CN100545084C - The preparation method of ordered porous hydroxyapatite material - Google Patents
The preparation method of ordered porous hydroxyapatite material Download PDFInfo
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- CN100545084C CN100545084C CNB200710171261XA CN200710171261A CN100545084C CN 100545084 C CN100545084 C CN 100545084C CN B200710171261X A CNB200710171261X A CN B200710171261XA CN 200710171261 A CN200710171261 A CN 200710171261A CN 100545084 C CN100545084 C CN 100545084C
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Abstract
The invention belongs to biomedical materials field, be specifically related to a kind of preparation method of ordered porous hydroxyapatite material, concrete steps are: the single SiO of dispersion that adopts silicon source hydrolytic polymerization to produce
2Microballoon is a template, forms orderly template by assembling, is infiltrating the hydroxyapatite precursor liquid in the template in order, and the dry solidification sintering is removed template after strong base solution soaks, and promptly gets ordered porous hydroxyapatite material.The hydroxyapatite of the present invention preparation has between the pore passage structure, aperture homogeneous of high-sequential and controllable, the Kong Yukong characteristics such as be interconnected, specific surface area is big, is with a wide range of applications in fields such as pharmaceutical carrier, biochip, immobilized enzyme.
Description
Technical field
The invention belongs to the bio-medical material technical field, be specifically related to a kind of preparation method of ordered porous hydroxyapatite.
Background technology
The pore structure of porous material has very big influence for the performance of material, especially ordered porous material, owing to have higher specific surface area, aperture that homogeneous is adjustable and regular pore passage structure, demonstrate important effect in fields such as optics, chemical industry and biomedicine, relevant preparation technology and performance study also become the research focus in material field.According to present domestic and international research achievement as can be known, template is one of most popular method of the ordered porous material of preparation.And, can be subdivided into several classes such as block copolymer template method, surfactant templates method, glue crystal template method again according to the difference of template.The block copolymer template method utilizes the constructional feature of segmented copolymer to prepare ordered porous material, and the surfactant templates rule utilizes tensio-active agent to prepare ordered porous material, and two kinds of template gained materials all have the pore passage structure of high-sequential.(2004, publication number: CN 1539733A) reported with the tensio-active agent to be the technology that template prepares the ordered mesoporous silica dioxide material, the aperture of gained material is 2～8nm to Chinese patent.Chinese patent (2006, publication number: CN 1785862A) reported to be the technology that template prepares ordered porous bioglass material with the segmented copolymer, and to its medicine carrying can masterpiece preliminary evaluation, the medicine carrying of discovering this material can force rate ordinary student thing glass have largely and improved.But because the duct of this material less (2～50nm), and not connected, thereby the perviousness of medicine and medicine carrying ability await further raising.As seen, surfactant templates method and block copolymer template method are owing to the restriction of this body structure of template, and the aperture of gained material is less, variable range is little, and is not communicated with between the Kong Yukong, and these characteristics have limited the application of material greatly.For example, need to increase the aperture of ordered porous material, realize the connection between the Kong Yukong simultaneously, just help the infiltration of medicine, help improving the medicine carrying ability of material in the medicament slow release field.Except the embedded material as drug release, the pore passage structure that is interconnected can also be realized mass transfer and the absorption in the finite space; Orderly and controlled pore structure also can be adsorbed the biomacromolecule of different sizes, realizes biomarker; Also can be used as the immobilization material of biomacromolecule, at enzyme with proteicly transport the effect of playing protective layer in the process.
Compare with preceding two kinds of template, glue crystal template method is a template with single dispersion gel microballoon, its pore size is decided by the size of gel micro-ball, thereby has a very big controllability, and the close-packed structure of microballoon makes microballoon after removal in the template in order, on hole wall, stay micropore, realize the connection between the Kong Yukong.These characteristics can make material satisfy more areas, particularly the service requirements in bio-medical field.
