type alpha tricalcium phosphate+dicalcium phosphate dehydrate " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.5mL/g, 0.25mol/L sodium hydrogen phosphate/phosphate sodium dihydrogen buffer solution is joined in this comparative example, and reconciles into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" tetracalcium phosphate+type alpha tricalcium phosphate+dicalcium phosphate dehydrate " system bone cement containing zinc carbonate and strontium silicate prepared by the present embodiment, syringeability, setting time and mechanical strength meet the demand of clinical practice.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 37.1%, residue Si constituent content is 12.7% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 0.78 μM, the stripping quantity of Si first day is 1.04mM, does not all exceed the highest limit value.Compared with contrast sample, in the present embodiment, the stripping of zinc ion and silicate ion significantly improves the bone formation performance of bone cement.
Embodiment 6
Select zinc doping bata-tricalcium phosphate and silicon doping bata-tricalcium phosphate as the inorganic additives containing zinc ion and silicate ion, be applied in " tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " system bone cement, implementation step comprises:
(11) chemical precipitation method is adopted to prepare zinc doping bata-tricalcium phosphate and silicon doping bata-tricalcium phosphate.Take the lime nitrate of certain mass, diammonium phosphate and zinc acetate, wherein the mol ratio of zinc and calcium is 1:9, and the mol ratio of zinc+calcium and phosphorus is 1.5:1.The solution of 0.2M diammonium phosphate is slowly joined in the mixed solution of 0.3M lime nitrate and zinc acetate, use ammonia adjust pH to 8 afterwards.Stir 8h, after ageing 12h, washing gained white precipitate, after oven dry at 1000 DEG C heat treatment, be incubated 2 hours, obtain testing required zinc doping bata-tricalcium phosphate.
Take the lime nitrate of certain mass, diammonium phosphate, measure the ethyl orthosilicate of certain volume, wherein the mol ratio of silicon and phosphorus is 1:9, and the mol ratio of calcium and phosphorus+silicon is 1.5:1.The mixed solution of 0.2M diammonium phosphate and ethyl orthosilicate is slowly joined in 0.3M calcium nitrate solution, uses ammonia adjust pH to 8 afterwards.Stir 8h, after ageing 12h, washing gained white precipitate, after oven dry at 1000 DEG C heat treatment, be incubated 2 hours, obtain testing required zinc doping bata-tricalcium phosphate.
(12) bata-tricalcium phosphate in zinc doping bata-tricalcium phosphate prepared in step (11) and silicon doping bata-tricalcium phosphate replacement " tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " system bone cement is adopted, wherein the mass ratio of zinc doping bata-tricalcium phosphate and silicon doping bata-tricalcium phosphate is 1:1, and both summations account for 40% of bone cement total amount.Choosing 0.1mol/L sodium citrate solution is distiller liquor, according to the ratio of liquid-solid ratio 0.6mL/g join prepared by the present embodiment containing in the bone cement powder body of zinc and silicon, and reconcile into paste.
(13) be respectively charged in injectable apparatus by the paste prepared by step (12), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.6mL/g, 0.1mol/L sodium citrate solution is joined in this comparative example, and reconciles into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" tetracalcium phosphate+zinc doping bata-tricalcium phosphate+silicon doping bata-tricalcium phosphate+dalcium biphosphate " bone cement prepared by the present embodiment, syringeability, setting time and mechanical strength meet the demand of clinical practice.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 78.4%, residue Si constituent content is 69.2% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 0.015 μM, the stripping quantity of Si first day is 0.04mM, does not all exceed the highest limit value.Although the stripping quantity of zinc ion and silicate ion is lower in the present embodiment bone cement, compared with contrast sample, the self-bone grafting performance of this bone cement still has and improved.
Embodiment 7
Select hardystonite as the inorganic additives containing zinc ion and silicate ion, added in " tetracalcium phosphate+dicalcium phosphate dehydrate " system bone cement, implementation step comprises:
(11) high-temperature solid phase reaction method is adopted to prepare hardystonite powder body.Take ethanol as medium, be the ratio ball milling mix homogeneously of 2:1:2 with mol ratio by calcium carbonate, zinc oxide, silicon-dioxide powdery, after 60 DEG C of oven dry ethanol, the powder body of the mix homogeneously of drying put into high temperature furnace, high-temperature calcination 2h at 1200 DEG C, thus obtain required hardystonite powder body.
(12) take the hardystonite powder body 0.15g prepared by step (11), take " tetracalcium phosphate+dicalcium phosphate dehydrate " system bone cement powder body 0.85g, by its mix homogeneously.According to the ratio of liquid-solid ratio 0.5mL/g, normal saline is joined prepared by the present embodiment containing in the bone cement powder body of hardystonite, and reconcile into paste.
