CN101462708A - Nano antibacterial hydroxylapatite and preparation thereof - Google Patents
Nano antibacterial hydroxylapatite and preparation thereof Download PDFInfo
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- CN101462708A CN101462708A CN 200810205056 CN200810205056A CN101462708A CN 101462708 A CN101462708 A CN 101462708A CN 200810205056 CN200810205056 CN 200810205056 CN 200810205056 A CN200810205056 A CN 200810205056A CN 101462708 A CN101462708 A CN 101462708A
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- hydroxyapatite
- rare earth
- zinc
- nano antibacterial
- nanometer
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Abstract
The invention provides nanometer antibiotic hydroxyapatite and a method for preparing the same, and belongs to the technical field of nanometer material. The nanometer antibiotic hydroxyapatite comprises the following components in percentage by weight: 5 to 11 percent of zinc, 6 to 12 percent of rare earth, 24 to 31 percent of calcium and 46 to 65 percent of nitric acid and phosphoric acid compound, wherein the ionized zinc and rare earth form a double-activity center, and the nanometer antibiotic hydroxyapatite is a liquating type solid solution. By the method, zinc and rare earth elements are liquated in crystal lattices of the nanometer antibiotic hydroxyapatite; by adopting sodium citrate as a surface modifying agent for nanometer materials, high-dispersibility grains with needle-shaped crystallographic form are prepared, and the nanometer antibiotic hydroxyapatite has the same structure as the nanometer hydroxyapatite in a natural bone; moreover, the nanometer antibiotic hydroxyapatite has better antibiotic capability, and the whole preparation process is safe and non-toxic.
Description
Technical field
The present invention relates to material of a kind of technical field of nano material and preparation method thereof, specifically is a kind of nano antibacterial hydroxylapatite and preparation method thereof.
Background technology
Biological active ceramic material is the special bio-medical material of a kind of function, can form chemical bonding with human body osseous tissue, soft tissue, this bonding reaches by the amorphous gel coat of formation at the interface in active ceramic and tissue, the formation of active ceramic surface gel layer makes it condition that possesses suitable microorganism growth and may form mycoderm; Main inorganic composition hydroxyapatite (HA) in natural bone and the tooth is closely similar with crystalline form and the structure of synthetic nanometer HA, has good biocompatibility, biological activity and bone conduction effect, is good hard tissue repairing material.And HA also contains other in the natural bone some as Mg
2+, Mn
2+, Zn
2+, Na
+, Sr
2+Positively charged ion, in order to satisfy the needs of clinical application, usually need in the HA of synthetic, add the clinical performance that some units usually improve material.Plant people person's infection for fear of the HA pottery, it is very necessary to improve its anti-microbial property.
Find through retrieval prior art, China Patent No. ZL200510029595.4, Granted publication CN1313005C, a kind of " activated by rare earth elements carrying silver antimicrobials and preparation method thereof " disclosed, with the carrier of phosphoric acid composite salt as the serial inorganic antiseptic of silver, utilize porous support to carry simultaneously and hold several antibiotic ions, and improve its germ resistance and discoloration-resistant performance with the activation characteristic of rare earth element, rare earth element adopts elements such as lanthanum, yttrium.
Find by retrieval again, China Patent No. ZL200510022274.1, Granted publication CN1316895C, a kind of " preparation method of inorganic nano-germicide powder " disclosed, it is 5～20% and suspension liquid slurry that regulate pH5～8 that nano-apatite is mixed with massfraction, after being 0.5%～10% antimicrobial component aqueous solution with massfraction, with frequency is the ultrasonication mixture 30～60 minutes of 40～200kHz, antimicrobial component is loaded on the carrier, the mode ageing of stirring with discontinuity is after 20～48 hours, water washing is precipitated in neutral and the eluting water does not have Cu2+, Zn2+, Ag+, La3+, Ce3+ and Nd3+, the throw out oven dry is also pulverized.
Find by retrieval again, Chinese patent application numbers 200810028762.7 has been put down in writing a kind of " preparation method of silver-hydroxyapatite nano-composite material ", adopt the cathode electrodeposition method, the aqueous solution with calcium ions, dihydrogen phosphate and silver ions, with the titanium sheet as working electrode, extra electric field carries out potentiostatic electrodeposition, by alkaline solution thermal treatment, promptly gets silver-hydroxyapatite nano-composite material then.
