CN101891175A - Enamel-like hydroxyapatite and its preparation method and application - Google Patents
Enamel-like hydroxyapatite and its preparation method and application Download PDFInfo
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- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 66
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 66
- 210000003298 dental enamel Anatomy 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 150000007519 polyprotic acids Polymers 0.000 claims abstract 6
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 13
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 12
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- 239000011575 calcium Substances 0.000 claims description 10
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 5
- 241000282414 Homo sapiens Species 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- 210000001519 tissue Anatomy 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
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- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims 1
- 229920002873 Polyethylenimine Polymers 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- 239000000316 bone substitute Substances 0.000 claims 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- 229960005069 calcium Drugs 0.000 claims 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 claims 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- 235000011087 fumaric acid Nutrition 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims 1
- 235000019796 monopotassium phosphate Nutrition 0.000 claims 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims 1
- 235000019799 monosodium phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 230000033558 biomineral tissue development Effects 0.000 abstract description 2
- 239000002073 nanorod Substances 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
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- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- 240000005373 Panax quinquefolius Species 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 229910001573 adamantine Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
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- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940009662 edetate Drugs 0.000 description 1
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- 235000001968 nicotinic acid Nutrition 0.000 description 1
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- Materials For Medical Uses (AREA)
- Dental Preparations (AREA)
Abstract
本发明属于生物医学材料技术领域，具体涉及一种牙釉质状羟基磷灰石及其制备方法和应用，具体来说，涉及一种双元聚电解质诱导合成牙釉质状羟基磷灰石的方法。该方法以可溶性钙盐和可溶性磷酸盐为原料，以由水溶性阳离子聚电解质和有机多元酸组成的双元聚电解质为模板，制备得到的羟基磷灰石纳米棒沿着特定的方向生长，并相互平行紧密堆积形成牙釉质状结构。纳米棒的直径为30～200nm。该方法提供了一种制备牙釉质状结构羟基磷灰石的方法，不仅有利于我们进一步理解釉质晶体的生物矿化过程，且有助于提高羟基磷灰石机械性能，扩展其在牙/骨替代材料方面的应用，为高质量医用羟基磷灰石材料的获取及推广提供了新的可能。The invention belongs to the technical field of biomedical materials, and in particular relates to an enamel-like hydroxyapatite and its preparation method and application, in particular to a method for synthesizing enamel-like hydroxyapatite induced by a binary polyelectrolyte. The method uses soluble calcium salt and soluble phosphate as raw materials, and uses a binary polyelectrolyte composed of water-soluble cationic polyelectrolyte and organic polybasic acid as a template to prepare hydroxyapatite nanorods to grow along a specific direction, and Closely packed parallel to each other to form a tooth enamel-like structure. The diameter of the nanorod is 30-200nm. This method provides a method for preparing hydroxyapatite with enamel-like structure, which not only helps us to further understand the biomineralization process of enamel crystals, but also helps to improve the mechanical properties of hydroxyapatite and expand its application in teeth/bone. The application of alternative materials provides new possibilities for the acquisition and promotion of 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 and its production and application.
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 complexity and enamel crystalline maturation are to finish by 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 dentology or all are significant in Materials science.
Hydroxyapatite 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 hydroxyapatite 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 hydroxyapatite of different-shape and structure.The characteristic of hydroxyapatite is closely related with its specific surface area, size, size distribution and sintering activity etc., the biological activity of hydroxyapatite is subjected to the influence of factors such as its Ca/P, carbonate and foreign matter content, crystal size, pattern, sample structure, sintering process, and the hydroxyapatite of preparing different shape is the key that the excellent properties of hydroxyapatite 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 easily causes charges to come off.In recent years, the research of class 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 Moradian-Oldak group of University of Southern California's school of dentistry studies show that, 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. with class 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 hydroxyapatite 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, be coated with mixed gel as the mineralising template at enamel surface, thus 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 of enamel complexity 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 play vital regulating and controlling effect in the process of tooth glaze mineralising.Studies show 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, realize the bionical synthetic of class enamel structure, and then form 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 and its production and application 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, preparation method of the present invention is under the regulation and control of double base compound polyelectrolyte, at first (width is 0.5-2 μ m to the block brushite of Sheng Chenging, length is 1-10 μ m) even phase transformation by crystals, form the hydroxyapatite with class 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 described block brushite is 0.5～2 μ m, length is 1～10 μ m; Described microcosmic component units with hydroxyapatite of class enamel structure is that diameter is the nanometer rod of 30～200nm, and described nanometer rod is along specific direction growth, and the enamel-shaped structure of tightly packed formation that is parallel to each other.
Preferable, described soluble calcium salt is selected from a kind of in four water-calcium nitrate and the Calcium dichloride dihydrate.
Preferable, described soluble phosphate is selected from a kind of in SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, potassium primary phosphate, dipotassium hydrogen phosphate, primary ammonium phosphate and the Secondary ammonium phosphate.
Preferable, described water-soluble polyelectrolyte is selected from one or more the mixing in polymine, polyacrylamide, chitosan and their derivative, more preferably polymine.
Preferable, described 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-hydroxy-butanedioic acid), more preferably toxilic acid.
Preferable, the preparation method of described 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 can make enamel-shaped hydroxyapatite behind air drying.
Preferably, in the described 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 described 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, described churning time is 5～30 minutes.
Preferably, the temperature of reaction of described hydro-thermal reaction is 70～150 ℃, and the reaction times is 20～120 hours.
Preferably, described 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, to take place to obtain enamel-shaped hydroxyapatite after the even phase transformation be by block brushite to the crystals of the brushite of Sheng Chenging then, the component units of this enamel-shaped hydroxyapatite is a nanometer rod, 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.
The enamel-shaped hydroxyapatite that makes among the present invention is carried out structural characterization and performance evaluation, and evaluation method is as follows:
The thing phase of wide-angle X ray diffractor (XRD) assay products, the instrument model of using is Rigaku D/Max2550V, adopts 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 by the double base polyelectrolyte of forming by water-soluble cationic polyelectrolyte and organic multicomponent acid, the hydroxyapatite that preparation has similar enamel structure, played the effect that is modeled to the glaze protein function, and help to improve the mechanical property of hydroxyapatite, therefore, not only help us and further understand enamel crystalline biomineralization process, simultaneously for the medical hydroxyapatite material of high quality obtain and promote provide new may.The resulting hydroxyapatite 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 hydroxyapatite 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 below by specific embodiment.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.
Comparative Examples 1:
Polymine (PEI) is induced the formation of hydroxyapatite, and concrete technology is as follows: 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 hydroxyapatite.
Comparative Examples 2:
Toxilic acid (MAc) is induced the formation of hydroxyapatite, and concrete technology is as follows: 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 hydroxyapatite.
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 as follows: 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 hydroxyapatite 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 hydroxyapatite 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 hydroxyapatite 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 hydroxyapatite.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.The result is similar to Example 1.
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.The result is similar to Example 1.
Embodiment 4:
Specified each component concentration repeats the method for embodiment 1 in the according to the form below 1, but replaces polymine with polyacrylamide.The result is similar to Example 1.
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.The result is similar to Example 1.
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.The result is similar to Example 1.
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.The result is similar to Example 1.
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, the temperature of hydro-thermal reaction is 70 ℃, 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 hydroxyapatite that makes in the present embodiment has and the similar structure of enamel.And hydroxyapatite 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, the temperature of hydro-thermal reaction is 150 ℃, 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 hydroxyapatite that makes in the present embodiment has and the similar structure of enamel.And hydroxyapatite is to be changed mutually by brushite to obtain mutually.
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