(13) be respectively charged in injectable apparatus by the paste prepared by step (12), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " tetracalcium phosphate+dicalcium phosphate dehydrate " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.5mL/g, normal saline is joined in this comparative example, and reconcile into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" tetracalcium phosphate+dicalcium phosphate dehydrate " system bone cement containing hardystonite prepared by the present embodiment, syringeability, setting time and mechanical strength meet the demand of clinical practice.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 35.5%, residue Si constituent content is 14.8% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 15.4 μMs, the stripping quantity of Si first day is 1.74mM, does not all exceed the highest limit value.Compared with comparative example, in the present embodiment, the stripping of zinc ion and silicate ion significantly improves the bone formation performance of bone cement.
Embodiment 8
Select zinc doping magnesium silicate and zinc oxide as the inorganic additives containing zinc ion and silicate ion, added in " type alpha tricalcium phosphate+dicalcium phosphate dehydrate+calcium carbonate " system bone cement, implementation step comprises:
(11) high-temperature solid phase reaction method is adopted to prepare zinc doping magnesium silicate powder.Take ethanol as medium, be the ratio ball milling mix homogeneously of 0.39:0.05:1 with mol ratio by basic magnesium carbonate, zinc oxide, silicon-dioxide powdery, after 60 DEG C of oven dry ethanol, the powder body of the mix homogeneously of drying is put into high temperature furnace, high-temperature process 3h at 1200 DEG C, thus obtain required zinc doping magnesium silicate powder.
(12) take the zinc doping magnesium silicate powder 0.05g prepared by step (11), take " type alpha tricalcium phosphate+dicalcium phosphate dehydrate+calcium carbonate " system bone cement powder body 0.95g, by its mix homogeneously.According to the ratio of liquid-solid ratio 0.55mL/g, 0.25mol/L disodium phosphate soln is joined prepared by the present embodiment containing in the bone cement powder body of zinc doping magnesium silicate and zinc oxide, and reconcile into paste.
(13) be respectively charged in injectable apparatus by the paste prepared by step (12), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " type alpha tricalcium phosphate+dicalcium phosphate dehydrate+calcium carbonate " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.55mL/g, 0.25mol/L disodium phosphate soln is joined in this comparative example, and reconciles into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" type alpha tricalcium phosphate+dicalcium phosphate dehydrate+calcium carbonate " system bone cement containing zinc doping magnesium silicate and zinc oxide prepared by the present embodiment, syringeability, setting time and mechanical strength meet the demand of clinical practice.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 60.8%, residue Si constituent content is 24.5% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 0.15 μM, the stripping quantity of Si first day is 0.76mM, does not all exceed the highest limit value.Compared with contrast sample, in the present embodiment, the stripping of zinc ion and silicate ion significantly improves the bone formation performance of bone cement.
Embodiment 9
Select zinc doping hydroxyapatite and silicon doping hydroxyapatite as the inorganic additives containing zinc ion and silicate ion, added in " tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " system bone cement, implementation step comprises:
(11) hydro-thermal method is adopted to prepare zinc doping hydroxyapatite and silicon doping hydroxyapatite.
Take the lime nitrate of certain mass, ammonium phosphate and zinc acetate, Qi Zhongxin: calcium: the mol ratio of phosphorus is 0.5:9.5:6.The lime nitrate of 0.025M and zinc acetate mixed solution are slowly joined in the ammonium phosphate solution of 0.015M, limit edged with ammonia adjust pH to 10.By white precipitate hydrothermal treatment consists 6h at 180 DEG C, then white precipitate washed, dry, obtain testing required zinc doping hydroxyapatite.
Take the lime nitrate of certain mass, ammonium phosphate, measure the ethyl orthosilicate of certain volume, wherein calcium: phosphorus: the mol ratio of silicon is 10:5.5:0.5.In the ammonium phosphate calcium nitrate solution of 0.025M slowly being joined 0.015M and ethyl orthosilicate mixed solution, use ammonia adjust pH to 10 afterwards.By white precipitate hydrothermal treatment consists 6h at 180 DEG C, then white precipitate washed, dry, obtain testing required silicon doping hydroxyapatite.
(12) take zinc doping hydroxyapatite prepared in step (1) and each 0.15g of silicone hydroxyl apatite, take " tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " system bone cement 0.7g, and by three kinds of powder body mix homogeneously.Choosing 0.1mol/L sodium citrate solution is distiller liquor, according to the ratio of liquid-solid ratio 0.6mL/g join prepared by the present embodiment containing in the bone cement powder body of zinc and silicon, and reconcile into paste.
(13) be respectively charged in injectable apparatus by the paste prepared by step (12), bone cement injects aftershaping and solidifies.
Contrast sample:
(21) " tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " system bone cement powder body 1g is taken, as the comparative example of the present embodiment.According to the ratio of liquid-solid ratio 0.6mL/g, 0.1mol/L sodium citrate solution is joined in this comparative example, and reconciles into paste.