Above-mentioned prior art all exists technical process long, the shortcoming that complicated operation, antibiotic ion run off easily, and need to use heavy metal ion such as silver ions in the operating process, and being fit to industrial application more, the material of preparing is difficult to be applicable to clinical medicine fields.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of nano antibacterial hydroxylapatite and preparation method thereof is provided, zinc element and rare earth element are dissolved in the nanometer hydroxyapatite lattice simultaneously, adopt trisodium citrate as nano-material surface properties-correcting agent, prepare high dispersancy nano particle with needle-like crystal formation, identical with the nanometer hydroxyapatite structure in the natural bone, has germ resistance preferably, whole process of preparation does not adopt heavy metal ion such as silver ions, the anti-biotic material safety non-toxic of preparation gained.
The present invention implements by the following technical programs:
The component and the mass percent that the present invention relates to nano antibacterial hydroxylapatite are: zinc content 5～11%, content of rare earth 6～12%, calcium contents 24～31% and nitric acid and phosphate cpd 46～65%, wherein: the zinc of ionic forms and rare earth are formed double activity center, and this nano antibacterial hydroxylapatite is dissolving property sosoloid.
Described zinc is meant a kind of or its combination in zinc nitrate, zinc acetate or the zinc chloride;
Described rare earth is meant a kind of or its combination in rare earth nitrate salt or the rare earth chloride salt;
Described calcium is meant a kind of or its combination in nitrocalcite, calcium acetate or the calcium chloride.
Nano antibacterial hydroxylapatite of the present invention has good biocompatibility and biological activity, and possesses biological safety, can be the various hard tissue implanting materials of preparation and supplies raw materials.
The present invention relates to preparation method, may further comprise the steps as above-mentioned nano antibacterial hydroxylapatite:
1. take by weighing calcium ion salts xmol respectively, zine ion salt ymol, rare earth ion salt zmol makes mixed solution, adds trisodium citrate when stirring under the mixed solution water-bath environment, forms metallic ion mixed liquor;
Wherein:
10％×(x+y+z)≤y≤20％×(x+y+z)，
5％×(x+y+z)≤z≤10％×(x+y+z)，
y+z≤30％×(x+y+z)，
x＝y＝z。
The add-on of described trisodium citrate is specially 10%～25% of required hydroxyapatite quality in the quality percentage composition.
Described water-bath environment specifically is meant 40～60 ℃ water-bath environment.
2. take by weighing
Phosphoric acid salt add in the deionized water, be configured to phosphate solution;
Described phosphoric acid salt is a kind of or its combination in ammonium phosphate or the Secondary ammonium phosphate.
3. metallic ion mixed liquor is carried out the intensively stirred heating that heats up simultaneously, then phosphate solution is slowly joined in the metallic ion mixed liquor after the heating, slowly add ammoniacal liquor again and make the precipitation of hydroxyapatite mixed solution, should precipitate mixed solution and leave standstill until pH to 8～10 and after keeping continuing to stir under the homothermic condition;
Described ammonia concn is 5～10mol/L.
Described intensification heating is meant at 80～90 ℃
4. after will precipitating mixed solution and being cooled to room temperature, isolate precipitation of hydroxyapatite, then precipitation of hydroxyapatite is cleaned the suction filtration several times, carry out high temperature drying at last again, obtain exsiccant hydroxyapatite filter cake;
Described high temperature drying is meant drying treatment 10～12h under 90 ℃～110 ℃ situation.
5. the hydroxyapatite filter cake is ground to form hydroxyapatite powder, carry out calcination processing then, make wide 18～22nm, the needle-like crystal powder of long 190～210nm.
Described calcination processing is meant under 300 ℃～500 ℃ environment calcines 2h.
The preparation method of nano antibacterial hydroxylapatite of the present invention has the following advantages:
1) technology is simple: not high to equipment requirements, employed stablizer is harmless substantially to environment and organism.
2) antimicrobial spectrum becomes wide: owing to contain zine ion and the two anti-microbial activity centers of rare earth ion, it is wide that its antimicrobial spectrum becomes, and can suppress the microbial growths such as bacterium, mould and spore in the environment effectively.
3) anti-microbial activity is higher: compare with carrying the zinc antiseptic-germicide, its anti-microbial activity increases substantially.
Embodiment
Following examples provided detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to following embodiment being to implement under the prerequisite with the invention technical scheme.
