CN104649284A - Mesoporous magnesium silicate-calcium sulfate hemihydrate composite material, and preparation method and application thereof - Google Patents
Mesoporous magnesium silicate-calcium sulfate hemihydrate composite material, and preparation method and application thereof Download PDFInfo
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- CN104649284A CN104649284A CN201510060612.4A CN201510060612A CN104649284A CN 104649284 A CN104649284 A CN 104649284A CN 201510060612 A CN201510060612 A CN 201510060612A CN 104649284 A CN104649284 A CN 104649284A
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Abstract
The invention discloses a mesoporous magnesium silicate-calcium sulfate hemihydrate composite material, and a preparation method and application thereof. The preparation method comprises the following steps: (1) adding hydrochloric acid into a P123-water mixture, uniformly mixing, adding soluble magnesium salt, dropwisely adding TEOS (tetraethyl orthosilicate) into the solution, stirring until the solution has white turbidity, and continuing stirring to obtain a sol-gel white emulsion; (2) aging the white emulsion, carrying out vacuum filtration to remove the supernatant liquid, drying the precipitate, and sintering to obtain mesoporous magnesium silicate; and mixing the mesoporous magnesium silicate-calcium sulfate hemihydrate powder mixture with a solidifying solution, carrying out compression molding, solidifying and baking to obtain the calcium sulfate hemihydrate composite material. The calcium sulfate hemihydrate composite material has favorable application prospects in bone prosthesis, has favorable bioactivity and biocompatibility especially when being used as bone cement, and can stimulate the bone growth and shorten the healing time after implanting the material into the bone.
Description
Technical field
The present invention relates to Material Field, particularly relate to mesoporous Magnesium Silicate q-agent, calcium sulphate hemihydrate matrix material and its preparation method and application.
Background technology
The bone implant material of current clinical application is more titanium base bone implant material and ceramic bone implant material, but those materials all still exist the shortcoming self being difficult to overcome.Metal structure character and bone differ greatly, and lack biological activity, cannot with bone forming Integrated implant, and easily cause bone resorption, and the stripping of metal ion easily causes the phenomenons such as hydrops, inflammation and necrosis; The shortcomings such as ceramic bone implant material then has not easily forming process, and toughness is poor.Therefore, the research and development of new substitute products are particularly important.
The existing history for many years of the application of calcium sulphate hemihydrate in Bone Defect Repari, because the controllable degradation property of its excellence, fast solidifiability, excellent biocompatibility and osteoconductive obtain numerous investigators and surgical accreditation.Calcium sulphate hemihydrate bone cement can be arbitrarily moulding when implanting, and leaves a large amount of micropore after solidification, and compared with other biological material, the absorption rate of calcium sulfate is very fast, therefore can osteocyte be allowed relatively earlier to enter, thus facilitate osteogenic response.High-purity medical calcium sulphate hemihydrate has good biocompatibility, and plasticity-is good, easy to operate, and isolated experiment and experimentation on animals find that it has certain ultimate compression strength after implanting, and can provide the support of defect.But its biological activity is general, the scarce capacity of induced osteogenesis, in addition, the acid-basicity in calcium sulphate hemihydrate bone cement degradation process changes and plasma diffusing W,Mo also instability, cannot provide most suitable healing environment for knitting.
Mg
2+can promote the deposition of calcium, have material impact to the mineralising of tissue, the shortage of magnesium elements can cause osteoporosis.Mg
2+have material impact to bone metabolism, the local release of magnesium ion in osseous tissue, can improve osteoclast and osteoblastic activity.Therefore, magnesium elements is added the physicochemical property and bone metabolism level that material in calcium sulfate, can be improved, effectively improve the biological activity of tissue scaffold design.The absorption level of element silicon directly can have influence on the development quality of bone, and especially in the area of new bone etap, element silicon at the region clustering of these new bone calcifications, and can promote the calcification of early stage osseous tissue under the synergy of calcium.If the quantity not sufficient of silicon, area of new bone can be caused to distort.Therefore silicon plays regulating and controlling effect to area of new bone mineralising and growth.There are some researches show, CaO-SiO
2the matrix material of-MgO system has good biological activity, and not showing in experiment in vitro has cytotoxicity to scleroblast, and in research in vivo, this material can pass through Surface Creation calcium-phosphate layer, thus combines closely with bone.But, CaO-SiO
2-MgO biological ceramic composite material fragility is not large, and mechanical property is not high, good with the mechanical compatibility of bone and bone renovating material that is that easily cause stress shielding to cause loosens and bone resorption, cannot with bone forming secure bond, limit its applicability.
