CN101327340B - Method for preparing bacterial inhibition-resistance petal-shaped or sheet-shaped Ag/Cu/HAP nano compound powder - Google Patents
Method for preparing bacterial inhibition-resistance petal-shaped or sheet-shaped Ag/Cu/HAP nano compound powder Download PDFInfo
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- CN101327340B CN101327340B CN200810150320A CN200810150320A CN101327340B CN 101327340 B CN101327340 B CN 101327340B CN 200810150320 A CN200810150320 A CN 200810150320A CN 200810150320 A CN200810150320 A CN 200810150320A CN 101327340 B CN101327340 B CN 101327340B
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Abstract
The invention relates to antimicrobial petaloid or schistic Ag/Cu/HAP composite nano-powder and a preparation method thereof. Ag<+> and Cu<2+> which have the strongest antimicrobial resistance are blended into HAP by a coprecipitation hydrolysis method, thus preparing petaloid crystals. The preparation method provided by the invention is simple in operation, uniform and total in doping. The nano-powder, as a raw material, is used for making a composite material with macromolecular substances. The composite material makes an implant which has strong antimicrobial resistance and enduring and wide antimicrobial spectrum. The doping ions, as ions of a transitional element, is composite with the macromolecular substances with strong chemical cohesion; besides, the petaloid crystal shape of the nano-powder is beneficial for attachment and propagation of cells, thereby the nano-powder has good biocompatibility.
Description
Technical field
The invention belongs to the advanced material preparation of biomedical and field of environment engineering, be specifically related to the method for preparing of a kind of anti-biocidal property petal-shaped or lamellar Ag/Cu/HAP composite nano-powder.
Background technology
Research shows: lamellar HAP has the good performance of impelling cell attachment and breeding (adhering to and grow like fibrocyte L929) (J.X.Zhang; M.Maeda; N.Kotobuki; Et al.Aqueous processing of hydroxyapatite [J] .Mater.Chem.and Phy., 2006,99 (2-3): 398-404.; K Yamauchi, T.Goda, N.Takeuchi; Et al.Preparation ofcollagen/calcium phosphate multilayer sheet using enzymaticmineralization [J] .Biomaterials, 2004,25 (24): 5481-5489.); The crystalline preparation research of lamellar HAP is less, and mainly concentrates on the preparation of lath-shaped, lamellar HAP crystal coating, adopts electrodeposition process and organic formwork method (Hu Ren more; Shi Haiyan, Lin Liwen, etc. electrochemical deposition hydroxyapatite process crystal growth behavior [J]. Acta PhySico-Chimica Sinica; 2005,21 (2): 197-201.; Huang Suping, Zhou Kechao, Liu Yong. the controlled growth [J] of hydroxyapatite on organic membrane. investigation of materials journal, 2004,18 (1): 66-70.; Huang Zhiliang opens alliance, Liu Yu, etc. organic formwork induce/homogeneous precipitation method is to the control growing [J] of hydroxyapatite (HAP) crystal morphology. artificial intraocular lenses's journal, 2006,35 (2): 261-264.; Zhao Yong, Deng Xia, Nie Rongrong; Deng. the experimentation [J] of the bionical sedimentary phosphor lime stone of fibroin protein film. stomatology research, 2006,22 (2): 116-119.); K.Loku (K.Loku, S.Yoshimura, H.Fujimori; Et al.Hydrothermal preparation of fibrous apatite and apatite sheet [J] .Solid StateIonics, 2002,151 (1-4): 147-150.), A.C.Lawson (AC Lawson; J.T.Czernuszka.Production and characterisation of a collagen-calciumphosphate composite for use as a bone substitute [C] .Mater.Res.Soc.Symposium-Proceedings; .1999,550:273-278.) adopting Hydrothermal Preparation to go out with people such as J.X.Zhang must shape and the mixed crystal of lamellar HAP, but belongs to the biomaterial of non-nano level; And, do not have anti-biocidal property.
Bacterial infection in the biomaterial use is the one of the main reasons that causes the bone graft failure, and this problem has caused people's attention, adopts antibiotic reorganization bone to address this problem, but has only the curative effect of short-term.
Summary of the invention
The object of the present invention is to provide the method for preparing of a kind of anti-biocidal property petal-shaped or lamellar Ag/Cu/HAP composite nano-powder; The gained composite granule had both had good biological activity, biocompatibility; Have antibiotic wide spectrum and persistency again, help Normocellular apposition growth simultaneously.