At present relevant ordered porous material is actually rare in the research of biological field, and only researchs also mainly concentrate on the research of ordered porous bioglass material.Chinese patent (2004, publication number: CN 1554607A) reported to be template, prepared the technology of mesoporous nano and mesopore-macropore bioglass material in conjunction with sol-gel technology with the tensio-active agent.Wherein, the mesoporous bio-vitric aperture of ordered nano is very little, and in the mesopore-macropore bio-vitric, the existence of macropore can influence mesoporous arrangement, causes the decline of the structurally ordered property of material hole.Infiltration and the pore passage structure of material in porous material is relative, and for uniform hole, material does not have specific directivity when infiltration is flowed, can permeate more equably in porous material and exist; And uneven hole, material the time has certain selectivity in infiltration, and the material monolithic homogeneity that obtains like this is not good, and local hole is not fully utilized, and therefore in a lot of Application Areass, aperture structure more has superiority than uneven aperture structure uniformly.In addition, bioglass material itself does not almost have adsorptive power, and this has also limited the use range of material to a certain extent.Therefore, when improving aperture, orderly hole, improve the absorption property of material itself, can widen the Application Areas of material greatly, increase its use value.
As everyone knows, hydroxyapatite (Hydroxyapatite) is the widely used biological active ceramic material of a class, has similar mineral composition to the skeleton tissue, and have excellent biological compatibility, safely, have no side effect, the growth of bootable new bone is a kind of ideal embedded type solid support material after implanting.In addition, hydroxyapatite also has excellent absorption property, and this performance has made it obtain using widely at biological fields such as blood purifying, enzyme and albumen sepn.
Based on this, we propose with single SiO of dispersion
2Gel micro-ball is a template, adopts glue crystal template method to prepare a kind of technical thought with wide-aperture ordered porous hydroxyapatite material.This material has excellent biological compatibility, biological activity and excellent absorption property, different needs can be satisfied in adjustable aperture, wide aperture and the sequential holes that is interconnected then can improve the infiltration of medicine and biomacromolecule greatly, thereby can be used for fields such as pharmaceutical carrier, biomarker and immobilized enzyme.
Summary of the invention
The object of the present invention is to provide a kind ofly have the homogeneous aperture, the aperture is adjustable, the preparation method of the ordered porous hydroxyapatite material that is interconnected between the Kong Yukong.
The preparation method of the ordered porous hydroxyapatite material that the present invention proposes comprises and adopts the silicon source to obtain single SiO of dispersion
2Microballoon and assembling form orderly template, hydroxyapatite precursor liquid in template in order infiltration and in order template remove, it is as follows specifically to wrap step:
(1) preparation of template in order
With silicon source, water is raw material, and ammoniacal liquor is catalyzer, silicon source, catalyzer and water is joined in the organic solvent by following mol ratio mix, and stirs in 20～40 ℃ water bath with thermostatic control 0.5～4 hour, forms monodisperse spherical SiO
2Microballoon, centrifugal, washing, drying is dispersed in the solvent again, forms 1～10wt% suspension liquid, leaves standstill, natural subsidence, drying at room temperature, promptly gets orderly SiO
2The glue crystal template, wherein: silicon source: catalyzer: water=1: (1.5～5): (10～40);
(2) infiltration of hydroxyapatite precursor liquid in orderly template
With calcium source, phosphorus source, water and ethanol stirring reaction 24～48h in 70-90 ℃ water bath with thermostatic control, the pH value of regulating colloidal sol is 7-9, obtains hydroxyapatite colloidal sols, is the precursor solution of final material; This precursor solution is splashed in the orderly glue crystal template of step (1) gained, dry solidification is then 500-900 ℃ of temperature lower calcination 2～4 hours;
(3) removal of template
After the sintered compact that obtains in the step (2) soaked, remove SiO in soak solution
2Template promptly gets ordered porous hydroxyapatite material.
Among the present invention, silicon source described in the step (1) can be tetraethoxy (TEOS).
Among the present invention, phosphorus source described in the step (2) can be trimethyl phosphite 99 (TMP) or triethyl phosphate (TEP).
Among the present invention, the calcium source can be four water-calcium nitrate described in the step (3).
Among the present invention, the concentration of described ammoniacal liquor is 25～28wt%.
Among the present invention, the described organic solvent of step (1) can be methyl alcohol, ethanol, propyl alcohol or butanols.
Among the present invention, soak solution described in the step (3) can be the sodium hydroxide solution of 0.1～10mol/L for volumetric molar concentration.
The present invention utilizes the template assembling, the ordered porous hydroxyapatite material that provides for preparing in conjunction with sol-gel method, this material has the aperture of homogeneous, pore size is adjustable (100～500nm), arrange in order in the aperture, be interconnected between the Kong Yukong, still having very high thermostability below 700 ℃, widened the kind and the purposes of large pore material.