Summary of the invention
Technical problem to be solved by this invention is to overcome that the mechanical compatibility of existing bone renovating material is not good and bone renovating material that is that cause stress shielding to cause loosens and bone resorption, or knitting speed is excessively slow, lack biological activity, cannot with the defect of bone forming secure bond.The invention provides a kind of mesoporous Magnesium Silicate q-agent and preparation method thereof, calcium sulphate hemihydrate matrix material and its preparation method and application, make matrix material have syringeability and strengthen its osteoinductive.The uniform diameter of this mesoporous Magnesium Silicate q-agent, and mesoporous pore size distribution is concentrated.Matrix material after modification calcium sulphate hemihydrate has good biological activity and biocompatibility, has good mechanical compatibility with osseous tissue, can stimulation of bone growth, and accelerated bone heals, and reduces the healing time after bone implant material.And matrix material is simple for process, can according to clinical demand corresponding using matrix material as bone cement injection fillers Cranial defect.This matrix material has good biocompatibility, biological activity, biomechanics of bone consistency and germ resistance as bone-repairing cement, can shorten bone healing time.Can not be caused inflammation after the implantation of this bone-repairing cement reaction, and its mechanical property is mated with people's bone photo, can meet the clinical needs for Bone Defect Repari.
The present invention solves the problems of the technologies described above by the following technical programs.
The invention provides a kind of preparation method of mesoporous Magnesium Silicate q-agent, it comprises the steps:
(1) in the mixture of P123 and water, it is even to add mixed in hydrochloric acid, then adds solubility magnesium salts, is dropped to by TEOS in solution, is stirred to after white opacity appears in solution, continues to stir, obtain collosol and gel white emulsion;
(2) by described white emulsion ageing, suction filtration removes supernatant liquid, and by drying precipitate, sintering, obtains mesoporous Magnesium Silicate q-agent.
In step (1), described P123 is polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (EO20PO70EO20) well known in the art, is purchased from Aldrich-sigma Reagent Company.
In step (1), described water is the water that this area routine uses, and is generally deionized water.
In step (1), the described temperature adding hydrochloric acid is preferably 36 ~ 55 DEG C, is more preferably 50 DEG C.
In step (1), described hydrochloric acid is the hydrochloric acid that this area routine uses, and the concentration of described hydrochloric acid is preferably 1 ~ 4mol/L, is more preferably 2mol/L.
In step (1), described solubility magnesium salts can be the solubility magnesium salts various soluble in water that this area routine uses, the preferred magnesium nitrate hexahydrate of the present invention.
In step (1), wherein, the mass ratio of described P123 and described water is preferably 1:(7 ~ 8.6), the mass volume ratio of described P123 and described hydrochloric acid is preferably 1g:(28 ~ 35) mL, the mass volume ratio of described P123 and described TEOS is preferably 1g:(2 ~ 3.3) mass ratio of mL, described P123 and described solubility magnesium salts is preferably 1:(2.1 ~ 2.8).
In step (1), described TEOS is the tetraethoxy that this area routine uses.The speed of described dropping is preferably 8/min ~ 20 droplet/min.
In step (1), the time that described continuation is stirred is preferably 5 ~ 7 hours.
In step (2), the method for described ageing and condition are method and the condition of this area routine.The temperature of described ageing is preferably 10 ~ 30 DEG C, is more preferably 25 DEG C.The time of described ageing is preferably 2 ~ 4 days, is more preferably 3 days.Described ageing is generally carried out in stink cupboard.
In step (2), the method for described drying and condition are method and the condition of this area routine.The temperature of described drying is preferably 78 ~ 82 DEG C, is more preferably 80 DEG C.
