CN109550974B - Preparation method for green synthesis of nano-silver by using carnosic acid - Google Patents

Preparation method for green synthesis of nano-silver by using carnosic acid Download PDF

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CN109550974B
CN109550974B CN201811527825.3A CN201811527825A CN109550974B CN 109550974 B CN109550974 B CN 109550974B CN 201811527825 A CN201811527825 A CN 201811527825A CN 109550974 B CN109550974 B CN 109550974B
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carnosic acid
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silver nitrate
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尹寿伟
鄢俐
杨晓泉
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of nano material preparation, and discloses a preparation method for green synthesis of nano silver by using carnosic acid. The method comprises the following steps: (1) preparing carnosic acid into a solution to obtain a carnosic acid solution; preparing silver nitrate into a solution by adopting water to obtain a silver nitrate solution; (2) mixing the carnosic acid solution with the silver nitrate solution, and heating for reaction to obtain the nano-silver. The method is simple, mild in condition and environment-friendly; the prepared nano silver has good dispersibility and stability, has good sterilization effect on escherichia coli and staphylococcus aureus and has no toxic or side effect.

Description

Preparation method for green synthesis of nano-silver by using carnosic acid
Technical Field
The invention belongs to the technical field of nano material preparation, and relates to a method for green synthesis of nano silver by using carnosic acid.
Background
Nanotechnology is one of the research hotspots in recent years. Many existing methods for producing nano-silver materials require the addition of various chemical reagents, may generate harmful byproducts, cause harm to human bodies and environment in the preparation process, and have high cost.
The nano silver particles have obvious and unique properties such as surface enhanced Raman scattering, catalysis, biological and medical sensors and strong broad-spectrum antibacterial activity, and have wide application prospects in the aspects of biological medicine, biological rapid detection, industrial catalysis, food safety and the like due to the non-toxicity, safety and the like. The current preparation methods of nano silver generally comprise two main types of chemical methods and physical methods. The chemical method is divided into: micro-emulsion method, sol-gel method, precipitation method, photochemical reduction method, chemical reduction method, etc.; the physical method is divided into: evaporative condensation, laser ablation, high-energy mechanical ball milling, microwave-assisted and ultrasonic-assisted reduction, magnetron sputtering, and the like. The principle of the physical method is simple, but the method has higher requirements on instruments and equipment and high production cost, and is mainly suitable for industrialized preparation with low requirements on the size and the shape of the nano silver particles. The key technology for synthesizing the nano silver particles by a chemical method is how to control the size of the particles, narrow particle size distribution and obtain a specific and uniform crystal structure. However, most chemical methods require the introduction of more chemical reagents, and have the problems of higher production cost, certain environmental pollution and the like.
The nano silver is easy to be oxidized and gathered in the air, so that the antibacterial activity is lost, and the defects cause that the practical application of the nano silver material is limited. According to the method, silver ions are reduced by using carnosic acid under mild reaction conditions, and no other reducing agent is adopted, so that the nano silver with controllable morphology and size is prepared.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a method for green synthesis of nano silver by using carnosic acid. The method solves the problems that the silver nano material produced by the existing chemical method needs to be added with a plurality of chemical reagents, which causes harm to the environment and human body in the preparation process and causes overhigh cost. Meanwhile, the nano silver prepared by the method has better dispersibility and stability, and has good bactericidal action on escherichia coli and staphylococcus aureus.
The purpose of the invention is realized by the following technical scheme:
a preparation method for green synthesis of nano-silver by using carnosic acid comprises the following steps:
(1) preparing carnosic acid into a solution to obtain a carnosic acid solution; preparing silver nitrate into a solution by adopting water to obtain a silver nitrate solution;
preparing carnosic acid into a solution by adopting an alcoholic solution, wherein the alcoholic solution is an ethanol water solution, and preferably an ethanol solution with the volume fraction of 95%; the mass concentration of the carnosic acid solution is 0.05-1.5%;
the concentration of the silver nitrate solution is 5 multiplied by 10-1～5×10-3mol/L；