Embodiment 1
Preparation contains the nano antibacterial hydroxylapatite of Ce elements
1) gets the ca nitrate soln 56mL of 0.5mol/L, 0.5mol/L zinc nitrate solution 16mL and the cerous nitrate solution 8mL of 0.5mol/L, place the there-necked flask in the water-bath to mix stirring and be warming up to 60 ℃, add the trisodium citrate of 1.25g then and continue to stir and heat up, make metallic ion mixed liquor until 90 ℃;
2) ammonium dibasic phosphate solution that in metallic ion mixed liquor, dropwise adds 0.5mol/L 48mL altogether, and be to continue stirring and be incubated 90 ℃ behind the ammoniacal liquor conditioned reaction system pH=9 of 5mol/L with concentration, 5h obtains the precipitation of hydroxyapatite mixed solution;
3) the throw out mixed solution is naturally cooled to room temperature after, isolate precipitation of hydroxyapatite, then precipitation is cleaned behind the suction filtration several times dry 10h under 100 ℃ of environment, obtain hydroxyapatite hydroxyapatite filter cake;
4) dried hydroxyapatite filter cake is carried out after the extra-fine grinding hydroxyapatite powder being calcined 2h through 300 ℃, make the nanometer needle-like white antibacterial hydroxylapatite powder that contains zinc and Ce elements, wherein, the component of product and mass percent are: zinc content 11%, cerium content 12%, calcium contents 24% and nitric acid and phosphate cpd 53%.
The obtained nano antibacterial hydroxylapatite of present embodiment is adopted antibacterial around-France intestinal bacteria and streptococcus aureus are tested, cultivated 24 hours, around sample, formed antibacterial ring, bacteriostasis rate reaches 99.4%, is higher than the bacteriostasis rate 88% of prior art for preparing gained hydroxyapatite.
Embodiment 2
Preparation contains the nano antibacterial hydroxylapatite of lanthanum element
1) gets the calcium acetate solution 60mL of 0.5mol/L, 0.5mol/L zinc acetate solution 12mL and the lanthanum nitrate hexahydrate 8mL of 0.5mol/L, place the there-necked flask in the water-bath to mix stirring and be warming up to 60 ℃, add trisodium citrate 1g then and continue to stir and heat up, make metallic ion mixed liquor until 90 ℃;
2) ammonium dibasic phosphate solution that dropwise adds 0.5mol/L 48mL altogether, and after being the ammoniacal liquor conditioned reaction system pH=9 of 8mol/L with concentration, continuing stirring and also be incubated 90 ℃, 5h obtains the precipitation of hydroxyapatite mixed solution;
3) will precipitate mixed solution and naturally cool to room temperature after, isolate precipitation of hydroxyapatite, then precipitation of hydroxyapatite is cleaned behind the suction filtration several times dry 10h under 100 ℃ of environment, obtain the hydroxyapatite filter cake;
4) dried hydroxyapatite filter cake is carried out after the extra-fine grinding hydroxyapatite powder being calcined 2h through 400 ℃, make the nanometer needle-like white antibacterial hydroxylapatite powder that contains zinc, lanthanum element, wherein, the component of product and mass percent are: zinc content 9%, lanthanum content 12%, calcium contents 26% and nitric acid and phosphate cpd 53%.
The obtained nano antibacterial hydroxylapatite of present embodiment is adopted antibacterial around-France intestinal bacteria and streptococcus aureus are tested, cultivated 24 hours, around sample, formed antibacterial ring, bacteriostasis rate reaches 99.7%, is higher than the bacteriostasis rate 88% of prior art for preparing gained hydroxyapatite.
Embodiment 3
Preparation contains the nano antibacterial hydroxylapatite of neodymium element
1) gets the calcium chloride solution 64mL of 0.5mol/L, 0.5mol/L liquor zinci chloridi 12mL and the neodymium chloride solution 4mL of 0.5mol/L, place the there-necked flask in the water-bath to mix stirring and be warming up to 60 ℃, add trisodium citrate 0.5g then and continue to stir and heat up, make metallic ion mixed liquor until 90 ℃;
2) ammonium dibasic phosphate solution that dropwise adds 0.5mol/L 60mL altogether, and after being the ammoniacal liquor conditioned reaction system pH=9 of 10mol/L with concentration, continuing stirring and also be incubated 90 ℃, 5h obtains the precipitation of hydroxyapatite mixed solution;
3) will precipitate mixed solution and naturally cool to room temperature after, isolate precipitation of hydroxyapatite, then precipitation of hydroxyapatite is cleaned behind the suction filtration several times dry 10h under 100 ℃ of environment, obtain the hydroxyapatite filter cake;
4) dried hydroxyapatite filter cake is carried out after the extra-fine grinding hydroxyapatite powder being calcined 2h through 500 ℃, make the nanometer needle-like white antibacterial hydroxylapatite powder that contains zinc, neodymium element, wherein, the component of product and mass percent are: zinc content 9%, neodymium content 7%, calcium contents 29% and nitric acid and phosphate cpd 55%.