In step (2), the method for described sintering and condition are method and the condition of this area routine.Contriver studies discovery, and the too high meeting of temperature of sintering causes the mesoporous material performance that obtains not good; The temperature of described sintering is preferably 550 ~ 620 DEG C, is more preferably 600 DEG C; The time of described sintering is preferably 5 ~ 7 hours, is more preferably 6 hours.
Present invention also offers a kind of mesoporous Magnesium Silicate q-agent obtained by above-mentioned preparation method, the mesoporous pore size of described mesoporous Magnesium Silicate q-agent is 5nm ~ 15nm, and preferably the mesoporous pore size of 80% above-described mesoporous Magnesium Silicate q-agent is 10nm ~ 15nm; The diameter of described mesoporous Magnesium Silicate q-agent is 7 μm ~ 10 μm.
Present invention also offers a kind of preparation method of calcium sulphate hemihydrate matrix material, it comprises the steps: the mixture by above-mentioned mesoporous Magnesium Silicate q-agent and sulfate hemihydrate calcium powder, and with solid solution mix and blend, compression molding, solidification, dries and get final product.
Wherein, described calcium sulphate hemihydrate is preferably β-calcium sulphate hemihydrate.Described sulfate hemihydrate calcium powder obtains preferably by following step: terra alba is carried out first sintering at 110 ~ 130 DEG C, then carries out second time sintering at 150 ~ 170 DEG C, namely obtains described sulfate hemihydrate calcium powder.
Wherein, the temperature rise rate of described first sintering and second time sintering is preferably 1 ~ 2 DEG C/min.The time of described first sintering is preferably 11 ~ 13 hours, and the time of described second time sintering is preferably 5 ~ 7 hours.
Wherein, it is preferably 1wt% ~ 50wt% that the consumption of described mesoporous Magnesium Silicate q-agent accounts for described mixture total weight amount, is more preferably 20wt% ~ 40wt%; It is preferably 50wt% ~ 99wt% that the consumption of described sulfate hemihydrate calcium powder accounts for described mixture total weight amount, is more preferably 60wt% ~ 80wt%.
Wherein, the mass ratio of described mixture and described solid solution is preferably 1:(0.5 ~ 1.5).
Wherein, described solid solution can be the solid solution that this area routine uses, and is generally water.
Wherein, the method for described compression molding and condition can be method and the condition of this area routine, preferably shaping for pressing in Teflon mould.
Wherein, described solidification is preferably be cured under the condition of 90% ~ 110% in relative humidity.
Wherein, the time of described solidification is preferably 2 ~ 7 days, is more preferably 1 ~ 3 day.
Wherein, the temperature of described oven dry is preferably 20 ~ 40 DEG C, is more preferably 36 ~ 38 DEG C.
Present invention also offers a kind of calcium sulphate hemihydrate matrix material obtained by above-mentioned preparation method.
Present invention also offers the application of above-mentioned calcium sulphate hemihydrate matrix material in bone prosthesis.
Wherein, described bone prosthesis is preferably bone cement.
In the present invention, the shape of described bone prosthesis can according to actual needs by selecting different moulds to change with specification.
In the present invention, the mechanical performance index of described calcium sulphate hemihydrate matrix material is as follows:
Ultimate compression strength is 3MPa ~ 8MPa, and tensile strength is 1MPa ~ 5MPa, and bending strength is 1MPa ~ 4MPa.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is:
(1) mesoporous Magnesium Silicate q-agent of the present invention is in long bar-shaped, and length on average about 30 μm, diameter is 7 ~ 10 μm, and its mesoporous pore size is 5nm ~ 15nm, and mesoporous pore size is evenly distributed.
(2) preparation is simple as bone prosthesis especially bone cement for mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material of the present invention, can prepare the bone prosthesis of different shapes, specification according to the preparation technology of corresponding this composite bone cement of adjustment of clinical demand.
(3) mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material of the present invention has good biological activity and biocompatibility as bone prosthesis especially bone cement, can stimulation of bone growth, and accelerated bone heals, and reduces the healing time after bone implant material.
(4) calcium sulphate hemihydrate in the present invention can degradablely absorb in vivo, has good biocompatibility and bone conduction effect, is beneficial to scleroblast and grows into material internal.