(22) be respectively charged in injectable apparatus by the paste prepared by step (21), bone cement injects aftershaping and solidifies.
" tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " bone cement containing zinc doping hydroxyapatite and silicon doping hydroxyapatite prepared by the present embodiment, syringeability, setting time and mechanical strength meet the demand of clinical practice.This bone cement is soaked according to the ratio of 5mL/g in the Tris-HCl buffer solution of pH=7.4 (37 DEG C), every day changes liquid, soak after 8 weeks and take out sample and drying, through X-ray fluorescence spectra analysis, remain in sample that Zn constituent content is initial Zn constituent content 83.4%, residue Si constituent content is 79.2% of initial Si constituent content, still have zinc element and element silicon to exist after illustrating 8 weeks in the material, the sustained release time of zinc ion and silicate ion can reach more than 8 weeks.Have detected the concentration of Zn and Si of immersion interior stripping every day in a week, result shows that the stripping quantity soaking first day is maximum, and the stripping quantity of Zn first day is 0.009 μM, the stripping quantity of Si first day is 0.016mM, does not all exceed the highest limit value.Although the stripping quantity of zinc ion and silicate ion is lower in the present embodiment bone cement, compared with contrast sample, the self-bone grafting performance of this bone cement still has and improved.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. discharge a preparation method for the calcium phosphate bone cement of zinc ion and silicate ion simultaneously, it is characterized in that, comprise the following steps:
(1) by calcium phoshate bone cement powder, the inorganic salt containing zinc ion, the inorganic salt mix homogeneously containing silicate ion, the calcium phosphate bone cement simultaneously containing zinc element and element silicon is obtained, i.e. solid phase; The described inorganic salt containing zinc ion in calcium phosphate bone cement in volume be 2.5 ~ 10wt.%; The described inorganic salt containing silicate ion in calcium phosphate bone cement in volume be 2.5 ~ 10wt.%;
(2) solid phase mud step (1) obtained and liquid phase are in harmonious proportion, and liquid phase volume and solid phase powder mass ratio are 0.3 ~ 0.6mL/g; The phosphate solution that described liquid phase is deionized water, normal saline, blood, pH are 7.0 ~ 7.4, pH are the one in the citrate solution of 7.0 ~ 7.4.
2. the preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion according to claim 1, is characterized in that, the described inorganic salt containing zinc ion is the inorganic salt simultaneously containing zinc ion and silicate ion; The described inorganic salt containing silicate ion is the inorganic salt simultaneously containing zinc ion and silicate ion.
3. the preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion according to claim 2, it is characterized in that, the described inorganic salt simultaneously containing zinc ion and silicate ion in calcium phosphate bone cement in volume be 5 ~ 20wt.%.
4. the preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion according to claim 1, it is characterized in that, the described inorganic salt containing zinc ion is the one in zinc carbonate, zinc phosphate, zinc oxide, zinc doping calcium phosphate, zinc doping hydroxyapatite.
5. the preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion according to claim 4, it is characterized in that, the described inorganic salt containing silicate ion is the one in magnesium silicate, strontium silicate, potassium silicate, silicon doping calcium phosphate, silicon doping hydroxyapatite; Or be the solid solution of the silicate of monocalcium silicate, dicalcium silicate, tricalcium silicate or calcium silicates and other ions; Other ions described are magnesium ion or strontium ion.
6. the preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion according to claim 2, it is characterized in that, the described inorganic salt simultaneously containing zinc ion and silicate ion is the one in zinc silicate, zinc doping monocalcium silicate, zinc doping dicalcium silicate, zinc doping tricalcium silicate, zinc doping magnesium silicate, zinc doping strontium silicate, hardystonite.
7. the preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion according to claim 1, it is characterized in that, described calcium phoshate bone cement powder is " tetracalcium phosphate+dicalcium phosphate dehydrate " system bone cement, " dalcium biphosphate+type alpha tricalcium phosphate+calcium carbonate " system bone cement, " unformed calcium phosphate+dicalcium phosphate dehydrate " system bone cement, " tetracalcium phosphate+type alpha tricalcium phosphate+dicalcium phosphate dehydrate " system bone cement, " tetracalcium phosphate+bata-tricalcium phosphate+dalcium biphosphate " system bone cement, any one in " partially crystallized calcium phosphate+calcium phosphate dibasic anhydrous " system bone cement or " type alpha tricalcium phosphate+dicalcium phosphate dehydrate+calcium carbonate " system bone cement.
8. the preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion according to claim 1, it is characterized in that, described phosphate solution is dibastic sodium phosphate solution or phosphoric acid hydrogen potassium solution.
9. the preparation method simultaneously discharging the calcium phosphate bone cement of zinc ion and silicate ion according to claim 1, it is characterized in that, described citrate solution is lemon acid sodium solution or potassium citrate solution.
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