The ordered porous hydroxyapatite material that utilizes the inventive method to make has than bigger serface, and biomacromolecules such as adsorbable albumen can be used for fields such as biomarker, pharmaceutical carrier, immobilized enzyme.
The present invention has the following advantages:
(1) reaction conditions gentleness of the present invention is easy to operation, and raw material is simple and easy to.
(2) the present invention can prepare the SiO of different pore sizes by changing proportioning raw materials
2Microballoon, thus make the ordered porous hydroxyapatite material in different apertures.
Characteristics such as (3) the present invention adopts the ordered porous hydroxyapatite material of glue crystal template method in conjunction with sol-gel method preparation, and it is orderly to have a pore passage structure, and the aperture is single, pore distribution is even, specific surface area is big; Material itself has excellent biocompatibility and biological activity, nontoxicity, and absorption property is strong, and the duct of hundreds of nm level helps adsorbing various albumen, enzyme and medical macromole, can be used for fields such as biomarker, immobilized enzyme, pharmaceutical carrier.
Description of drawings
Fig. 1 is single SiO of dispersion among the embodiment 2
2The transmission electron microscope photo of gel micro-ball shows prepared SiO
2Have the round profile and the size of homogeneous.
Fig. 2 is orderly SiO among the embodiment 2
2The environmental scanning electronic microscope photo of template shows SiO
2Microballoon is arranged very orderly.
Fig. 3 is the environmental scanning electronic microscope photo of ordered porous hydroxyapatite among the embodiment 2, has intuitively provided the pore passage structure of the orderly homogeneous of material.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
(1) gets 12ml water, 7ml ammoniacal liquor, 6ml tetraethoxy and 70ml methyl alcohol stirring reaction in 25 ℃ of waters bath with thermostatic control and after the centrifuge washing drying, obtain the SiO about 130nm after 3.5 hours
2Microballoon; Microballoon is dispersed in the ethanol again, is made into the 5wt% suspension liquid, can get SiO after static 7 days
2The glue crystal template;
(2) get 13.753g four water-calcium nitrate, 10.5ml water, 4ml triethyl phosphate and 10ml ethanol and mix after, splash into ammoniacal liquor and regulate pH value=8, in 80 ℃ of waters bath with thermostatic control, stir then and obtained hydroxyapatite colloidal sols in 24 hours, this colloidal sol is splashed into the SiO that has prepared in the step (1)
2In the glue crystal template, 50 ℃ of dryings were calcined 3 hours at 600 ℃ in muffle furnace after 12 hours;
(3) promptly get ordered porous hydroxyapatite material after the sodium hydroxide solution that the sintered compact of step (2) gained is put into 3.75mol/L soaks, the gained aperture is about 100nm.
Embodiment 2
(1) gets 14ml water, 18ml ammoniacal liquor, 8ml tetraethoxy and 40ml ethanol stirring reaction in 30 ℃ of waters bath with thermostatic control and after the centrifuge washing drying, obtain the SiO about 300nm after 2 hours
2Microballoon; Microballoon is dispersed in the ethanol again, is made into the 5wt% suspension liquid, can get SiO after static 7 days
2The glue crystal template;
(2) get 13.753g four water-calcium nitrate, 10.5ml water, 5ml trimethyl phosphite 99 and 14ml ethanol and mix after, splash into ammoniacal liquor and regulate pH value=8, in 75 ℃ of waters bath with thermostatic control, stir then and obtained hydroxyapatite colloidal sols in 30 hours, this colloidal sol is splashed into the SiO that has prepared in the step (1)
2In the glue crystal template, 50 ℃ of dryings were calcined 3 hours at 600 ℃ in muffle furnace after 12 hours;
(3) promptly get ordered porous hydroxyapatite material after the sodium hydroxide solution that the sintered compact of step (2) gained is put into 5mol/L soaks, the gained aperture is about 250nm.
Embodiment 3
(1) gets 24ml water, 40ml ammoniacal liquor, 12ml tetraethoxy and 40ml ethanol stirring reaction in 40 ℃ of waters bath with thermostatic control and after the centrifuge washing drying, obtain the SiO about 550nm after 1 hour
2Microballoon; Microballoon is dispersed in the ethanol again, is made into the 5wt% suspension liquid, can get SiO after static 7 days
2The glue crystal template;
(2) get 13.753g four water-calcium nitrate, 10.5ml water, 5ml trimethyl phosphite 99 and 14ml ethanol and mix after, splash into ammoniacal liquor and regulate pH value=8, in 80 ℃ of waters bath with thermostatic control, stir then and obtained hydroxyapatite colloidal sols in 24 hours, this colloidal sol is splashed into the SiO that has prepared in the step (1)
2In the glue crystal template, 70 ℃ of dryings were calcined 3 hours at 550 ℃ in muffle furnace after 5 hours;
(3) promptly get ordered porous hydroxyapatite material after the sodium hydroxide solution that the sintered compact in the step (2) is put into 7mol/L soaks, the gained aperture is about 500nm.
Embodiment 4
(1) gets 24ml water, 40ml ammoniacal liquor, 12ml tetraethoxy and 40ml butanols stirring reaction in 40 ℃ of waters bath with thermostatic control and after the centrifuge washing drying, obtain the SiO about 550nm after 1 hour
2Microballoon; Microballoon is dispersed in the ethanol again, is made into the 10wt% suspension liquid, can get SiO after static 5 days
2The glue crystal template;
(2) get 13.753g four water-calcium nitrate, 10.5ml water, 5ml trimethyl phosphite 99 and 14ml ethanol and mix after, splash into ammoniacal liquor and regulate pH value=9, in 80 ℃ of waters bath with thermostatic control, stir then and obtained hydroxyapatite colloidal sols in 36 hours, this colloidal sol is splashed into the SiO that has prepared in the step (1)
2In the glue crystal template, 70 ℃ of dryings were calcined 3 hours at 550 ℃ in muffle furnace after 5 hours;
(3) promptly get ordered porous hydroxyapatite material after the sodium hydroxide solution that the sintered compact in the step (2) is put into 1mol/L soaks, the gained aperture is about 500nm.
Embodiment 5
(1) gets 18ml water, 20ml ammoniacal liquor, 12ml tetraethoxy and 40ml propyl alcohol stirring reaction in 30 ℃ of waters bath with thermostatic control and after the centrifuge washing drying, obtain the SiO about 380nm after 2 hours
2Microballoon; Microballoon is dispersed in the ethanol again, is made into the 7.5wt% suspension liquid, can get SiO after static 5 days
2The glue crystal template;
(2) get 13.753g four water-calcium nitrate, 10.5ml water, 4ml triethyl phosphate and 10ml ethanol and mix after, splash into ammoniacal liquor and regulate pH value=7.5, in 80 ℃ of waters bath with thermostatic control, stir then and obtained hydroxyapatite colloidal sols in 48 hours, this colloidal sol is splashed into the SiO that has prepared in the step (1)
2In the glue crystal template, 50 ℃ of dryings were calcined 2.5 hours at 600 ℃ in muffle furnace after 24 hours;
(3) promptly get ordered porous hydroxyapatite material after the sodium hydroxide solution that the sintered compact in the step (2) is put into 0.5mol/L soaks, the gained aperture is about 300nm.
Claims (5)
1, a kind of preparation method of ordered porous hydroxyapatite material is characterized in that comprising and adopts the silicon source to obtain single SiO of dispersion
2Microballoon and assembling form orderly template, hydroxyapatite precursor liquid in template in order infiltration and in order template remove, it is as follows specifically to wrap step:
(1) preparation of template in order
With silicon source, water is raw material, and ammoniacal liquor is catalyzer, silicon source, catalyzer and water is joined in the organic solvent by following mol ratio mix, and stirs in 20～40 ℃ water bath with thermostatic control 0.5～4 hour, forms monodisperse spherical SiO
2Microballoon, centrifugal, washing, drying is dispersed in the solvent again, forms 1～10wt% suspension liquid, leaves standstill, natural subsidence, drying at room temperature, promptly gets orderly SiO
2The glue crystal template, wherein: silicon source: catalyzer: water=1: (1.5～5): (10～40);
(2) infiltration of hydroxyapatite precursor liquid in orderly template
With calcium source, phosphorus source, water and ethanol stirring reaction 24～48h in 70-90 ℃ water bath with thermostatic control, the pH value of regulating colloidal sol is 7-9, obtains hydroxyapatite colloidal sols, is the precursor solution of final material; This precursor solution is splashed in the orderly glue crystal template of step (1) gained, dry solidification is then 500-900 ℃ of temperature lower calcination 2～4 hours;
(3) removal of template
After the sintered compact that obtains in the step (2) soaked, remove SiO in soak solution
2Template promptly gets ordered porous hydroxyapatite material;
Wherein, the silicon source is a tetraethoxy described in the step (1), and described organic solvent is methyl alcohol, ethanol, propyl alcohol or butanols, and the concentration of described ammoniacal liquor is 25～28wt%.It is the sodium hydroxide solution of 0.1～10mol/L that soak solution described in the step (3) adopts volumetric molar concentration.
2, the preparation method of ordered porous hydroxyapatite material according to claim 1 is characterized in that the phosphorus source is trimethyl phosphite 99 or triethyl phosphate described in the step (2).
3, the preparation method of ordered porous hydroxyapatite material according to claim 1 is characterized in that the calcium source is a four water-calcium nitrate described in the step (3).
4, the preparation method of ordered porous hydroxyapatite material according to claim 1, it is characterized in that resulting ordered porous hydroxyapatite material, the aperture is 100～500nm, and arrange in order in the aperture, be interconnected between the Kong Yukong, still having very high thermostability below 700 ℃.
5, the ordered porous hydroxyapatite material for preparing of a kind of the method for claim 1 is in the application in biomarker, pharmaceutical carrier and immobilized enzyme field.
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| CN102153059B (en) * | 2011-04-13 | 2013-04-17 | 上海师范大学 | Method for preparing monodisperse hydroxyapatite by taking blue algae as template |
| CN102745660B (en) * | 2011-04-18 | 2014-03-26 | 中国科学院大连化学物理研究所 | Microfluidic chip based method for synthesizing needle-like hydroxyapatite nanoparticle |
| CN103083731A (en) * | 2011-11-08 | 2013-05-08 | 上海交通大学医学院附属第九人民医院 | Fiber porous titanium microsphere with drug loading capability |
| CN102701172B (en) * | 2012-06-21 | 2014-04-02 | 昆明理工大学 | Method for preparing hydroxyapatite nanocrystals or microcrystals by using plant as template |
| CN103086339A (en) * | 2013-02-18 | 2013-05-08 | 中国人民解放军南京军区南京总医院 | Porous hydroxyapatite flower-like microspheres and preparation method thereof |
| CN103588500B (en) * | 2013-11-17 | 2014-11-05 | 北华航天工业学院 | Preparation method of porous hydroxyapatite biological ceramic material |
| CN105255853B (en) * | 2015-11-10 | 2018-03-06 | 河南工业大学 | A kind of preparation method of magnetic hydroxylapatite immobilized lipase and the application in edible oil and fat processing |
| CN107265426B (en) * | 2016-04-07 | 2019-12-10 | 武汉亚洲生物材料有限公司 | template-mediated synthesis of silicon-containing hydroxyapatite material and preparation method thereof |
| CN106115644B (en) * | 2016-06-24 | 2017-12-01 | 张文凯 | A kind of preparation method of hydroxyapatite structure |
| CN109793898A (en) * | 2019-03-15 | 2019-05-24 | 吉林大学 | The application of hydroxyapatite in tablets |
| CN110000375B (en) * | 2019-04-17 | 2021-04-09 | 中国工程物理研究院激光聚变研究中心 | Ultrahigh-porosity porous metal material and preparation method thereof |
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| CN1397518A (en) * | 2002-08-28 | 2003-02-19 | 中国科学院长春应用化学研究所 | Process for preparing nano-class hydroxyphosphorite/alumina bioceramics |
| CN1475280A (en) * | 2003-06-17 | 2004-02-18 | 武汉理工大学 | Method of establishing nano organic silane dressing layer on hydroxy apatite surfac |
| CN1647778A (en) * | 2004-11-29 | 2005-08-03 | 西安理工大学 | Method for preparing hole structure gradient changing spherical inner hole artificial bone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1397518A (en) * | 2002-08-28 | 2003-02-19 | 中国科学院长春应用化学研究所 | Process for preparing nano-class hydroxyphosphorite/alumina bioceramics |
| CN1475280A (en) * | 2003-06-17 | 2004-02-18 | 武汉理工大学 | Method of establishing nano organic silane dressing layer on hydroxy apatite surfac |
| CN1647778A (en) * | 2004-11-29 | 2005-08-03 | 西安理工大学 | Method for preparing hole structure gradient changing spherical inner hole artificial bone |
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