(5) the mesoporous Magnesium Silicate q-agent in the present invention, not only has the advantage of traditional mg-based material, and its meso-hole structure can be used as slow releasing carrier of medication, slowly-releasing microbiotic and osteogenic factor etc.The magnesium ion of high density can improve osteoblastic activity; In vitro in environment, magnesium can promote the deposition of phosphatic rock, increases mediation osteogenesis.It has significant advantage as slow releasing carrier of medication: medication of locally fixing a point, drug level is high, less to systemic effects.
Accompanying drawing explanation
Fig. 1 is stereoscan photograph (a) and the transmission electron microscope photo (b) of mesoporous Magnesium Silicate q-agent in embodiment 1.
Fig. 2 is the N of the mesoporous Magnesium Silicate q-agent in embodiment 1
2adsorption/desorption curve (a) and pore size distribution curve (b).
The infrared spectrogram of mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material (c) that mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material (b) that Fig. 3 is calcium sulphate hemihydrate (a), embodiment 4 is obtained, embodiment 6 obtain.
The XRD figure of mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material (c) that mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material (b) that Fig. 4 is calcium sulphate hemihydrate (a), embodiment 4 is obtained, embodiment 6 obtain.
Fig. 5 is the digital photograph figure of obtained mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material (b) of obtained mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material (a) of embodiment 4, embodiment 6.
Fig. 6 is the stereoscan photograph figure of obtained mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material (b) of obtained mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material (a) of embodiment 4, embodiment 6.
Fig. 7 is the composite degradation rate curve figure in effect example 1, wherein curve a represents calcium sulphate hemihydrate, curve b represents that mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material that embodiment 4 is obtained, curve c represent mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material that embodiment 6 is obtained.
Fig. 8 is the stereoscan photograph figure of the mineralising result of matrix material in effect example 2.Wherein a represents calcium sulphate hemihydrate, and b represents that mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material that embodiment 4 is obtained, c represent mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material that embodiment 6 is obtained.
Fig. 9 is the cell adhesion propagation stereoscan photograph figure of the matrix material in effect example 3, wherein a represents calcium sulphate hemihydrate, b represents that mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material that embodiment 4 is obtained, c represent mesoporous Magnesium Silicate q-agent-calcium sulphate hemihydrate matrix material that embodiment 6 is obtained.
Figure 10 is the elution profiles figure of the matrix material in effect example 4 to Vitamin D3 500,000 I.U/GM.A represents calcium sulphate hemihydrate, and b represents that, by the obtained 20%m-MS+VD/CS composite bone cement material of embodiment 4 method, c represents by the obtained 40%m-MS+VD/CS composite bone cement material of embodiment 6 method.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
In following embodiment, the relative molecular mass of P123 used is 5800, is purchased from Aldrich-sigma Reagent Company.
Embodiment 1
A preparation method for mesoporous Magnesium Silicate q-agent, it comprises the steps:
(1) water of P123 and the 30mL of 4.0g is mixed, to solution clarification, at 50 DEG C, add 120mL concentration is that the hydrochloric acid of 2mol/L is uniformly mixed 1h, then the magnesium nitrate hexahydrate of 9.6g is added, the TEOS of 9.12mL is dropped in solution with the speed of 15/min, be stirred to after white opacity appears in solution, continue stirring 5 hours, obtain collosol and gel white emulsion;
(2) by the ageing 3 days at 25 DEG C of collosol and gel white emulsion, then suction filtration removing upper liquid, carries out drying by throw out at 80 DEG C, then sinters 6 hours at 600 DEG C, to obtain final product.
Stereoscan photograph and the transmission electron microscope photo of this mesoporous Magnesium Silicate q-agent are shown in Fig. 1 (a), (b) respectively; The mesoporous pore size of this mesoporous Magnesium Silicate q-agent is at 10nm ~ 15nm, and obtained mesoporous Magnesium Silicate q-agent is in long bar-shaped, and length on average about 30 μm, diameter is 7 ~ 10 μm.
