CN107281555B - Preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects and product thereof - Google Patents

Preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects and product thereof Download PDF

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CN107281555B
CN107281555B CN201710480423.1A CN201710480423A CN107281555B CN 107281555 B CN107281555 B CN 107281555B CN 201710480423 A CN201710480423 A CN 201710480423A CN 107281555 B CN107281555 B CN 107281555B
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张川
吴吉洋
董寅生
郭超
耿银雪
李强
王巧凤
张立民
蔚丽
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Jiangsu Leezo Biochemistry Technology Co ltd
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Abstract

The invention discloses a preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects and a product thereof: the method comprises the following steps: neutralizing: dropwise adding a phosphoric acid solution containing silver nitrate into a calcium hydroxide suspension for reaction, and after the reaction is finished, centrifuging, ball-milling, aging, washing, drying at 80 ℃ for 12 hours, and calcining for 2 hours to prepare silver-doped nano hydroxyapatite; step two: chemical reduction: and (2) dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to be from turbid to clear to form a silver ammonia solution, adding water into the silver-doped nano hydroxyapatite to form a turbid liquid, sequentially adding the silver ammonia solution and a dispersing agent into the turbid liquid, finally adding a reducing agent solution to react, and drying at 80 ℃ after the reaction is completed to obtain the silver-loaded nano hydroxyapatite. The invention simultaneously adopts two methods of doping and depositing to add silver into the nano-hydroxyapatite, simultaneously realizes the powerful antibacterial effect of depositing the nano-silver and the long-acting antibacterial effect of doping the silver, and effectively improves the antibacterial performance of the nano-hydroxyapatite.

Description

Preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects and product thereof
Technical Field
The invention relates to a preparation method of silver-loaded nano hydroxyapatite and a product prepared by the method, and belongs to the field of preparation of biomedical materials.
Background
The artificially synthesized nano hydroxyapatite is nano hydroxyapatite, has the components similar to natural hydroxyapatite which is the main inorganic component of human skeleton and teeth, has good biocompatibility and bioactivity, has an inhibiting effect on the growth of partial tumor cells, and can be used as a bone repair material, a scaffold material or a drug slow-release material carrier. However, the nano-hydroxyapatite has a weak antibacterial property, and is difficult to solve the problem of implant infection which often occurs in clinical use. Therefore, the nano hydroxyapatite has good antibacterial performance and can expand the application range.
The currently leading method for improving the antibacterial performance of the nano hydroxyapatite is to carry out ion doping by using metal or nonmetal elements with antibacterial performance. A hydroxyapatite inorganic antibacterial agent containing silver and zinc ions and a preparation method thereof (China, publication No. 1711847, publication date 2005-12-28) disclose that the hydroxyapatite inorganic antibacterial agent containing silver and zinc ions is prepared by an ion exchange method. A process for preparing the nm-class composite Ag-carried hydroxy apatite/titanium dioxide as disinfecting material (China, publication No. 1739357, publication date 2006-03-01) features that the inorganic salts of Ti, Ag, Ca and ammonium are used as raw materials and the Ag-carried hydroxy apatite is prepared by liquid-phase co-precipitation method. Silicon and silver double-substituted hydroxyapatite material and a preparation method thereof (China: China, publication No. 104724687A, publication date: 2015-06-24) disclose silicon and silver double-substituted hydroxyapatite material obtained by reacting calcium, phosphorus, silver and silicon-containing reactants under the condition that the pH value is more than or equal to 9 and carrying out heat treatment and a preparation method thereof.
In addition to ion doping, methods of depositing antimicrobial nanomaterials have also been used to improve the antimicrobial properties of nano-hydroxyapatite. DI z etc. (i z M, Barba F, Miranda M,
Figure BDA0001329210050000011
f, Torrellias R, Moya JS. synthetic and antimicrobial activity of silver-hydroxide nanoparticles, Journal of nanoparticles, 2009,2009:1-6) deposited nano silver on the surface of hydroxyapatite by depositing and calcining the reduced silver oxide, Nirma et al (Nirma R, Shell FA, Kanjac MA, et al. synthetic and catalytic activity of bone cement nanoparticles for the biological applications, Journal of nanoparticle research 2011,13(5): 1917. 1927) deposited nano silver on the surface of bovine femoral bone hydroxyapatite, guest C, synthetic and antimicrobial activity of nanoparticles, Zlay et al&Nano Letters,2012,7(9): 904-.
