CN102488920A - Alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with nuclear shell structure and preparation thereof - Google Patents
Alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with nuclear shell structure and preparation thereof Download PDFInfo
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Abstract
The invention discloses an alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with a nuclear shell structure and preparation thereof. The composite granule has a microstructure in which the hydroxyapatite wraps the alpha-calcium sulfate hemihydrate. The preparation method comprises the steps of: using deionized water as a solvent, dissolving a proper dosage of organic crystal modifier and inorganic salt crystal modifier, adding calcium sulfate dehydrate and hydroxyapatite, and performing hydrothermal synthesis under certain technical parameters. According to the invention, the alpha-calcium sulfate hemihydrate and the hydroxyapatite are compounded in the microstructure so as to adjust the quick consolidation defect of pure alpha-calcium sulfate hemihydrate to improve the injection performance thereof, and a microstructure with a controllable wrapping degree can be formed to adjust and control the biodegradation performance thereof, so that the composite granule has a brilliant clinical application prospect.
Description
Technical field
The invention belongs to the bio-medical material preparing technical field, be specifically related to α-half-H 2 O calcium sulphate/hydroxyapatite composite particles of a kind of nucleocapsid structure and preparation method thereof.
Background technology
Calcium sulfate (CS) is applied to clinical existing more than 100 year history as bone grafting material, and it is confirmed by numerous experiment in the intravital safety of people already.It is good that calcium sulfate has histocompatibility, and the slightly acidic environment and the calcium phosphate crystal that form after bone-inducting active height, the biodegradation can attract osteoclast, quicken characteristics such as new bone formation.But calcium sulfate degradation in vivo excessive velocities becomes a factor that limits its clinical practice.
Medical calcium sulfate bone substitute OsteoSet that U.S. Wright Healtech S.A. develops in succession and MIIG series, all α-the half-H 2 O calcium sulphate with given shape and size is the basis.This medical grade calcium sulfate has stable 3-d modelling, makes new bone to reinvent by this configuration, and quality, intensity and the profile of new bone and normal bone are matched.Its purity is high, impurity is few, and the crystal structure height is consistent, and its absorption rate of back that implants is stable, but the relative new bone growth speed of its absorption rate is still very fast.
Studying and use the more calcium phosphate as bioactive materials at present is hydroxyapatite and tricalcium phosphate.Wherein, hydroxyapatite has similar chemical constituent, crystal structure with osseous tissue, is easy to by the host bone utilization, and degraded slowly has good bone conduction effect.The syringeability calcium phosphate bone cement is claimed the self-curing bone cement again, and is easy and simple to handle, and good biocompatibility can be injected defect to the marrow, and in-situ solidifying adapts to that bone is damaged to carry out mouldingly, meets the requirement of minimally invasive surgery, has become various countries scholar's a research focus.But its degraded slowly usually, and RT is long in vivo, do not reach the requirement of degraded fully in the treatment phase, influenced growing into of new bone, and extensive use receives restriction to a certain degree.
Too fast to the calcium sulfate absorption rate, and calcium phosphate slow degradation problem is studied and it is also a lot of to report, purpose all is the advantage that combines both, prepares the composite with good biological performance.The patent No. is that the Chinese invention patent of ZL200710063903.4 discloses a kind of new-type of inorganic bone grafting material, is made up of by certain quality mark proportioning bata-tricalcium phosphate and α-half-H 2 O calcium sulphate; Application number is the method for preparing that 201010201897.6 Chinese invention patent application discloses a kind of self pore-forming calcium phosphate cement bracket, and certain calcium sulfate is joined the injectable calcium phosphate bone cement, prepares novel composite bone cement; Application number is that 201010185090.8 Chinese invention patent application discloses a kind of compound bone based on nanometer hydroxyapatite and half-H 2 O calcium sulphate and repairs material and preparation method thereof, and α-half-H 2 O calcium sulphate, hydroxyapatite and additive are formed composite bone repairing material.Mix but calcium sulfate and calcium phosphate are just simple in its microstructure, its dissolving and degradation behavior characteristic are still followed the characteristics of calcium sulfate and calcium phosphate self, do not obtain good regulation and control.