Fig. 2 is the N of the mesoporous Magnesium Silicate q-agent that this embodiment obtains
2adsorption/desorption curve (a) and pore size distribution curve (b), as can be seen from Fig. 2 (a), mesoporous Magnesium Silicate q-agent is to N
2adsorption/desorption cycle performance better; And as can be seen from Fig. 2 (b), the mesoporous pore size of the mesoporous Magnesium Silicate q-agent of more than 80% is at 10nm ~ 15nm.
Embodiment 2
(1) water of P123 and the 28mL of 4.0g is mixed, to solution clarification, at 50 DEG C, add 140mL concentration is that the hydrochloric acid of 1mol/L is uniformly mixed 1h, then the magnesium nitrate hexahydrate of 9.6g is added, the TEOS of 9.12mL is dropped in solution with the speed of 15/min, be stirred to after white opacity appears in solution, continue stirring 6 hours, obtain collosol and gel white emulsion;
(2) by the ageing 3 days at 25 DEG C of collosol and gel white emulsion, then suction filtration removing upper liquid, carries out drying by throw out at 80 DEG C, then sinters 6 hours at 550 DEG C, to obtain final product.
The parameter index of the mesoporous Magnesium Silicate q-agent that this embodiment obtains is with embodiment 1.
Embodiment 3
(1) water of P123 and the 30mL of 4.0g is mixed, to solution clarification, at 50 DEG C, add 120mL concentration is that the hydrochloric acid of 2mol/L is uniformly mixed 1h, then the magnesium nitrate hexahydrate of 8.4g is added, the TEOS of 13.2mL is dropped in solution with the speed of 18/min, be stirred to after white opacity appears in solution, continue stirring 7 hours, obtain collosol and gel white emulsion;
(2) by the ageing 3 days at 25 DEG C of collosol and gel white emulsion, then suction filtration removing upper liquid, carries out drying by throw out at 80 DEG C, then sinters 6 hours at 600 DEG C, to obtain final product.
The parameter index of the mesoporous Magnesium Silicate q-agent that this embodiment obtains is with embodiment 1.
Embodiment 4
The preparation method of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material, it comprises the steps:
(1) calcination method is used to prepare β-sulfate hemihydrate calcium powder by terra alba.Use chamber type electric resistance furnace to calcine (twice temperature rise rate is 1 DEG C/min) terra alba, first 120 DEG C time, be incubated 12 hours, be then warmed up to 160 DEG C and keep 6 hours, its Isothermal Dehydration is reacted completely.Namely obtain calcium sulphate hemihydrate after naturally cooling, namely planetary ball mill obtains sulfate hemihydrate calcium powder after pulverizing.
(2) by mesoporous magnesium silicate powders obtained for 0.2g (20wt%) embodiment 1 and 0.8g (80wt%) sulfate hemihydrate calcium powder mixing and stirring, composite powder is obtained.Be solid solution with deionized water, add 600 μ L deionized waters, namely solid-to-liquid ratio is 1:0.6, stirs to obtain material-mud.This material-mud is inserted in corresponding Teflon mould, is placed in 100% relative humidity, 37 DEG C of environment curing 3 days, obtains composite bone cement sample, be designated as 20%m-MS/CS.
The infrared spectrogram of this composite bone cement sample as shown in Figure 3; XRD figure as shown in Figure 4; Digital photograph as shown in Figure 5; Stereoscan photograph as shown in Figure 6.
Embodiment 5
The preparation method of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material, it comprises the steps:
By the sulfate hemihydrate calcium powder mixing and stirring that mesoporous magnesium silicate powders obtained for 0.2g (20wt%) embodiment 1 and 0.8g (80wt%) embodiment 4 (1) obtain, obtain composite powder.Be solid solution with deionized water, add 700 μ L deionized waters, namely solid-to-liquid ratio is 1:0.7, stirs to obtain material-mud.This material-mud is inserted in corresponding Teflon mould, is placed in 100% relative humidity, 37 DEG C of environment curing 2 days, obtains composite bone cement sample, be designated as 20%m-MS/CS-2.