For achieving the above object, the method for preparing that the present invention adopts is:
1) at first, gets lime nitrate (Ca (NO
3)
2) and diammonium phosphate ((NH
4)
2HPO
4) solution that is mixed with 0.1mol/L soluble in water respectively, and press Ca (NO
3)
2: (NH
4)
2HPO
4Be that 1.67 volume ratio is mixed, with nitric acid (HNO
3) adjusting acidity to mixed solution clear;
2) then, by 1: 1 mass ratio with water and mass concentration be 25% ammonia mix ammonia spirit, get the 0.1-0.2 ammonia spirit doubly of above-mentioned clear and transparent mixed solution cumulative volume, with AgNO
3And Cu (NO
3)
2Join together in the prepared ammonia spirit, its concentration is controlled at 0.001～0.01mol/L respectively;
3) secondly, with the Ag that obtains
+, Cu
2+Mix ammonia solution in 40 ℃, the speed with 60ml/h under powerful the stirring is added drop-wise to synthetic petal-shaped or flake nano HAP composite granule in the mixed solution, behind reinforced the end, obtains Ag/Cu/HAP composite granule suspension;
4) last, with the Ag/Cu/HAP suspension under agitation heating in water bath and keep 3-5h to 95-100 ℃; Then; In 40 ℃ of-60 ℃ of water-baths, leave standstill 24-36h, after this, vacuum filtration and 100 ℃ of dry 20-24h; Cool to room temperature with the furnace, can obtain fluffy petal-shaped or lamellar Ag/Cu/HAP composite granule.
The present invention adopts the co-precipitation Hydrolyze method will resist the strongest Ag of biocidal property
+And Cu
2+Mix among the HAP, prepare the petal-shaped crystal, not only simple to operate, and, uniform doping, complete; Form composite as raw material and polymer substance, the implant that this composite is processed has strong anti-biocidal property, and antibiotic wide spectrum, lasting; Because dopant ion is the ion of transition elements, compound with polymer substance, its chemical bond power is strong; Owing to have the petal-shaped crystal morphology, help adhering to and breeding of cell, thereby have excellent biological compatibility.
Description of drawings
Fig. 1 is the crystalline SEM figure of Ag/Cu/HAP that makes according to method for preparing of the present invention, (a) 100 ℃, and (b) 300 ℃.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.
Embodiment 1:
1) at first, gets lime nitrate (Ca (NO
3)
2) and diammonium phosphate ((NH
4)
2HPO
4) solution that is mixed with 0.1mol/L soluble in water respectively, and press Ca (NO
3)
2: (NH
4)
2HPO
4Be that 1.67 volume ratio is mixed, with nitric acid (HNO
3) adjusting acidity to mixed solution clear;
2) then, by 1: 1 mass ratio with water and mass concentration be 25% ammonia mix ammonia spirit, get 0.2 times ammonia spirit of above-mentioned clear and transparent mixed solution cumulative volume, with AgNO
3And Cu (NO
3)
2Join together in the prepared ammonia spirit, its concentration is controlled at 0.001mol/L respectively;
3) secondly, with the Ag that obtains
+, Cu
2+Mix ammonia solution in 40 ℃, the speed with 60ml/h under powerful the stirring is added drop-wise to synthetic petal-shaped or flake nano HAP composite granule in the mixed solution, behind reinforced the end, obtains Ag/Cu/HAP composite granule suspension;
4) last, with Ag/Cu/HAP suspension heating in water bath to 98 ℃ under agitation, and keep 4h; Then, in 60 ℃ of water-baths, leave standstill 24h, after this; Vacuum filtration and 100 ℃ of dry 20h cool to room temperature with the furnace, can obtain fluffy petal-shaped or lamellar Ag/Cu/HAP composite granule.
Embodiment 2:
1) at first, gets lime nitrate (Ca (NO
3)
2) and diammonium phosphate ((NH
4)
2HPO
4) solution that is mixed with 0.1mol/L soluble in water respectively, and press Ca (NO
3)
2: (NH
4)
2HPO
4Be that 1.67 volume ratio is mixed, with nitric acid (HNO
3) adjusting acidity to mixed solution clear;
2) then, by 1: 1 mass ratio with water and mass concentration be 25% ammonia mix ammonia spirit, get 0.15 times ammonia spirit of above-mentioned clear and transparent mixed solution cumulative volume, with AgNO
3And Cu (NO
3)
2Join together in the prepared ammonia spirit, its concentration is controlled at 0.01mol/L respectively;
3) secondly, with the Ag that obtains
+, Cu
2+Mix ammonia solution in 40 ℃, the speed with 60ml/h under powerful the stirring is added drop-wise to synthetic petal-shaped or flake nano HAP composite granule in the mixed solution, behind reinforced the end, obtains Ag/Cu/HAP composite granule suspension;
4) last, with Ag/Cu/HAP suspension heating in water bath to 95 ℃ under agitation, and keep 5h; Then, in 40 ℃ of water-baths, leave standstill 36h, after this; Vacuum filtration and 100 ℃ of dry 22h cool to room temperature with the furnace, can obtain fluffy petal-shaped or lamellar Ag/Cu/HAP composite granule.
Embodiment 3:
1) at first, gets lime nitrate (Ca (NO
3)
2) and diammonium phosphate ((NH
4)
2HPO
4) solution that is mixed with 0.1mol/L soluble in water respectively, and press Ca (NO
3)
2: (NH
4)
2HPO
4Be that 1.67 volume ratio is mixed, with nitric acid (HNO
3) adjusting acidity to mixed solution clear;
2) then, by 1: 1 mass ratio with water and mass concentration be 25% ammonia mix ammonia spirit, get 0.1 times ammonia spirit of above-mentioned clear and transparent mixed solution cumulative volume, with AgNO
3And Cu (NO
3)
2Join together in the prepared ammonia spirit, its concentration is controlled at 0.005mol/L respectively;
3) secondly, with the Ag that obtains
+, Cu
2+Mix ammonia solution in 40 ℃, the speed with 60ml/h under powerful the stirring is added drop-wise to synthetic petal-shaped or flake nano HAP composite granule in the mixed solution, behind reinforced the end, obtains Ag/Cu/HAP composite granule suspension;
4) last, with Ag/Cu/HAP suspension heating in water bath to 97 ℃ under agitation, and keep 4.5h; Then, in 55 ℃ of water-baths, leave standstill 26h, after this; Vacuum filtration and 100 ℃ of dry 24h cool to room temperature with the furnace, can obtain fluffy petal-shaped or lamellar Ag/Cu/HAP composite granule.
Embodiment 4:
1) at first, gets lime nitrate (Ca (NO
3)
2) and diammonium phosphate ((NH
4)
2HPO
4) solution that is mixed with 0.1mol/L soluble in water respectively, and press Ca (NO
3)
2: (NH
4)
2HPO
4Be that 1.67 volume ratio is mixed, with nitric acid (HNO
3) adjusting acidity to mixed solution clear;
2) then, by 1: 1 mass ratio with water and mass concentration be 25% ammonia mix ammonia spirit, get 0.18 times ammonia spirit of above-mentioned clear and transparent mixed solution cumulative volume, with AgNO
3And Cu (NO
3)
2Join together in the prepared ammonia spirit, its concentration is controlled at 0.003mol/L respectively;
3) secondly, with the Ag that obtains
+, Cu
2+Mix ammonia solution in 40 ℃, the speed with 60ml/h under powerful the stirring is added drop-wise to synthetic petal-shaped or flake nano HAP composite granule in the mixed solution, behind reinforced the end, obtains Ag/Cu/HAP composite granule suspension;
4) last, with Ag/Cu/HAP suspension heating in water bath to 100 ℃ under agitation, and keep 3h; Then, in 45 ℃ of water-baths, leave standstill 32h, after this; Vacuum filtration and 100 ℃ of dry 21h cool to room temperature with the furnace, can obtain fluffy petal-shaped or lamellar Ag/Cu/HAP composite granule.
Embodiment 5:
1) at first, gets lime nitrate (Ca (NO
3)
2) and diammonium phosphate ((NH
4)
2HPO
4) solution that is mixed with 0.1mol/L soluble in water respectively, and press Ca (NO
3)
2: (NH
4)
2HPO
4Be that 1.67 volume ratio is mixed, with nitric acid (HNO
3) adjusting acidity to mixed solution clear;
2) then, by 1: 1 mass ratio with water and mass concentration be 25% ammonia mix ammonia spirit, get 0.13 times ammonia spirit of above-mentioned clear and transparent mixed solution cumulative volume, with AgNO
3And Cu (NO
3)
2Join together in the prepared ammonia spirit, its concentration is controlled at 0.008mol/L respectively;
3) secondly, with the Ag that obtains
+, Cu
2+Mix ammonia solution in 40 ℃, the speed with 60ml/h under powerful the stirring is added drop-wise to synthetic petal-shaped or flake nano HAP composite granule in the mixed solution, behind reinforced the end, obtains Ag/Cu/HAP composite granule suspension;
4) last, with Ag/Cu/HAP suspension heating in water bath to 96 ℃ under agitation, and keep 3.5h; Then, in 50 ℃ of water-baths, leave standstill 28h, after this; Vacuum filtration and 100 ℃ of dry 23h cool to room temperature with the furnace, can obtain fluffy petal-shaped or lamellar Ag/Cu/HAP composite granule.
In the present invention's preparation, dopant ion slowly adds synthesis system, uniform doping under solution state; Silver ion, copper ion all exist in the reaction solution with the ionic formation of ammino in synthetic; The reinforced heating in water bath that finishes under agitation is to 95-100 ℃; And keep 3-5h; Main effect is that the ammonia in the solution is removed in volatilization, and two kinds of dopant ions are discharged from complex ion, forms deposition or makes it enter into the nano-HAP composite granule fully through ion exchange through hydrolysis takes place; In synthetic ammonia solution silver-colored, copper being joined in tart calcium, the phosphorus precursor solution is one of committed step of synthetic petal-shaped HAP composite granule, and reinforced order can not be put upside down, otherwise, will obtain acicular crystal.
Distinguishing feature of the present invention is: under the condition that does not add template, synthesize petal-like silver-bearing copper dopen Nano HAP composite granule; Has antibiotic property; Uniform doping, reaction finish the back gets in the product dopant ion through the stirring that heats up fully, and doping is easy to control.
The result of Fig. 1 shows that 100 ℃ of oven dry products obtained therefroms are thick 20-50nm, and area is 500 * 500-1000nm
2, handle 2h for 300 ℃, petal is launched into leaf shape.With pure HAP is reference, the Ag/Cu/HAP composite nano-powder of argentiferous 1%, copper 0.5%, and its minimal inhibitory concentration is 3000ppm.
Claims (1)
1. the method for preparing of anti-biocidal property petal-shaped or lamellar Ag/Cu/HAP composite nano-powder is characterized in that:
1) at first, gets lime nitrate (Ca (NO
3)
2) and diammonium phosphate ((NH
4)
2HPO
4) solution that is mixed with 0.1mol/L soluble in water respectively, and press Ca (NO
3)
2: (NH
4)
2HPO
4Be that 1.67 volume ratio is mixed, with nitric acid (HNO
3) adjusting acidity to mixed solution clear;
2) then, by 1: 1 mass ratio with water and mass concentration be 25% ammonia mix ammonia spirit, get the 0.1-0.2 ammonia spirit doubly of above-mentioned clear and transparent mixed solution cumulative volume, with AgNO
3And Cu (NO
3)
2Join together in the prepared ammonia spirit, its concentration is controlled at 0.001～0.01mol/L respectively;
3) secondly, with the Ag that obtains
+, Cu
2+Mix ammonia solution in 40 ℃, the speed with 60ml/h under powerful the stirring is added drop-wise in the mixed solution, behind reinforced the end, obtains Ag/Cu/HAP composite granule suspension;
4) last, with the Ag/Cu/HAP suspension under agitation heating in water bath and keep 3-5h to 95-100 ℃; Then; In 40 ℃ of-60 ℃ of water-baths, leave standstill 24-36h, after this, vacuum filtration and 100 ℃ of dry 20-24h; Cool to room temperature with the furnace, can obtain fluffy petal-shaped or lamellar Ag/Cu/HAP composite granule.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810150320A CN101327340B (en) | 2008-07-11 | 2008-07-11 | Method for preparing bacterial inhibition-resistance petal-shaped or sheet-shaped Ag/Cu/HAP nano compound powder |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810150320A CN101327340B (en) | 2008-07-11 | 2008-07-11 | Method for preparing bacterial inhibition-resistance petal-shaped or sheet-shaped Ag/Cu/HAP nano compound powder |
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| CN101327340B true CN101327340B (en) | 2012-09-05 |
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| CN104724687B (en) * | 2015-02-27 | 2017-03-08 | 杨智杰 | Silicon, silver-colored two-way replacement hydroxyapatite 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 |
| CN113908324B (en) * | 2021-09-26 | 2022-05-17 | 杭州淑洁卫生用品有限公司 | Disposable hygienic product with antibacterial function |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1402989A (en) * | 2002-09-12 | 2003-03-19 | 中国科学院广州地球化学研究所 | Delay-released inorganic nano antiseptic with high whiteness and its prepn |
| CN1426683A (en) * | 2001-12-17 | 2003-07-02 | 北京有色金属研究总院 | High temp. resistant, colour fastness inorganic antimicrobial mildew preventive agent and its preparing method |
| CN1711847A (en) * | 2004-06-23 | 2005-12-28 | 北京圣鑫泽房地产经纪有限公司 | Hydroxyl apatite inorganic antibacterial agent containing silver and zinc ions |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426683A (en) * | 2001-12-17 | 2003-07-02 | 北京有色金属研究总院 | High temp. resistant, colour fastness inorganic antimicrobial mildew preventive agent and its preparing method |
| CN1402989A (en) * | 2002-09-12 | 2003-03-19 | 中国科学院广州地球化学研究所 | Delay-released inorganic nano antiseptic with high whiteness and its prepn |
| CN1711847A (en) * | 2004-06-23 | 2005-12-28 | 北京圣鑫泽房地产经纪有限公司 | Hydroxyl apatite inorganic antibacterial agent containing silver and zinc ions |
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