Both methods of ion doping and deposition of antimicrobial nanomaterials have drawbacks. The doping of antibacterial ions such as silver ions and the like can endow the nano hydroxyapatite with relatively long-acting antibacterial performance, but when the doping amount of silver is higher (generally higher than 1% -2%), a small amount of tricalcium phosphate appears, the purity of the hydroxyapatite is reduced, and the lower doping amount cannot ensure the strong antibacterial effect at the initial use stage. The nano silver deposition method can generate large specific surface area of nano silver, and the low deposition amount can form strong antibacterial performance, but the release speed is too high, so that long-acting antibacterial can not be formed, and the application of nano hydroxyapatite in long-term service environment is not facilitated.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above problems, the present invention aims to provide a method for preparing a silver-loaded nano hydroxyapatite biomaterial having both strong antibacterial performance and long-lasting antibacterial performance, and a product prepared by the preparation method.
The technical scheme is as follows: a preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting effect and antibacterial effect comprises the following steps:
the method comprises the following steps: neutralizing: dropwise adding a phosphoric acid solution containing silver nitrate into a calcium hydroxide suspension for reaction, and after the reaction is finished, centrifuging, ball-milling, aging, washing, drying at 80 ℃ for 12 hours, and calcining for 2 hours to prepare silver-doped nano hydroxyapatite;
step two: chemical reduction: and (2) dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to be from turbid to clear to form a silver ammonia solution, adding water into the silver-doped nano hydroxyapatite to form a turbid liquid, sequentially adding the silver ammonia solution and a dispersing agent into the turbid liquid, finally adding a reducing agent solution to react, and drying at 80 ℃ after the reaction is completed to obtain the silver-loaded nano hydroxyapatite.
In the first step, the molar ratio of the sum of Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide to P atoms in the phosphoric acid is 1.67: 1, and the Ag atoms in the silver nitrate account for 0.5-1.0% of the sum of the Ag atoms in the silver nitrate and the Ca atoms in the calcium hydroxide, and the percentage is mass percentage.
Wherein, in the step one, the reaction time is 5 to 7 hours.
Wherein, in the first step, the calcining temperature is 450-750 ℃.
Wherein, in the first step, the calcium hydroxide suspension is formed at a stirring speed of 600 r/min.
In the second step, the molar ratio of silver nitrate in the silver nitrate solution to the silver-doped nano-hydroxyapatite is 1: 15-1: 5.
In the second step, the dispersant is polyvinylpyrrolidone or soluble starch, and the molar ratio of the dispersant to the silver-doped nano-hydroxyapatite is 1: 10.
In the second step, the reducing agent is glucose, and the molar ratio of the reducing agent to the silver nitrate in the silver nitrate solution is 1: 2. The reducing agent is used for reducing silver simple substance in the silver ammonia solution.
Wherein in the second step, the average particle size of the silver-loaded nano-hydroxyapatite is 60-80 nm.
A silver-carrying nano-hydroxyapatite with strong effect, long-acting and antibacterial property is a product prepared by any one of the preparation methods.
Has the advantages that: compared with the prior art, the invention has the advantages that: simultaneously, the silver is added into the nano-hydroxyapatite by adopting two methods of doping and depositing, so that the strong antibacterial effect of depositing the nano-silver and the long-acting antibacterial effect of doping the silver are realized simultaneously, the antibacterial performance of the nano-hydroxyapatite can be effectively improved, and the application range of the nano-hydroxyapatite is expanded.