Embodiment 6
The preparation method of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material, it comprises the steps:
By the sulfate hemihydrate calcium powder mixing and stirring that mesoporous magnesium silicate powders obtained for 0.4g (40wt%) embodiment 1 and 0.6g (60wt%) embodiment 4 (1) obtain, obtain composite powder.Be solid solution with deionized water, add 1000 μ L deionized waters, namely solid-to-liquid ratio is 1:1, stirs to obtain material-mud.This material-mud is inserted in corresponding Teflon mould, is placed in 100% relative humidity, 37 DEG C of environment curing 2 days, obtains composite bone cement sample, be designated as 40%m-MS/CS.
The infrared spectrogram of this composite bone cement sample as shown in Figure 3; XRD figure as shown in Figure 4; Digital photograph as shown in Figure 5; Stereoscan photograph as shown in Figure 6.
Embodiment 7
The preparation method of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material, it comprises the steps:
By the sulfate hemihydrate calcium powder mixing and stirring that mesoporous magnesium silicate powders obtained for 0.4g (40wt%) embodiment 1 and 0.6g (60wt%) embodiment 4 (1) obtain, obtain composite powder.Be solid solution with deionized water, add 1100 μ L deionized waters, namely solid-to-liquid ratio is 1:1.1, stirs to obtain material-mud.This material-mud is inserted in corresponding Teflon mould, is placed in 100% relative humidity, 37 DEG C of environment curing 2 days, obtains composite bone cement sample, be designated as 40%m-MS/CS-2.
Effect example 1
The degradation experiment of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material:
Carry out degradation experiment to mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material that embodiment 4 and embodiment 6 obtain, wherein sample diameter is 12mm, and thickness is 2mm, and degradation experiment concrete grammar is as follows:
After 50mL 0.1mol/L Tutofusin tris (Tris) solution and 42mL 0.1mol/L hydrochloric acid mix, be diluted with water to 100mL, be mixed with the Tris-HCl damping fluid of the material of pH=7.4, real for densification sheet is immersed in Tris-HCl solution with 0.1g/20mL solid-liquid ratio, in (pH=7.4's), degeneration system is put into tetrafluoroethylene bottle, bottle is placed on the shaking table that steady temperature is 37 DEG C.1,2,3,4,5,6,7,8,10, and after 12 weeks, take out support, and be dried to constant weight in 120 DEG C of baking ovens.Record the final weight of each sample.Degradation rate represents with the rate of weight loss of different time points sample (weightlessness/initial weight).In this research, calcium sulphate hemihydrate (being designated as CS) real sheet in contrast.As shown in Figure 7, the degradation rate of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material that the present invention obtains is better than calcium sulphate hemihydrate sample to result.
Effect example 2
The Bioactivity experiment of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material:
Carry out Bioactivity experiment to mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material that embodiment 4 and embodiment 6 obtain, wherein sample diameter is 12mm, and thickness is 2mm, and Bioactivity experiment concrete grammar is as follows:
First simulated body fluid (simulated body fluid is prepared, SBF), related reagent must be added successively in strict accordance with operating process, and will keep configuring the clean of container used, add-on and the addition sequence of each reagent are as follows: the amount of each reagent needed for the SBF solution of preparation 1L:
NaCl 7.996g，NaHCO
30.353g，KCl 0.224g，K
2HPO
4·3H
2O 0.228g，MgCl
2·6H
2O0.305g，HCl 0.045mol，CaCl
20.278g，Na
2SO
40.071g，CNH
2(CH
2OH)
36.057g。
The situation that the biological activity (calcium sulphate hemihydrate (CS) in contrast) of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material is immersed in simulated body fluid (SBF) different time rear surface generation phosphatic rock by working sample is weighed.The sample of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate composite bone cement with solid-liquid mass ratio for 0.1g/20mL is immersed in SBF.This system is placed in the constant-temperature table of 37 DEG C.From solution, shift out sample, with deionized water, the sample be separated from solution is carefully cleaned, dry in the baking oven of 37 DEG C.After immersion, the pattern SEM of material is characterized.As shown in Figure 8, mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material that the present invention obtains is more conducive to the deposition of phosphatic rock to result relative to calcium sulphate hemihydrate sample.
