CN101891175B - Enamel-shaped hydroxyapatite and preparation method and application thereof - Google Patents
Enamel-shaped hydroxyapatite and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of biomedical materials and relates to an enamel-shaped hydroxyapatite and a preparation method and application thereof, in particular to a method for synthesizing the enamel-shaped hydroxyapatite by induction of dual polyelectrolyte. In the method, soluble calcium salt and soluble phosphate are used as raw materials, and the dual polyelectrolyte comprising water-soluble cationic polyelectrolyte and organic polyatomic acid is used as a template; the prepared hydroxyapatite nano rods grow along the specific direction and are mutually stacked closely in parallel to form an enamel-shaped structure; and the diameter of each nano rod is 30-200nm. The method for preparing the hydroxyapatite with the enamel-shaped structure, which is provided by the invention, is not only favorable for people to further understand the biological mineralization processes of enamel crystals but also favorable for improving the mechanical properties of the hydroxyapatite, expands the application of the hydroxyapatite in tooth/bone replacing materials, and provides a new possibility for acquiring and popularizing high-quality medical hydroxyapatite materials.
Description
Technical field
The invention belongs to technical field of biomedical materials, be specifically related to a kind of enamel-shaped hydroxyapatite.
Background technology
Enamel is the highest hard tissues of the translucent calcification degree of the outer field white of corona, and it is inner mainly to play a part to take care of one's teeth, and is material the hardest in the human body, and its hardness is only second to diamond.Its special mechanical properties mainly gives the credit to the high-precision multilevel hierarchy of enamel.The formation of the multilevel hierarchy of this complicacy and enamel crystalline maturation are to accomplish through the consumption to organic constituent element.In the enamel forming process, along with the maturation of mineral, protein mass reduces, so obtain the enamel of high mineral content.This has also caused enamel after being destroyed, regeneration that can't be spontaneous.Therefore, the reconstruction of enamel structure and preparation are at clinical stomatology or in Materials science, all are significant.
Win 40350 is the main inorganic composition of animals and human beings body bone, has good biological activity and biocompatibility.Chemical method is adopted in the preparation of Win 40350 mostly, and preparation method commonly used has liquid-phase precipitation method, hydrothermal method, sol-gel method etc.The employing diverse ways prepares, and obtains the Win 40350 of different-shape and structure.The characteristic of Win 40350 is closely related with its specific surface area, size, size distribution and sintering activity etc.; The biological activity of Win 40350 receives the influence of factors such as its Ca/P, carbonate and foreign matter content, crystal size, pattern, sample structure, sintering process, and the Win 40350 of preparing different shape is the key that the excellent properties of Win 40350 is fully used.
Many clinically in recent years employing glass-ion cements spit of fland, light-cured composite and Dyract complex body are repaired damaged enamel.Yet these combination filling material all can not obtain the ideal effect, and the chemical bonding of depending merely on material is prone to cause charges to come off.In recent years, the research of type enamel biomaterial both at home and abroad mainly concentrates on the exploration of organic substrate (protein, non-protein macromolecule and polymer gel etc.) to the aspects such as regulation and control of hydroxyapatite crystal growth.The research of the Moradian-Oldak group of University of Southern California's school of dentistry shows, is becoming under the proteic regulation and control of glaze, and the enamel surfaces after the corrosion is in calcium phosphorus supersaturation liquid, and mineralising generates HAp crystal [Fan, the Y. of type of having enamel structure again; Sun, Z.; Moradian-Oldak, J.Biomaterials.2009,30,478-483].Old seapeak seminar of Peking University is adjusting control agent with the edetate, has synthesized Win 40350 array [Chen, HF.et al.Adv.Mater.200618,1846-1851] in the metallic surface.The Busch of Germany Ma Pu institute etc. utilizes the molecular bionics synthetic technology first; At enamel surface coating mixed gel as the mineralising template, thereby the fluoridated apatite layer [Busch, the S.Angew.Chem.Int.Edit.2004 that have obtained having similar enamel structure; 43,1428-1431].At present, the research of bionical tooth material does not still have big progress, and people are for the tissue of tooth reparation and survive and be in the desk study stage, and the artificial regeneration of the multilevel ordered structure that enamel is complicated still can't realize.