Drawings
FIG. 1 is an X-ray diffraction pattern of silver-loaded nano-hydroxyapatite prepared in example 1;
fig. 2 is a transmission electron microscope picture of the silver-loaded nano-hydroxyapatite prepared in example 1.
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
Example 1
A preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects specifically comprises the following steps:
the method comprises the following steps: and (4) neutralizing.
And (2) dripping phosphoric acid solution containing silver nitrate into calcium hydroxide suspension formed at the stirring speed of 600r/min for reaction for 6 hours, and after the reaction is finished, centrifuging, ball milling, aging, washing, drying at 80 ℃ for 12 hours, and calcining at 750 ℃ for 2 hours to prepare the silver-doped nano hydroxyapatite.
Wherein the molar ratio of the sum of Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide to P atoms in the phosphoric acid is 1.67: 1; the silver doping amount of the silver-doped nano hydroxyapatite is that Ag atoms in the silver nitrate account for 0.5 percent of the sum of the Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide, and the percentage is the mass percentage.
Step two: and (4) chemically reducing.
And (2) dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to be from turbid to clear to form a silver ammonia solution, adding water into the silver-doped nano hydroxyapatite to form a turbid liquid, sequentially adding the silver ammonia solution and polyvinylpyrrolidone into the turbid liquid, finally adding a glucose solution to react, and drying at 80 ℃ after complete reaction to obtain the silver-loaded nano hydroxyapatite.
Wherein, the molar ratio of silver nitrate in the silver nitrate solution to silver-doped nano-hydroxyapatite is 1: 10, the molar ratio of polyvinylpyrrolidone to silver-doped nano-hydroxyapatite is 1: 10, and the molar ratio of glucose to silver nitrate in the silver nitrate solution is 1: 2.
The silver-loaded nano-hydroxyapatite prepared in the embodiment is detected, the phase composition of the product is confirmed to be hydroxyapatite and silver by an X-ray diffraction spectrum in the attached drawing 1, and the average particle size of the hydroxyapatite is 68nm and the average particle size of the silver is 6nm through the observation of a transmission electron microscope in the attached drawing 2.
Example 2
A preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects specifically comprises the following steps:
the method comprises the following steps: and (4) neutralizing.
And (2) dripping phosphoric acid solution containing silver nitrate into calcium hydroxide suspension formed at the stirring speed of 600r/min for reaction for 7 hours, and after the reaction is finished, centrifuging, ball-milling, aging, washing, drying at 80 ℃ for 12 hours, and calcining at 450 ℃ for 2 hours to prepare the silver-doped nano hydroxyapatite.
Wherein the molar ratio of the sum of Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide to P atoms in the phosphoric acid is 1.67: 1; the silver doping amount of the silver-doped nano hydroxyapatite is that Ag atoms in the silver nitrate account for 1 percent of the sum of the Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide, and the percentage is the mass percentage.
Step two: and (4) chemically reducing.
And (2) dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to be from turbid to clear to form a silver ammonia solution, adding water into the silver-doped nano hydroxyapatite to form a turbid liquid, sequentially adding the silver ammonia solution and polyvinylpyrrolidone into the turbid liquid, finally adding a glucose solution to react, and drying at 80 ℃ after complete reaction to obtain the silver-loaded nano hydroxyapatite.
Wherein the molar ratio of silver nitrate in the silver nitrate solution to silver-doped nano-hydroxyapatite is 1: 15, the molar ratio of polyvinylpyrrolidone to silver-doped nano-hydroxyapatite is 1: 10, and the molar ratio of glucose to silver nitrate in the silver nitrate solution is 1: 2.
The silver-loaded nano-hydroxyapatite prepared by the embodiment is detected, the phase composition of the silver-loaded nano-hydroxyapatite is hydroxyapatite and silver, the average particle size of the hydroxyapatite is 60nm, and the average particle size of the silver is 6 nm.
Example 3
A preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects specifically comprises the following steps:
the method comprises the following steps: and (4) neutralizing.