Effect example 3
The cell adhesion proliferation experiment of mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material:
Carry out degradation experiment to mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material that embodiment 4 and embodiment 6 obtain, wherein sample diameter is 12mm, and thickness is 2mm, and the concrete grammar of cell adhesion proliferation experiment is as follows:
MC3T3-E1 cell is seeded in two kinds of samples (three groups of Duplicate Samples, calcium sulfate material) with every hole 1w quantity cultivate, after 24h uses stationary liquid that cell is fixing, under scanning electron microscope, observation of cell adheres to situation, as Fig. 9.In Fig. 9, (a) is cell adhesion situation on calcium sulphate hemihydrate, b (), (c) are mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material group cell adhesion situation, result shows, all there are cell adhesion and propagation in bi-material surface, but the cell quantity that mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material group adheres to is more and have and better adhere to form, show that it has better biological activity and cell compatibility.
Effect example 4
Mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material is tested the slowly-releasing of Vitamin D3 500,000 I.U/GM:
Vitamin D3 500,000 I.U/GM is dissolved in deionized water, is mixed with the VD solution that concentration is 10mg/mL.Paired for solution dilution different gradient concentration (0.4mg/mL, 0.2mg/mL, 0.1mg/mL, 0.08mg/mL, 0.06mg/mL, 0.04mg/mL, 0.02mg/mL, 0.02mg/mL), measure solution in the absorbancy of 264nm with ultra-violet absorption spectrum instrument, make the typical curve of Vitamin D3 500,000 I.U/GM.
4g m-MS (mesoporous Magnesium Silicate q-agent) powder is added in 100mL Vitamin D3 500,000 I.U/GM solution.Adsorption experiment: carry out in the shaking table of 37 DEG C of constant temperature, oscillation frequency 80r/min.After 24 hours, by solution centrifugal, remove supernatant liquor, put into 40 DEG C of oven dryings, dried powder (being designated as m-MS+VD) is prepared m-MS+VD/CS composite bone cement material by the method for embodiment 4 and embodiment 6, and wherein sample diameter is 12mm, and thickness is 2mm.
Above-mentioned sample is put into PBS solution, in the shaking table of 37 DEG C of constant temperature, carries out the releasing research of medicine, oscillation frequency 80r/min.Respectively 6,12,24,48,72,96,120,144,168 is little constantly by solution centrifugal, gets supernatant liquor 0.5mL, surveys absorbancy at 264nm, adds PBS 0.5mL in solution simultaneously.The amount of cumulative release medicine is calculated according to typical curve.
In this experiment, often organize three Duplicate Samples, and the sulfate hemihydrate calcium material without m-MS is used the same method test in contrast.
Experimental result as shown in Figure 10, curve a represents calcium sulphate hemihydrate, curve b represents by the obtained 20%m-MS+VD/CS composite bone cement material (being namely adsorbed with the mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material of Vitamin D3 500,000 I.U/GM) of embodiment 4 method, curve c represents by the obtained 40%m-MS+VD/CS composite bone cement material (being namely adsorbed with the mesoporous Magnesium Silicate q-agent/calcium sulphate hemihydrate matrix material of Vitamin D3 500,000 I.U/GM) of embodiment 6 method, as can be seen from the figure, mesoporous Magnesium Silicate q-agent/the slow release effect of calcium sulphate hemihydrate matrix material to Vitamin D3 500,000 I.U/GM that the present invention obtains is better, it has significant advantage as slow releasing carrier of medication.
Effect example 5
Mechanical property test:
Carried out Mechanics Performance Testing to the matrix material of embodiment 4 ~ 7, test result is in table 1.
The mechanical property of the matrix material that each embodiment of table 1 obtains
Claims (10)
1. a preparation method for mesoporous Magnesium Silicate q-agent, is characterized in that, it comprises the steps:
(1) in the mixture of P123 and water, it is even to add mixed in hydrochloric acid, then adds solubility magnesium salts, is dropped to by TEOS in solution, is stirred to after white opacity appears in solution, continues to stir, obtain collosol and gel white emulsion;
(2) by described white emulsion ageing, suction filtration removes supernatant liquid, and by drying precipitate, sintering, obtains mesoporous Magnesium Silicate q-agent.