The obtained nano antibacterial hydroxylapatite of present embodiment is adopted antibacterial around-France intestinal bacteria and streptococcus aureus are tested, cultivated 24 hours, around sample, formed antibacterial ring, bacteriostasis rate reaches 99.2%, is higher than the bacteriostasis rate 88% of prior art for preparing gained hydroxyapatite.
The application test data of the foregoing description show: the bacteriostasis rate that this hydroxyapatite that contains zinc, rare earth ion does not have powder reaches more than 90%, can be applied in the raw material of medical hard tissue repair and embedded material.
Claims (8)
1, a kind of nano antibacterial hydroxylapatite, it is characterized in that, component and mass percentage content are: zinc content 5～11%, content of rare earth 6～12%, calcium contents 24～31% and nitric acid and phosphate cpd 46～65%, wherein: the zinc of ionic forms and rare earth are formed double activity center, and this nano antibacterial hydroxylapatite is for dissolving type sosoloid.
2, nano antibacterial hydroxylapatite according to claim 1 is characterized in that, described zinc is meant a kind of or its combination in zinc nitrate, zinc acetate or the zinc chloride.
3, nano antibacterial hydroxylapatite according to claim 1 is characterized in that, described rare earth is meant a kind of or its combination in rare earth nitrate salt or the rare earth chloride salt.
4, a kind of preparation method of nano antibacterial hydroxylapatite as claimed in claim 1 is characterized in that, may further comprise the steps:
1. take by weighing calcium ion salts x mol respectively, zine ion salt ymol, rare earth ion salt z mol makes mixed solution, adds trisodium citrate when stirring under the mixed solution water-bath environment, forms metallic ion mixed liquor;
Wherein:
10％×(x+y+z)≤y≤20％×(x+y+z)，
5％×(x+y+z)≤z≤10％×(x+y+z)，
y+z≤30％×(x+y+z)；
x＝y＝z；
2. take by weighing
Phosphoric acid salt add in the deionized water, be configured to phosphate solution;
3. metallic ion mixed liquor is carried out the intensively stirred heating that heats up simultaneously, then phosphate solution is slowly joined in the metallic ion mixed liquor after the heating, slowly add ammoniacal liquor again and make the precipitation of hydroxyapatite mixed solution, should precipitate mixed solution and leave standstill until pH to 8～10 and after keeping continuing to stir under the homothermic condition;
4. after will precipitating mixed solution and being cooled to room temperature, isolate precipitation of hydroxyapatite, then precipitation of hydroxyapatite is cleaned the suction filtration several times, carry out high temperature drying at last again, obtain exsiccant hydroxyapatite filter cake;
5. the hydroxyapatite filter cake is ground to form hydroxyapatite powder, carry out calcination processing then, make wide 18～22nm, the needle-like crystal powder of long 190～210nm.
5, the preparation method of nano antibacterial hydroxylapatite according to claim 4 is characterized in that, the add-on of the trisodium citrate of step described in 1. is specially 10%～25% of required hydroxyapatite quality by percentage to the quality.
6, the preparation method of nano antibacterial hydroxylapatite according to claim 4 is characterized in that, the intensification heating of step described in 3. is meant at 80～90 ℃.
7, the preparation method of nano antibacterial hydroxylapatite according to claim 4 is characterized in that, the high temperature drying of step described in 4. is meant drying treatment 10～12h under 90 ℃～110 ℃ situation.