Phase transformation is considered to the important step in the biomineral forming process.Although the crystal-phase transformation mechanism in the enamel generative process is not also verified as yet, universal theory is thought into glaze proteic " nanometer ball chain " packaging assembly and in the process of tooth glaze mineralising, is played vital regulating and controlling effect.Research shows that the N end of protein molecular plays an important role in the process of assembling, its C end then is exposed to outside the assembly and hydroxyapatite crystal interacts and regulate and control its growth.According to these principles, just can design a kind of double base compound polyelectrolyte and be modeled to the proteic function of glaze, the bionical of type of realization enamel structure synthesizes, and then forms enamel-shaped hydroxyapatite.Yet the report that this area is relevant therewith at present is also considerably less.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of enamel-shaped hydroxyapatite is provided.Specifically; The present invention relates to a kind of in the synthetic method of double base polyelectrolyte regulation and control with hydroxyapatite crystal of enamel-shaped structure; Preparing method of the present invention is under the regulation and control of double base compound polyelectrolyte, and the block brushite (width is 0.5-2 μ m, and length is 1-10 μ m) that at first generates is through the even phase transformation of crystals; Form the Win 40350 of type of having enamel structure gradually, the diameter of the hydroxyapatite crystal that makes with this method is 30～200nm.
The present invention adopts following technical scheme to solve the problems of the technologies described above:
A kind of preparation method of enamel-shaped hydroxyapatite; This method is a raw material with soluble calcium salt and soluble phosphate; Under the regulating and controlling effect of the double base compound polyelectrolyte of forming by the acid of water-soluble cationic polyelectrolyte and organic multicomponent, make through hydro-thermal reaction and to have enamel-shaped hydroxyapatite.
Preferable, the width of said block brushite is 0.5～2 μ m, length is 1～10 μ m; The microcosmic component units of the Win 40350 of said type of having enamel structure is that diameter is the nanometer rod of 30～200nm, and said nanometer rod is along specific direction growth, and the enamel-shaped structure of tightly packed formation that is parallel to each other.
Preferable, said soluble calcium salt is selected from a kind of in four water-calcium nitrate and the Calcium dichloride dihydrate.
Preferable, said soluble phosphate is selected from a kind of in SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate, dibasic, potassium primary phosphate, potassium hydrogenphosphate, primary ammonium phosphate and the Secondary ammonium phosphate.
Preferable, said water-soluble polyelectrolyte is selected from one or more the mixing in polymine, SEPIGEL 305, chitosan and their verivate, further is preferably polymine.
Preferable; Said organic multicomponent acid is selected from toxilic acid (maleic acid), fumaric acid (FUMARIC ACID TECH GRADE), oxalic acid (oxalic acid), succsinic acid (Succinic Acid), tartrate (2; The mixing of one or more the 3-dyhydrobutanedioic acid) and in the oxysuccinic acid (2-Malic acid, D-) further is preferably toxilic acid.
Preferable, the preparation method of said enamel-shaped hydroxyapatite comprises the steps: that preparation contains the water-soluble cationic polyelectrolyte, the aqueous solution of organic multicomponent acid and urea; Then in the aqueous solution that makes, add soluble calcium salt and soluble phosphate, make reaction solution after the stirring; Reaction solution carries out hydro-thermal reaction, and hydro-thermal reaction is cooled to room temperature after finishing, and reaction product is washed through suction filtration, washing and alcohol, and behind air drying, can make enamel-shaped hydroxyapatite.
Preferably, in the said aqueous solution, the content of water-soluble cationic polyelectrolyte is 10～100mg/ml, and content of urea is 10wt%～30wt%, and the concentration of organic multicomponent acid is 5～50mg/ml.