2. preparation method as claimed in claim 1, it is characterized in that, in step (1), the described temperature adding hydrochloric acid is 36 ~ 55 DEG C;
In step (1), the concentration of described hydrochloric acid is 1 ~ 4mol/L;
In step (1), described solubility magnesium salts is magnesium nitrate hexahydrate;
In step (1), the time that described continuation is stirred is 5 ~ 7 hours;
And/or, in step (1), the mass ratio of described P123 and described water is 1:(7 ~ 8.6), the mass volume ratio of described P123 and described hydrochloric acid is 1g:(28 ~ 35) mL, the mass volume ratio of described P123 and described TEOS is 1g:(2 ~ 3.3) mL, the speed of described dropping is 8/min ~ 20 droplet/min; The mass ratio of described P123 and described solubility magnesium salts is 1:(2.1 ~ 2.8).
3. preparation method as claimed in claim 1, it is characterized in that, in step (2), the temperature of described ageing is 10 ~ 30 DEG C, and the time of described ageing is 2 ~ 4 days;
In step (2), the temperature of described drying is 78 ~ 82 DEG C;
And/or in step (2), the temperature of described sintering is 550 ~ 620 DEG C, and the time of described sintering is 5 ~ 7 hours.
4. the mesoporous Magnesium Silicate q-agent that the preparation method according to any one of claims 1 to 3 obtains, is characterized in that, described mesoporous Magnesium Silicate q-agent is in long bar-shaped, and the diameter of described mesoporous Magnesium Silicate q-agent is 7 μm ~ 10 μm; The mesoporous pore size of described mesoporous Magnesium Silicate q-agent is 5nm ~ 15nm, and preferably the mesoporous pore size of 80% above-described mesoporous Magnesium Silicate q-agent is 10nm ~ 15nm.
5. a preparation method for calcium sulphate hemihydrate matrix material, is characterized in that, it comprises the steps: the mixture by mesoporous Magnesium Silicate q-agent as claimed in claim 4 and sulfate hemihydrate calcium powder, and with solid solution mix and blend, compression molding, solidification, dries and get final product.
6. preparation method as claimed in claim 5, it is characterized in that, described sulfate hemihydrate calcium powder is obtained by following step: terra alba is carried out first sintering at 110 ~ 130 DEG C, then carries out second time sintering at 150 ~ 170 DEG C, namely obtains described sulfate hemihydrate calcium powder;
It is 1wt% ~ 50wt% that the consumption of described mesoporous Magnesium Silicate q-agent accounts for described mixture total weight amount; It is 50wt% ~ 99wt% that the consumption of described sulfate hemihydrate calcium powder accounts for described mixture total weight amount;
The mass ratio of described mixture and described solid solution is 1:(0.5 ~ 1.5);
And/or described solid solution is water.
7. preparation method as claimed in claim 6, is characterized in that, the temperature rise rate of described first sintering and second time sintering is 1 ~ 2 DEG C/min; The time of described first sintering is 11 ~ 13 hours, and the time of described second time sintering is 5 ~ 7 hours;
And/or it is 20wt% ~ 40wt% that the consumption of described mesoporous Magnesium Silicate q-agent accounts for described mixture total weight amount; It is 60wt% ~ 80wt% that the consumption of described sulfate hemihydrate calcium powder accounts for described mixture total weight amount.
8. preparation method as claimed in claim 5, is characterized in that, described compression molding is shaping for pressing in Teflon mould;
The described relative humidity that is solidificated in is be cured under the condition of 90% ~ 110%;
The time of described solidification is 2 ~ 7 days, is preferably 1 ~ 3 day;
And/or the temperature of described oven dry is 20 ~ 40 DEG C, is preferably 36 ~ 38 DEG C.
9. the calcium sulphate hemihydrate matrix material that obtains of the preparation method according to any one of claim 5 ~ 8.
10. the application of a calcium sulphate hemihydrate matrix material as claimed in claim 9 in bone prosthesis.
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| CN112408968A (en) * | 2020-11-13 | 2021-02-26 | 武汉大学 | Bioactive 3D printing ceramic and preparation method thereof |
| CN112408968B (en) * | 2020-11-13 | 2021-09-24 | 武汉大学 | Bioactive 3D printing ceramic and preparation method thereof |
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