8, the preparation method of nano antibacterial hydroxylapatite according to claim 4 is characterized in that, the calcination processing of step described in 5. is meant under 300 ℃～500 ℃ environment calcines 2h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102784069A (en) * | 2012-08-27 | 2012-11-21 | 上海交通大学医学院附属第九人民医院 | Zinc-loaded calcium phosphate antibacterial material and preparation method thereof |
| CN104910597A (en) * | 2015-05-08 | 2015-09-16 | 常州龙骏天纯环保科技有限公司 | Preparation method of active antibiotic biodegradable composite material |
| CN107189372A (en) * | 2017-06-26 | 2017-09-22 | 俞惠英 | A kind of antibacterial polyester film and preparation method thereof |
| CN108187136A (en) * | 2017-12-29 | 2018-06-22 | 连云港碳谷材料科技有限公司 | A kind of preparation method of nanometer of load zinc hydroxyapatite |
| CN108653803A (en) * | 2018-04-25 | 2018-10-16 | 东南大学 | A kind of nano silver, nano zine oxide two-phase deposition mix the preparation method and its resulting materials of zinc nanometer hydroxyapatite |
| CN110104974A (en) * | 2019-03-11 | 2019-08-09 | 山东天汇研磨耐磨技术开发有限公司 | A kind of anticollision and the dedicated micro-crystalline ceramic abrasive material of modified machine tool industry and its manufacturing method |
| CN112250439A (en) * | 2020-10-20 | 2021-01-22 | 哈工宁伯医疗科技泰州有限公司 | Ceramic material for tooth restoration and manufacturing method thereof |
| CN112830463A (en) * | 2021-01-15 | 2021-05-25 | 南京尚迪纳米科技有限公司 | Preparation method and application of nano fresh-keeping material |
| CN113632614A (en) * | 2021-08-13 | 2021-11-12 | 金华生物质产业科技研究院 | Preparation and application methods of compound heavy metal contaminated soil remediation material |
| CN115029752A (en) * | 2022-06-28 | 2022-09-09 | 郑州大学 | Preparation method of composite coating suitable for bone implantation magnesium or magnesium alloy |
| CN115475271A (en) * | 2022-08-19 | 2022-12-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing |
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2008
- 2008-12-30 CN CN2008102050565A patent/CN101462708B/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784069B (en) * | 2012-08-27 | 2014-06-25 | 上海交通大学医学院附属第九人民医院 | Zinc-loaded calcium phosphate antibacterial material and preparation method thereof |
| CN102784069A (en) * | 2012-08-27 | 2012-11-21 | 上海交通大学医学院附属第九人民医院 | Zinc-loaded calcium phosphate antibacterial material and preparation method thereof |
| CN104910597A (en) * | 2015-05-08 | 2015-09-16 | 常州龙骏天纯环保科技有限公司 | Preparation method of active antibiotic biodegradable composite material |
| CN107189372A (en) * | 2017-06-26 | 2017-09-22 | 俞惠英 | A kind of antibacterial polyester film and preparation method thereof |
| CN108187136A (en) * | 2017-12-29 | 2018-06-22 | 连云港碳谷材料科技有限公司 | A kind of preparation method of nanometer of load zinc hydroxyapatite |
| CN108653803B (en) * | 2018-04-25 | 2021-08-10 | 东南大学 | Preparation method of nano-silver and nano-zinc oxide double-phase deposition zinc-doped nano-hydroxyapatite and material obtained by preparation method |
| CN108653803A (en) * | 2018-04-25 | 2018-10-16 | 东南大学 | A kind of nano silver, nano zine oxide two-phase deposition mix the preparation method and its resulting materials of zinc nanometer hydroxyapatite |
| CN110104974A (en) * | 2019-03-11 | 2019-08-09 | 山东天汇研磨耐磨技术开发有限公司 | A kind of anticollision and the dedicated micro-crystalline ceramic abrasive material of modified machine tool industry and its manufacturing method |
| CN110104974B (en) * | 2019-03-11 | 2021-06-08 | 山东天汇研磨耐磨技术开发有限公司 | Special anti-collision and modified microcrystalline ceramic abrasive for machine tool industry and manufacturing method thereof |
| CN112250439A (en) * | 2020-10-20 | 2021-01-22 | 哈工宁伯医疗科技泰州有限公司 | Ceramic material for tooth restoration and manufacturing method thereof |
| CN112830463A (en) * | 2021-01-15 | 2021-05-25 | 南京尚迪纳米科技有限公司 | Preparation method and application of nano fresh-keeping material |
| CN113632614A (en) * | 2021-08-13 | 2021-11-12 | 金华生物质产业科技研究院 | Preparation and application methods of compound heavy metal contaminated soil remediation material |
| CN113632614B (en) * | 2021-08-13 | 2022-08-16 | 金华生物质产业科技研究院 | Preparation and application methods of compound heavy metal contaminated soil remediation material |
| CN115029752A (en) * | 2022-06-28 | 2022-09-09 | 郑州大学 | Preparation method of composite coating suitable for bone implantation magnesium or magnesium alloy |
| CN115475271A (en) * | 2022-08-19 | 2022-12-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing |
| CN115475271B (en) * | 2022-08-19 | 2023-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing |
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