Preferably, in the said reaction solution, the concentration of soluble calcium salt is 0.1～1mol/L, and the mol ratio of calcium/phosphorus (Ca/P) is 1～2.7: 1.
Preferably, said churning time is 5～30 minutes.
Preferably, the temperature of reaction of said hydro-thermal reaction is 70～150 ℃, and the reaction times is 20～120 hours.
Preferably, said drying process is at air drying, and drying temperature is 20～90 ℃, and be 2～48h time of drying.
It is 0.5～2 μ m that method of the present invention at first generates width; Length is the brushite of 1～10 μ m; It is by block brushite that the crystals of the brushite that generates then takes place to obtain enamel-shaped hydroxyapatite after the even phase transformation, and the component units of this enamel-shaped hydroxyapatite is a nanometer rod, and its diameter is 30～200nm; Nanometer rod is along specific direction growth, and the enamel-shaped structure of tightly packed formation that is parallel to each other.The enamel-shaped hydroxyapatite that makes among the present invention can be used for the damaged filling renovation material of human body hard tissue tooth (or bone), the injection defect is solidified or tooth (or bone) equivalent material.
Enamel-shaped hydroxyapatite to making among the present invention carries out structural characterization and performance evaluation, and evaluation method is following:
The thing phase of wide-angle X ray diffractor (XRD) assay products; The instrument model of using is Rigaku D/Max2550V; Adopt the copper target, Cu K alpha-ray
Field emission scanning electron microscope (SEM) is used for observing the pattern of product, and the instrument model of using is JSM-6700F, and acceleration voltage is 10kv.
The pattern of field transmission Electronic Speculum (TEM) assay products, particle diameter etc., the instrument model of using is JEOLJEM-2100F, acceleration voltage is 200kv.
The present invention is a template through the double base polyelectrolyte of forming through water-soluble cationic polyelectrolyte and organic multicomponent acid; The Win 40350 that preparation has similar enamel structure; Played the effect that is modeled to the glaze protein function, and helped to improve the mechanical property of Win 40350, therefore; Not only help us and further understand enamel crystalline biomineralization process, obtain and promote the possibility that provides new for the medical hydroxyapatite material of high quality simultaneously.The resulting Win 40350 of the present invention can be used for the damaged filling renovation material of human body hard tissue tooth (bone), the injection defect is solidified or tooth (bone) equivalent material.Defectives such as it is wayward to have overcome the Win 40350 size, the pattern that exist in the prior art, and mechanical property is relatively poor, and application performance and range of application are limited.
Description of drawings
Fig. 1 is the sem photograph of the enamel-shaped hydroxyapatite that makes among Natural tooth Enamel and the embodiment 1; Wherein Fig. 1 (a) is adamantine sem photograph, and Fig. 1 (b) is for making the sem photograph of product among the embodiment 1.
Fig. 2 composes for the XRD figure of the product that the differential responses time obtains; Fig. 2 (a) 1h, Fig. 2 (b) 4h, Fig. 2 (c) 8h, Fig. 2 (d) 12h, Fig. 2 (e) 24h, Fig. 2 (f) 96h.
Fig. 3 obtains transmission electron microscope picture, electron-diffraction diagram and the high resolution photo of product for the differential responses time; Fig. 3 (a) 1h, Fig. 3 (b) 8h, Fig. 3 (c) 96h.
Embodiment
Further describe technical scheme of the present invention through specific embodiment below.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.
Comparative Examples 1:
Polymine (PEI) is induced the formation of Win 40350, and concrete technology is following: at first preparation contains the aqueous solution of 40mg/ml polymine (PEI) and 24wt% urea.Then in above-mentioned solution, add nitrocalcite and SODIUM PHOSPHATE, MONOBASIC, and stirred 15 minutes.Wherein, wherein the concentration of nitrocalcite is 0.14mol/L, and the mol ratio of calcium/phosphorus (Ca/P) is 1.7.Subsequently reaction solution is poured in the water heating kettle, 80 ℃ of reactions 96 hours.Reaction naturally cools to room temperature after finishing.At last, product is through suction filtration, and washing and alcohol are washed, and is following dry 48 hours at 40 ℃ again.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.Characterization result shows that the product of gained is block Win 40350.