Summary of the invention
The invention provides α-half-H 2 O calcium sulphate/hydroxyapatite composite particles of a kind of nucleocapsid structure and preparation method thereof; Realize α-half-H 2 O calcium sulphate/hydroxyapatite compound in microstructure; To adjust the fast setting of simple α-half-H 2 O calcium sulphate; Improve its injection performance, and, can regulate and control its biodegradability according to the difference of wrapping up degree in the microstructure.
A kind of α-half-H 2 O calcium sulphate of nucleocapsid structure/hydroxyapatite composite particles has the microstructure that hydroxyapatite wraps up α-half-H 2 O calcium sulphate, and described α-half-H 2 O calcium sulphate is generally cylindric or six side's α-half-H 2 O calcium sulphates.
α-the half-H 2 O calcium sulphate of said nucleocapsid structure/hydroxyapatite composite particles is prepared by following method:
(1) in deionized water, add organic type of crystal modifier and inorganic salts crystal modifier, be stirred to dissolving fully, making changes brilliant solution; Wherein, said organic type of crystal modifier is sodium citrate, citric acid, succinic acid or potassium oxalate, and said inorganic salts crystal modifier is magnesium sulfate, aluminum sulfate or potassium sulfate; The quality of said organic type of crystal modifier is 0.05%～0.2% of a said deionized water quality, and the quality of said inorganic salts crystal modifier is 0.5%～2% of a said deionized water quality;
(2) in the brilliant solution of said commentaries on classics, add calcium sulphate dihydrate and hydroxyapatite successively, form solid-liquid mixing system; Wherein, the mass ratio of said calcium sulphate dihydrate and said deionized water is 1: (2～6), and said hydroxyapatite: the mass ratio of calcium sulphate dihydrate is (0.1～1): 1;
(3) place 130～160 ℃ water heating kettle constant temperature to handle 4～8 hours said solid-liquid mixing system after, from said water heating kettle, leach crude product;
(4) water of said crude product with 90～100 ℃ is cleaned,, obtain α-half-H 2 O calcium sulphate/hydroxyapatite composite particles again 90～110 ℃ of dryings.
In the optimized technical scheme, the quality of said organic type of crystal modifier is 0.05% of a said deionized water quality, and the quality of said inorganic salts crystal modifier is 2% of a said deionized water quality.
In the optimized technical scheme, the mass ratio of said calcium sulphate dihydrate and said deionized water is 1: 4, said hydroxyapatite: the mass ratio of calcium sulphate dihydrate is 0.75: 1.
Among the present invention; With the deionized water is solvent; Be dissolved into an amount of organic type of crystal modifier and inorganic salts crystal modifier; Add sulfate dihydrate calcium powder and hydroxyapatite, and under the certain process parameter, prepare the α-half-H 2 O calcium sulphate/hydroxyapatite composite particles with nucleocapsid structure through the synthetic method of hydro-thermal, this composite particles has the microstructure of hydroxyapatite parcel α-half-H 2 O calcium sulphate.
The present invention through the method for hydrothermal treatment consists, dissolves and recrystallization the sulfate dihydrate calcium powder through in aqueous medium, introducing organic carboxyl acid root and inorganic ion under certain pressure and temperature, be transformed into α-half-H 2 O calcium sulphate, and particle size is 5～30 μ m; Simultaneously, because the existence of additive hydroxyapatite, it forms clad at α-half-H 2 O calcium sulphate on surface, influences the hydration characteristics of α-half-H 2 O calcium sulphate, improves its injection performance; And along with the difference of both ratios, the coating degree of microstructure is different, when influence its hydration characteristics, and the degradation property when also influencing its clinical practice, thus realization is to the regulation and control of biodegradability.
Compared with prior art, the present invention has following beneficial technical effects:
Composite particles of the present invention has been realized compound in microstructure of α-half-H 2 O calcium sulphate/hydroxyapatite; The hydroxyapatite that is wrapped in α-half-H 2 O calcium sulphate surface is because dissolution characteristics is different fully with α-half-H 2 O calcium sulphate; Played the effect of regulation and control surface with the water reaction rate; Thereby can adjust the granule degradation characteristic effectively, have good clinical application prospect.Method for preparing of the present invention is simple, and is simple to operate, and cost is low, is easy to industrialization.
Description of drawings
The XRD figure of the composite particles that Fig. 1 prepares for embodiment 1.
The microscopic appearance figure of the composite particles that Fig. 2 prepares for embodiment 1.
The ability spectrogram in the composite particles centre position that Fig. 3 prepares for embodiment 1.
The ability spectrogram at the composite particles edge that Fig. 4 prepares for embodiment 1.
The XRD figure of the composite particles that Fig. 5 prepares for embodiment 2.
The microscopic appearance figure of the composite particles that Fig. 6 prepares for embodiment 2.
The specific embodiment
Specify the present invention below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Embodiment 1
The deionized water of getting 40ml is as solvent, and the sodium citrate and the mass fraction that add 0.02g are the magnesium sulfate of 0.8g, is stirred to dissolving fully, and making changes brilliant solution; To wherein adding 10g sulfate dihydrate calcium powder (analytical pure level), add the hydroxyapatite of 7.5g again, form solid-liquid mixing system.
To join solid-liquid mixing system place 130 ℃ water heating kettle constant temperature to handle 6 hours, exit after the hydrothermal treatment consists, take out water heating kettle fast; And from water heating kettle, leach crude product; Clean in the baking oven that is placed on 90 ℃ with 90 ℃ hot water sucking filtration and to dry, obtain end product, be graininess.
Adopt X-ray diffractometer that the end product of gained is carried out component analysis and component sign, the XRD figure spectrum is as shown in Figure 1.Among Fig. 1, curve a and b are respectively the standard spectrogram of α-half-H 2 O calcium sulphate (CSH) and hydroxyapatite (HA), and curve c is corresponding to the XRD figure spectrum of end product, and is visible, ● locate peak position and belong to α-half-H 2 O calcium sulphate, zero place's peak position belongs to hydroxyapatite.Fig. 1 shows that the end product of present embodiment preparation is α-half-H 2 O calcium sulphate/hydroxyapatite composite particles.
The employing scanning electron microscope is carried out the microscopic appearance sign to the end product of gained, and SEM figure is as shown in Figure 2, and visible, end product has nucleocapsid structure, on the surface clad is arranged at columned α-half-H 2 O calcium sulphate.
Through the energy spectrum analysis to end product granule centre position (corresponding to (1) among Fig. 2) and edge (corresponding to (2) among Fig. 2) of gained, respectively like Fig. 3 and shown in Figure 4, the P constituent content on visible top layer is higher than inside, shows that clad is a hydroxyapatite.
Embodiment 2
The deionized water of getting 40ml adds the succinic acid of 0.04g and the aluminum sulfate of 0.6g as solvent, is stirred to dissolving fully, and making changes brilliant solution; To wherein adding 10g sulfate dihydrate calcium powder (analytical pure level), add the hydroxyapatite of 5g again, form solid-liquid mixing system.
To join solid-liquid mixing system place 160 ℃ water heating kettle constant temperature to handle 4 hours, exit after the hydrothermal treatment consists, take out water heating kettle fast; And from water heating kettle, leach crude product; Clean in the baking oven that is placed on 110 ℃ with 95 ℃ hot water sucking filtration and to dry, obtain end product, be graininess.
Adopt X-ray diffractometer that the end product of gained is carried out component analysis and component sign, the XRD figure spectrum is as shown in Figure 5.Among Fig. 5, curve a and b are respectively the standard spectrogram of α-half-H 2 O calcium sulphate (CSH) and hydroxyapatite (HA), and curve d is corresponding to the XRD figure spectrum of end product, and is visible, ● locate peak position and belong to α-half-H 2 O calcium sulphate, zero place's peak position belongs to hydroxyapatite.Fig. 5 shows that the end product of present embodiment preparation is α-half-H 2 O calcium sulphate/hydroxyapatite composite particles.
The employing scanning electron microscope is carried out the microscopic appearance sign to the end product of gained; SEM figure is as shown in Figure 6, and particle surface has more covering to exist, and visible end product has nucleocapsid structure; Further the particle surface clad is carried out energy spectrum analysis, show that clad is a hydroxyapatite.
Embodiment 3
The deionized water of getting 40ml adds the citric acid of 0.08g and the magnesium sulfate of 0.2g as solvent, is stirred to dissolving fully, and making changes brilliant solution; To wherein adding 10g sulfate dihydrate calcium powder (analytical pure level), add the hydroxyapatite of 2.5g again, form solid-liquid mixing system.
To join solid-liquid mixing system place 140 ℃ water heating kettle constant temperature to handle 8 hours, exit after the hydrothermal treatment consists, take out water heating kettle fast; And from water heating kettle, leach crude product; Clean in the baking oven that is placed on 90 ℃ with 100 ℃ hot water sucking filtration and to dry, obtain end product, be graininess.Through characterizing, end product is the α-half-H 2 O calcium sulphate/hydroxyapatite composite particles of nucleocapsid structure.
Embodiment 4
The deionized water of getting 40ml adds the potassium oxalate of 0.06g and the potassium sulfate of 0.4g as solvent, is stirred to dissolving fully, and making changes brilliant solution; To wherein adding 10g sulfate dihydrate calcium powder (analytical pure level), add the hydroxyapatite of 10g again, form solid-liquid mixing system.
To join solid-liquid mixing system place 150 ℃ water heating kettle constant temperature to handle 6 hours, exit after the hydrothermal treatment consists, take out water heating kettle fast; And from water heating kettle, leach crude product; Clean in the baking oven that is placed on 100 ℃ with 95 ℃ hot water sucking filtration and to dry, obtain end product, be graininess.Through characterizing, end product is the α-half-H 2 O calcium sulphate/hydroxyapatite composite particles with nucleocapsid structure.
Claims (4)
1. α-the half-H 2 O calcium sulphate of a nucleocapsid structure/hydroxyapatite composite particles is characterized in that, has the microstructure of hydroxyapatite parcel α-half-H 2 O calcium sulphate.
2. the method for preparing of the α-half-H 2 O calcium sulphate of nucleocapsid structure as claimed in claim 1/hydroxyapatite composite particles comprises:
(1) in deionized water, add organic type of crystal modifier and inorganic salts crystal modifier, be stirred to dissolving fully, making changes brilliant solution; Wherein, said organic type of crystal modifier is sodium citrate, citric acid, succinic acid or potassium oxalate, and said inorganic salts crystal modifier is magnesium sulfate, aluminum sulfate or potassium sulfate; The quality of said organic type of crystal modifier is 0.05%～0.2% of a said deionized water quality, and the quality of said inorganic salts crystal modifier is 0.5%～2% of a said deionized water quality;
(2) in the brilliant solution of said commentaries on classics, add calcium sulphate dihydrate and hydroxyapatite successively, form solid-liquid mixing system; Wherein, the mass ratio of said calcium sulphate dihydrate and said deionized water is 1: (2～6), and said hydroxyapatite: the mass ratio of calcium sulphate dihydrate is (0.1～1): 1;
(3) place 130～160 ℃ water heating kettle constant temperature to handle 4～8 hours said solid-liquid mixing system after, from said water heating kettle, leach crude product;
(4) water of said crude product with 90～100 ℃ is cleaned,, obtain α-half-H 2 O calcium sulphate/hydroxyapatite composite particles again 90～110 ℃ of dryings.
3. the method for preparing of the α-half-H 2 O calcium sulphate of nucleocapsid structure as claimed in claim 2/hydroxyapatite composite particles; It is characterized in that; The quality of said organic type of crystal modifier is 0.05% of a said deionized water quality, the quality of said inorganic salts crystal modifier be said deionized water quality 2%.
4. the method for preparing of the α-half-H 2 O calcium sulphate of nucleocapsid structure as claimed in claim 2/hydroxyapatite composite particles; It is characterized in that; The mass ratio of said calcium sulphate dihydrate and said deionized water is 1: 4, said hydroxyapatite: the mass ratio of calcium sulphate dihydrate is 0.75: 1.
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Cited By (11)
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| CN102815683A (en) * | 2012-09-07 | 2012-12-12 | 浙江大学 | Biomedical alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle and preparation method thereof |
| CN102815682A (en) * | 2012-09-07 | 2012-12-12 | 浙江大学 | Biomedical beta-Ca(HPO4)*(SO4)1-*.1/2H2O solid solution particle and preparation method thereof |
| CN103251976A (en) * | 2013-05-06 | 2013-08-21 | 浙江大学 | Biomedical calcium sulfate based composite particle for slowly releasing metal ions and preparation method of biomedical calcium sulfate based composite particle |
| CN105597158A (en) * | 2015-07-01 | 2016-05-25 | 李亚屏 | Degradable porous composite stent material for bone transplantation |
| CN108525004A (en) * | 2018-05-09 | 2018-09-14 | 湖北民族学院 | Alpha-semi water plaster stone/hydroxyapatite composite microspheres and preparation method thereof |
| CN109224125A (en) * | 2018-09-28 | 2019-01-18 | 福州大学 | A kind of syringeability shell/calcium sulfate bone cement and preparation method thereof |
| CN109793922A (en) * | 2019-03-01 | 2019-05-24 | 昆明理工大学 | A kind of calcium sulphate dihydrate/monetite Core-shell structure material and preparation method thereof |
| CN109821066A (en) * | 2019-03-04 | 2019-05-31 | 昆明理工大学 | A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support |
| CN114477261A (en) * | 2020-10-26 | 2022-05-13 | 北京威达峰医学生物材料有限责任公司 | Preparation method of high-purity surgical grade alpha-calcium sulfate hemihydrate with adjustable crystal size |
| CN114522276A (en) * | 2022-03-04 | 2022-05-24 | 武汉理工大学 | Zinc-doped semi-hydrated calcium sulfate based composite artificial bone material and preparation method and application thereof |
| CN115414525A (en) * | 2022-09-26 | 2022-12-02 | 杭州归领医疗器械有限公司 | Medical calcium sulfate artificial bone powder with core-shell structure and preparation method thereof |
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| CN102815682A (en) * | 2012-09-07 | 2012-12-12 | 浙江大学 | Biomedical beta-Ca(HPO4)*(SO4)1-*.1/2H2O solid solution particle and preparation method thereof |
| CN102815683B (en) * | 2012-09-07 | 2014-06-25 | 浙江大学 | Biomedical alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle and preparation method thereof |
| CN102815683A (en) * | 2012-09-07 | 2012-12-12 | 浙江大学 | Biomedical alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle and preparation method thereof |
| CN103251976A (en) * | 2013-05-06 | 2013-08-21 | 浙江大学 | Biomedical calcium sulfate based composite particle for slowly releasing metal ions and preparation method of biomedical calcium sulfate based composite particle |
| CN103251976B (en) * | 2013-05-06 | 2015-01-14 | 浙江大学 | Biomedical calcium sulfate based composite particle for slowly releasing metal ions and preparation method of biomedical calcium sulfate based composite particle |
| CN105597158A (en) * | 2015-07-01 | 2016-05-25 | 李亚屏 | Degradable porous composite stent material for bone transplantation |
| CN105597158B (en) * | 2015-07-01 | 2018-07-03 | 李亚屏 | A kind of degradable multiporous compound support frame material of bone collection |
| CN108525004B (en) * | 2018-05-09 | 2020-11-17 | 湖北民族学院 | Alpha-hemihydrate gypsum/hydroxyapatite composite microsphere and preparation method thereof |
| CN108525004A (en) * | 2018-05-09 | 2018-09-14 | 湖北民族学院 | Alpha-semi water plaster stone/hydroxyapatite composite microspheres and preparation method thereof |
| CN109224125A (en) * | 2018-09-28 | 2019-01-18 | 福州大学 | A kind of syringeability shell/calcium sulfate bone cement and preparation method thereof |
| CN109793922A (en) * | 2019-03-01 | 2019-05-24 | 昆明理工大学 | A kind of calcium sulphate dihydrate/monetite Core-shell structure material and preparation method thereof |
| CN109821066A (en) * | 2019-03-04 | 2019-05-31 | 昆明理工大学 | A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support |
| CN114477261A (en) * | 2020-10-26 | 2022-05-13 | 北京威达峰医学生物材料有限责任公司 | Preparation method of high-purity surgical grade alpha-calcium sulfate hemihydrate with adjustable crystal size |
| CN114522276A (en) * | 2022-03-04 | 2022-05-24 | 武汉理工大学 | Zinc-doped semi-hydrated calcium sulfate based composite artificial bone material and preparation method and application thereof |
| CN115414525A (en) * | 2022-09-26 | 2022-12-02 | 杭州归领医疗器械有限公司 | Medical calcium sulfate artificial bone powder with core-shell structure and preparation method thereof |
| CN115414525B (en) * | 2022-09-26 | 2023-08-18 | 杭州归领医疗器械有限公司 | Medical calcium sulfate artificial bone powder with core-shell structure and preparation method thereof |
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