And (2) dripping phosphoric acid solution containing silver nitrate into calcium hydroxide suspension formed at the stirring speed of 600r/min for reaction for 5 hours, and after the reaction is finished, centrifuging, ball milling, aging, washing, drying at 80 ℃ for 12 hours, and calcining at 600 ℃ for 2 hours to prepare the silver-doped nano hydroxyapatite.
Wherein the molar ratio of the sum of Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide to P atoms in the phosphoric acid is 1.67: 1; the silver doping amount of the silver-doped nano hydroxyapatite is that Ag atoms in the silver nitrate account for 0.5 percent of the sum of the Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide, and the percentage is the mass percentage.
Step two: and (4) chemically reducing.
And (2) dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to be from turbid to clear to form a silver ammonia solution, adding water into the silver-doped nano hydroxyapatite to form a turbid liquid, sequentially adding the silver ammonia solution and polyvinylpyrrolidone into the turbid liquid, finally adding a glucose solution to react, and drying at 80 ℃ after complete reaction to obtain the silver-loaded nano hydroxyapatite.
Wherein, the molar ratio of silver nitrate in the silver nitrate solution to silver-doped nano-hydroxyapatite is 1: 12, the molar ratio of polyvinylpyrrolidone to silver-doped nano-hydroxyapatite is 1: 10, and the molar ratio of glucose to silver nitrate in the silver nitrate solution is 1: 2.
The silver-loaded nano-hydroxyapatite prepared by the embodiment is detected, the phase composition of the silver-loaded nano-hydroxyapatite is hydroxyapatite and silver, the average particle size of the hydroxyapatite is 72nm, and the average particle size of the silver is 6 nm.
Example 4
A preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects specifically comprises the following steps:
the method comprises the following steps: and (4) neutralizing.
And (2) dripping phosphoric acid solution containing silver nitrate into calcium hydroxide suspension formed at the stirring speed of 600r/min for reaction for 6 hours, and after the reaction is finished, centrifuging, ball milling, aging, washing, drying at 80 ℃ for 12 hours, and calcining at 700 ℃ for 2 hours to obtain the silver-doped nano hydroxyapatite.
Wherein the molar ratio of the sum of Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide to P atoms in the phosphoric acid is 1.67: 1; the silver doping amount of the silver-doped nano hydroxyapatite is that Ag atoms in the silver nitrate account for 0.8 percent of the sum of the Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide, and the percentage is the mass percentage.
Step two: and (4) chemically reducing.
And (2) dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to be from turbid to clear to form a silver ammonia solution, adding water into the silver-doped nano hydroxyapatite to form a turbid liquid, sequentially adding the silver ammonia solution and soluble starch into the turbid liquid, finally adding a glucose solution to react, and drying at 80 ℃ after complete reaction to obtain the silver-loaded nano hydroxyapatite.
Wherein, the molar ratio of silver nitrate in the silver nitrate solution to silver-doped nano-hydroxyapatite is 1: 5, the molar ratio of soluble starch to silver-doped nano-hydroxyapatite is 1: 10, and the molar ratio of glucose to silver nitrate in the silver nitrate solution is 1: 2.
The silver-loaded nano-hydroxyapatite prepared by the embodiment is detected, the phase composition of the silver-loaded nano-hydroxyapatite is hydroxyapatite and silver, the average particle size of the hydroxyapatite is 80nm, and the average particle size of the silver is 6 nm.
Example 5
A preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects specifically comprises the following steps:
the method comprises the following steps: and (4) neutralizing.
And (2) dripping phosphoric acid solution containing silver nitrate into calcium hydroxide suspension formed at the stirring speed of 600r/min for reaction for 7 hours, and after the reaction is finished, centrifuging, ball-milling, aging, washing, drying at 80 ℃ for 12 hours, and calcining at 450 ℃ for 2 hours to prepare the silver-doped nano hydroxyapatite.
Wherein the molar ratio of the sum of Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide to P atoms in the phosphoric acid is 1.67: 1; the silver doping amount of the silver-doped nano hydroxyapatite is that Ag atoms in the silver nitrate account for 0.5 percent of the sum of the Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide, and the percentage is the mass percentage.