Comparative Examples 2:
Toxilic acid (MAc) is induced the formation of Win 40350, and concrete technology is following: at first preparation contains the aqueous solution of 20mg/ml toxilic acid (MAc) and 24wt% urea.Then in above-mentioned solution, add nitrocalcite and SODIUM PHOSPHATE, MONOBASIC, and stirred 15 minutes.Wherein, wherein the concentration of nitrocalcite is 0.14mol/L, and the mol ratio of calcium/phosphorus (Ca/P) is 1.7.Subsequently reaction solution is poured in the water heating kettle, 80 ℃ of reactions 96 hours.Reaction naturally cools to room temperature after finishing.At last, product is through suction filtration, and washing and alcohol are washed, and is following dry 48 hours at 40 ℃ again.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.Characterization result shows that the product of gained is poroid Win 40350.
Embodiment 1:
Specified each component and parameter in the according to the form below 1 utilize polymine (P EI) and maleic acid (MAc) to induce the formation of calcium phosphate salt jointly respectively, and concrete technology is following: at first preparation contains the aqueous solution of PEI, MAc and 24wt% urea.Then in above-mentioned solution, add nitrocalcite and SODIUM PHOSPHATE, MONOBASIC, and stirred 15 minutes.Subsequently reaction solution is poured in the water heating kettle, 80 ℃ of reactions.Reaction naturally cools to room temperature after finishing.At last, product is through suction filtration, and washing and alcohol are washed, and is following dry 48 hours at 40 ℃ again.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.Fig. 1 is the sem photograph of the enamel-shaped hydroxyapatite that makes among Natural tooth Enamel and the embodiment 1; Wherein Fig. 1 (a) is adamantine sem photograph, and Fig. 1 (b) is for making the sem photograph of product among the embodiment 1.The result shows that the Win 40350 that makes in the present embodiment has and the similar structure of enamel.Fig. 2 composes for the XRD figure of the product that the differential responses time obtains; Fig. 2 (a) 1h, Fig. 2 (b) 4h, Fig. 2 (c) 8h, Fig. 2 (d) 12h, Fig. 2 (e) 24h, Fig. 2 (f) 96h.The result shows that Win 40350 is to be changed mutually by brushite to obtain mutually.Fig. 3 obtains transmission electron microscope picture, electron-diffraction diagram and the high resolution photo of product for the differential responses time; Fig. 3 (a) 1h, Fig. 3 (b) 8h, Fig. 3 (c) 96h.The result shows that Win 40350 is to be changed mutually by brushite to obtain mutually, and transformation is by the inner even variation that causes of crystalline mutually.Characterization result shows that the product of gained is enamel-shaped Win 40350.Its component units (nanometer rod) is all along specific direction growth, and parallel tight arrangement.The diameter of nanometer rod is 30-200nm.
Embodiment 2:
Specified each component concentration repeats the method for embodiment 1 in the according to the form below 1, but replaces nitrocalcite with calcium chloride.Result and embodiment 1 are similar.
Embodiment 3:
Specified each component concentration repeats the method for embodiment 1 in the according to the form below 1, but replaces SODIUM PHOSPHATE, MONOBASIC with potassium primary phosphate.Result and embodiment 1 are similar.
Embodiment 4:
Specified each component concentration repeats the method for embodiment 1 in the according to the form below 1, but replaces polymine with SEPIGEL 305.Result and embodiment 1 are similar.
Embodiment 5:
Specified each component concentration repeats the method for embodiment 1 in the according to the form below 1, but replaces polymine with chitosan.Result and embodiment 1 are similar.