(2) Mixing the carnosic acid solution with the silver nitrate solution, and heating for reaction to obtain the nano-silver.
The volume ratio of the carnosic acid solution to the silver nitrate solution in the step (2) is 1: 9-9: 1.
In the step (2), the heating reaction temperature is 20-100 ℃, the reaction pH is 3-11 (adjusted by hydrochloric acid or sodium hydroxide), and the heating reaction time is 15-120 min.
Compared with the prior art, the invention has the following advantages and effects:
(1) the method is simple to operate, mild in condition, green and environment-friendly, and does not harm the environment and human bodies.
(2) The invention has the advantages of high production efficiency, high product quality and the like. The obtained nano-silver has good dispersibility and stability, has good bactericidal effect on escherichia coli and staphylococcus aureus, and has good application prospect.
Drawings
FIG. 1 is a UV-VIS spectrum of green synthesis of nano-silver particles from carnosic acid in example 1, wherein a is the UV-VIS spectrum of nano-silver obtained in example 1, and b and c are 0.5% carnosic acid and 5X 10, respectively-2Ultraviolet-visible spectrum of mol/L silver nitrate solution;
FIG. 2 is TEM image of green synthesis of nano-silver particles from carnosic acid in example 1;
FIG. 3 is a UV-Vis spectrum of green synthesis of nano-silver particles using carnosic acid in example 2 and example 1, wherein a is the UV-Vis spectrum of nano-silver obtained in example 2, and b is the UV-Vis spectrum of nano-silver obtained in example 1;
FIG. 4 is a UV-Vis spectrum of green synthesis of nano-silver particles using carnosic acid in example 3 and example 1, wherein a is the UV-Vis spectrum of nano-silver obtained in example 3, and b is the UV-Vis spectrum of nano-silver obtained in example 1;
FIG. 5 is a UV-Vis spectrum of green synthesis of nano-silver particles using carnosic acid in example 4 and example 1, wherein a is the UV-Vis spectrum of nano-silver obtained in example 4, and b is the UV-Vis spectrum of nano-silver obtained in example 1;
fig. 6 is a uv-vis spectrum of nano silver particles synthesized using carnosic acid green in example 5 and example 1, wherein a is the uv-vis spectrum of nano silver obtained in example 5, and b is the uv-vis spectrum of nano silver obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparing a carnosic acid solution: dissolving carnosic acid into an ethanol solution with the volume fraction of 95%, stirring, and fully dissolving to obtain a carnosic acid solution, wherein the mass concentration of the carnosic acid is 0.5%;
preparing silver nitrate solution in the second step: dissolving silver nitrate in water, and fully hydrating to obtain silver nitrate solution with silver nitrate concentration of 5 × 10-2mol/L；
The third step: mixing carnosic acid solution and silver nitrate solution according to the ratio of 5: 5, heating in a constant-temperature water bath, controlling the temperature at 60 ℃, controlling the reaction pH to be 5, and controlling the reaction time to be 15min to prepare the nano silver particles. The ultraviolet-visible spectrum of the obtained product is shown in figures 1 and 3-6.
The ultraviolet-visible spectrum is an important index for characterizing the synthesis and stability of the nano-silver. The SPR peak in the visible spectrum is determined by the shape, particle size and degree of aggregation of the metal particles. The stronger the SPR peak is, the narrower the peak width is, the higher the nano silver particle yield is, the better the stability is, the smaller the particle size is, and the better the antibacterial effect is. As shown in FIG. 1, the nano-silver obtained in the example has an absorption peak in the range of 400-450nm and the peak intensity is stronger than that of carnosic acid, silver nitrate solution. The nano silver synthesized by the carnosic acid and the silver nitrate is good in stability, high in yield and good in antibacterial property.
The morphology of nano-silver in the nano-silver composite material was observed by a transmission electron microscope, and the result is shown in fig. 2. Fig. 2 is a TEM image of nano silver obtained in example 1. The result shows that the nano silver particles prepared by the method have good dispersibility, and most of the nano silver particles have uniform particle size.
The antibacterial effect of the nano silver is determined by utilizing an agar diffusion experiment. Table 1 shows the bacteriostatic effect of the nano silver obtained in example 1. One colony of E.coli ATCC8739 (purchased) and Staphylococcus aureus ATCC6538 was dispersed in the nutrient broth and incubated at 37 ℃ for 16 hours, and the density of the broth was diluted to 10 with sterile water5-106cfu/mL. And 100. mu.L of the bacterial suspension was spread evenly on nutrient agar (25mL nutrient broth agar). A flat punch was then used to make a hole of approximately 6 mm in the plate. 50 μ L of nanosilver, AgNO3, CA and 50% ethanol were dispersed in the wells, respectively. After incubation at 37 ℃ for 24 hours, the width of the zone of inhibition around the disc was measured with a ruler. Each experiment was performed in triplicate and repeated twice.
Table 1 bacteriostatic effect of nano silver obtained in example 1
Figure BDA0001904907060000041
Example 2
Preparing a carnosic acid solution: dissolving carnosic acid into an ethanol solution with the volume fraction of 95%, stirring, and fully dissolving to obtain a carnosic acid solution, wherein the mass concentration of the carnosic acid is 0.05%;
preparing silver nitrate solution in the second step: dissolving silver nitrate in water, fully hydrating to obtain silver nitrate solution,silver nitrate concentration of 5 × 10-2mol/L；
The third step: mixing carnosic acid solution and silver nitrate solution according to the ratio of 5: 5, heating in a constant-temperature water bath, controlling the temperature at 60 ℃, controlling the reaction pH to be 5, and controlling the reaction time to be 15min to prepare the nano silver particles. The UV-Vis spectra of the obtained product are shown in FIG. 3. Compared with the example 1, the higher the carnosic acid mass concentration is, the better the stability, yield and antibacterial property of the nano silver are.
Example 3
Preparing a carnosic acid solution: dissolving carnosic acid into an ethanol solution with the volume fraction of 95%, stirring, and fully dissolving to obtain a carnosic acid solution, wherein the mass concentration of the carnosic acid is 0.5%;
preparing silver nitrate solution in the second step: dissolving silver nitrate in water, and fully hydrating to obtain silver nitrate solution with silver nitrate concentration of 5 × 10-1mol/L；
The third step: mixing carnosic acid solution and silver nitrate solution according to the ratio of 5: 5, heating in a constant-temperature water bath, controlling the temperature at 60 ℃, controlling the reaction pH to be 3, and controlling the reaction time to be 15min to prepare the nano silver particles. The UV-Vis spectrum of the obtained product is shown in FIG. 4. In this example, it was shown that when the reaction pH was 5, the nano silver had good stability, high yield and good antibacterial property, as compared with example 1, which showed that pH was 3.
Example 4
Preparing a carnosic acid solution: dissolving carnosic acid into an ethanol solution with the volume fraction of 95%, stirring, and fully dissolving to obtain a carnosic acid solution, wherein the mass concentration of the carnosic acid is 0.5%;
preparing silver nitrate solution in the second step: dissolving silver nitrate in water, and fully hydrating to obtain silver nitrate solution with silver nitrate concentration of 5 × 10-1mol/L；
The third step: mixing carnosic acid solution and silver nitrate solution according to the ratio of 5: 5, heating in a constant-temperature water bath, controlling the temperature at 40 ℃, controlling the reaction pH at 5, and reacting for 60min to prepare the nano silver particles. The UV-Vis spectrum of the obtained product is shown in FIG. 5. Compared with the example 1, the embodiment shows that when the reaction temperature is higher, the nano silver has good stability, high yield and good antibacterial property.
Example 5
Preparing a carnosic acid solution: dissolving carnosic acid into an ethanol solution with the volume fraction of 95%, stirring, and fully dissolving to obtain a carnosic acid solution, wherein the mass concentration of the carnosic acid is 0.5%;
preparing silver nitrate solution in the second step: dissolving silver nitrate in water, and fully hydrating to obtain silver nitrate solution with silver nitrate concentration of 5 × 10-1mol/L；
The third step: mixing carnosic acid solution with silver nitrate solution according to the ratio of 5: 5, heating in a constant-temperature water bath, controlling the temperature at 60 ℃, controlling the reaction pH to be 5, and controlling the reaction time to be 120min to prepare the nano silver particles. The UV-Vis spectrum of the obtained product is shown in FIG. 6. Compared with the example 1, the longer the reaction time is, the better the stability, the higher the yield and the antibacterial property of the nano silver are.
Finally, it should be noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.

Claims (2)

1. A preparation method for green synthesis of nano-silver by using carnosic acid is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing carnosic acid into a solution to obtain a carnosic acid solution; preparing silver nitrate into a solution by adopting water to obtain a silver nitrate solution;
(2) mixing the carnosic acid solution with the silver nitrate solution, and heating for reaction to obtain nano silver;
the mass concentration of the carnosic acid solution is 0.5-1.5%;
the concentration of the silver nitrate solution is 5 multiplied by 10-1~5×10-3mol/L；
In the step (2), the heating reaction temperature is 60-100 ℃, the reaction pH is 5, and the heating reaction time is 60-120 min;
preparing carnosic acid into a solution by adopting an alcoholic solution, wherein the alcoholic solution is an ethanol water solution, and the alcoholic solution is an ethanol solution with the volume fraction of 95%;
the volume ratio of the carnosic acid solution to the silver nitrate solution in the step (2) is 1: 1.
2. Nano silver obtained by the production method according to claim 1.
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