Step two: and (4) chemically reducing.
And (2) dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to be from turbid to clear to form a silver ammonia solution, adding water into the silver-doped nano hydroxyapatite to form a turbid liquid, sequentially adding the silver ammonia solution and soluble starch into the turbid liquid, finally adding a glucose solution to react, and drying at 80 ℃ after complete reaction to obtain the silver-loaded nano hydroxyapatite.
Wherein, the molar ratio of silver nitrate in the silver nitrate solution to silver-doped nano-hydroxyapatite is 1: 6, the molar ratio of soluble starch to silver-doped nano-hydroxyapatite is 1: 10, and the molar ratio of glucose to silver nitrate in the silver nitrate solution is 1: 2.
The silver-loaded nano-hydroxyapatite prepared by the embodiment is detected, the phase composition of the silver-loaded nano-hydroxyapatite is hydroxyapatite and silver, the average particle size of the hydroxyapatite is 75nm, and the average particle size of the silver is 6 nm.

Claims (8)

1. A preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects is characterized by comprising the following steps:
the method comprises the following steps: neutralizing: dropwise adding a phosphoric acid solution containing silver nitrate into a calcium hydroxide suspension for reaction, and after the reaction is finished, centrifuging, ball-milling, aging, washing, drying at 80 ℃ for 12 hours, and calcining for 2 hours to prepare silver-doped nano hydroxyapatite; in the step, the molar ratio of the sum of Ag atoms in the silver nitrate and Ca atoms in the calcium hydroxide to P atoms in the phosphoric acid is 1.67: 1, the Ag atoms in the silver nitrate account for 0.5-1.0 percent of the sum of the Ag atoms in the silver nitrate and the Ca atoms in the calcium hydroxide, and the percentage is the mass percentage;
step two: chemical reduction: dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to be from turbid to clear to form a silver ammonia solution, adding water into silver-doped nano hydroxyapatite to form a suspension, sequentially adding the silver ammonia solution and a dispersing agent into the suspension, finally adding a reducing agent solution to react, and drying at 80 ℃ after the reaction is completed to obtain silver-loaded nano hydroxyapatite; in the step, the molar ratio of silver nitrate in the silver nitrate solution to the silver-doped nano hydroxyapatite is 1: 15-1: 5.
2. The preparation method of the silver-loaded nano-hydroxyapatite with strong effect, long-acting and antibacterial effects according to claim 1, which is characterized in that: in the first step, the reaction time is 5 to 7 hours.
3. The preparation method of the silver-loaded nano-hydroxyapatite with strong effect, long-acting and antibacterial effects according to claim 1, which is characterized in that: in the first step, the calcining temperature is 450-750 ℃.
4. The preparation method of the silver-loaded nano-hydroxyapatite with strong effect, long-acting and antibacterial effects according to claim 1, which is characterized in that: in step one, the calcium hydroxide suspension is formed at a stirring speed of 600 r/min.
5. The preparation method of the silver-loaded nano-hydroxyapatite with strong effect, long-acting and antibacterial effects according to claim 1, which is characterized in that: in the second step, the dispersant is polyvinylpyrrolidone or soluble starch, and the molar ratio of the dispersant to the silver-doped nano-hydroxyapatite is 1: 10.
6. The preparation method of the silver-loaded nano-hydroxyapatite with strong effect, long-acting and antibacterial effects according to claim 1, which is characterized in that: in the second step, the reducing agent is glucose, and the molar ratio of the reducing agent to the silver nitrate in the silver nitrate solution is 1: 2.
7. The preparation method of the silver-loaded nano-hydroxyapatite with strong effect, long-acting and antibacterial effects according to claim 1, which is characterized in that: in the second step, the average particle size of the silver-loaded nano hydroxyapatite is 60-80 nm.
8. A powerful long-acting antibacterial silver-loaded nano-hydroxyapatite is characterized in that: is a product obtained by the preparation method of any one of claims 1 to 7.
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