Embodiment 6:
Specified each component concentration repeats the method for embodiment 1 in the according to the form below 1, but replaces toxilic acid with oxalic acid.Result and embodiment 1 are similar.
Embodiment 7:
Specified each component concentration repeats the method for embodiment 1 in the according to the form below 1, but replaces toxilic acid with tartrate.Result and embodiment 1 are similar.
Reaction parameter tabulation among table 1 embodiment 1～7
Embodiment 8:
Preparation contains polymine, the aqueous solution of succsinic acid and urea, and in the aqueous solution, the concentration of polymine is 10mg/ml, and the concentration of succsinic acid is 5mg/ml, and the concentration of urea is 10wt%; Then adding calcium nitrate tetrahydrate and Secondary ammonium phosphate stir after 5 minutes and make reaction solution in the aqueous solution that makes, and in this reaction solution, the concentration of calcium nitrate tetrahydrate is 0.1mol/L, and Ca/P is 1: 1; Reaction solution carries out hydro-thermal reaction, and the temperature of hydro-thermal reaction is 70 ℃, and the reaction times is 120 hours; Hydro-thermal reaction is cooled to room temperature after finishing, and reaction product is washed through suction filtration, washing and alcohol; And at air drying; Drying temperature is 20 ℃, and be 48 hours time of drying, can make enamel-shaped hydroxyapatite after the drying.The result shows that the Win 40350 that makes in the present embodiment has and the similar structure of enamel.And Win 40350 is to be changed mutually by brushite to obtain mutually.
Embodiment 9:
Preparation contains polymine, the aqueous solution of fumaric acid and urea, and in the aqueous solution, the concentration of polymine is 100mg/ml, and the concentration of fumaric acid is 50mg/ml, and the concentration of urea is 30wt%; Then adding calcium nitrate tetrahydrate and Secondary ammonium phosphate stir after 30 minutes and make reaction solution in the aqueous solution that makes, and in this reaction solution, the concentration of calcium nitrate tetrahydrate is 1mol/L, and Ca/P is 2.7: 1; Reaction solution carries out hydro-thermal reaction, and the temperature of hydro-thermal reaction is 150 ℃, and the reaction times is 20 hours; Hydro-thermal reaction is cooled to room temperature after finishing, and reaction product is washed through suction filtration, washing and alcohol; And at air drying; Drying temperature is 90 ℃, and be 2 hours time of drying, can make enamel-shaped hydroxyapatite after the drying.The result shows that the Win 40350 that makes in the present embodiment has and the similar structure of enamel.And Win 40350 is to be changed mutually by brushite to obtain mutually.
Claims (8)
1. the preparation method of an enamel-shaped hydroxyapatite; This method is a raw material with soluble calcium salt and soluble phosphate; Under the regulating and controlling effect of the double base compound polyelectrolyte of forming by water-soluble cationic polyelectrolyte and organic multicomponent acid; Make through hydro-thermal reaction and to have enamel-shaped Win 40350; Said water-soluble cationic polyelectrolyte is selected from one or more the mixing in polymine, SEPIGEL 305 and the chitosan, and said organic multicomponent acid is selected from one or more the mixing in toxilic acid, fumaric acid, oxalic acid, succsinic acid, tartrate and the oxysuccinic acid.
2. the preparation method of the enamel-shaped hydroxyapatite described in claim 1 is characterized in that, said soluble calcium salt is selected from a kind of in four water-calcium nitrate and the Calcium dichloride dihydrate; Said soluble phosphate is selected from a kind of in SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate, dibasic, potassium primary phosphate, potassium hydrogenphosphate, primary ammonium phosphate and the Secondary ammonium phosphate.
3. like the preparation method of arbitrary described enamel-shaped hydroxyapatite in the claim 1～2; It is characterized in that; The preparation method of said enamel-shaped hydroxyapatite comprises the steps: that preparation contains the water-soluble cationic polyelectrolyte, the aqueous solution of organic multicomponent acid and urea; Then in the aqueous solution that makes, add soluble calcium salt and soluble phosphate, make reaction solution after the stirring; Reaction solution carries out hydro-thermal reaction, and hydro-thermal reaction is cooled to room temperature after finishing, and reaction product is washed through suction filtration, washing and alcohol, and after drying, can make enamel-shaped hydroxyapatite.
4. the preparation method of the enamel-shaped hydroxyapatite described in claim 3; It is characterized in that; The said water-soluble cationic polyelectrolyte that contains, in the aqueous solution of organic multicomponent acid and urea, the content of water-soluble cationic polyelectrolyte is 10～100mg/mL; Content of urea is 10wt%～30wt%, and the concentration of organic multicomponent acid is 5～50mg/mL.
5. the preparation method of the enamel-shaped hydroxyapatite described in claim 3 is characterized in that, in the said reaction solution, the concentration of soluble calcium salt is 0.1～1mol/L, and the mol ratio of calcium/phosphorus is 1～2.7: 1.
6. the preparation method of the enamel-shaped hydroxyapatite described in claim 3 is characterized in that, the temperature of reaction of said hydro-thermal reaction is 70～150 ℃, and the reaction times is 20～120 hours.
7. an enamel-shaped hydroxyapatite is made by arbitrary described preparation method in the claim 1～6.
8. the enamel-shaped hydroxyapatite described in the claim 7 solidifies or tooth/bone alternate material as the damaged filling renovation material of human body hard tissue tooth/bone, injection defect.
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| CN102294034B (en) * | 2011-06-14 | 2012-10-31 | 四川大学 | Biomineralization material, and preparation method and application thereof |
| GB201417020D0 (en) * | 2014-09-26 | 2014-11-12 | Univ Leeds And Univ St Andrews The | Formulation |
| CN105063618A (en) * | 2015-08-22 | 2015-11-18 | 山东建筑大学 | Method for preparing hydroxyapatite film layer on magnesium alloy surface |
| CN105147526B (en) * | 2015-08-25 | 2018-09-18 | 福建省诺希科技园发展有限公司 | A kind of preparation method of hydro-thermal method synthesis nano-antibacterial tooth enamel layer |
| CN105106022B (en) * | 2015-08-25 | 2018-05-01 | 福建省诺希科技园发展有限公司 | A kind of preparation method of antibacterial dental growth repair materials |
| CN106115644B (en) * | 2016-06-24 | 2017-12-01 | 张文凯 | A kind of preparation method of hydroxyapatite structure |
| CN106539693B (en) * | 2016-10-13 | 2019-10-29 | 浙江大学 | The method that macromolecule filming material loads the biomimetic mineralization pad pasting and its external evoked remineralization of ACP |
| CN107343857B (en) * | 2017-06-23 | 2019-10-25 | 浙江大学 | One type tooth enamel structural hydroxyl apatite and its preparation method and application |
| CN109809809A (en) * | 2019-03-07 | 2019-05-28 | 华南理工大学 | A kind of construction method of the hexagonal prisms microarray of hydroxyapatite scaffold apparent height orientation |
| CN115282063B (en) * | 2022-09-02 | 2023-11-24 | 米乐医疗科技有限公司 | Tooth desensitizer |
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| JP5061341B2 (en) * | 2006-05-23 | 2012-10-31 | 国立大学法人 岡山大学 | Method for producing crystalline hydroxyapatite fine particles |
| CN101538028B (en) * | 2009-04-15 | 2011-08-03 | 中国科学院上海硅酸盐研究所 | Plate-like phosphoric acid calcium salt and preparation method and application thereof |
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Effective date of registration: 20220927 Address after: 215400 No.6 Liangfu Road, Taicang City, Suzhou City, Jiangsu Province Patentee after: Jiangsu Institute of advanced inorganic materials Address before: 200050 No. 1295 Dingxi Road, Shanghai, Changning District Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |