Attapulgite-silver ion modified Prussian blue analogue nano-composite antibacterial agent as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of antibacterial materials, and particularly relates to a nano composite antibacterial agent for in-situ growth of a silver ion modified Prussian blue analogue on attapulgite as well as a preparation method and application of the nano composite antibacterial agent. According to the method, the attapulgite-silver ion modified prussian blue analogue nano composite antibacterial agent is synthesized by adopting a simple wet chemical method and an electrochemical replacement method, in the preparation process, natural nano rod-like mineral attapulgite is used as a carrier, and nano particle prussian blue and the nano rod-like attapulgite are combined by adopting an in-situ precipitation method; the antibacterial property of the natural mineral material is effectively improved; furthermore, the composite material is modified through silver nitrate by using an electrochemical replacement method, so that the killing effect of the composite material on bacteria and fungi can be effectively enhanced, and the purpose of long-acting bacteriostasis is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial materials, and in particular relates to an attapulgite-silver ion modified Prussian blue analog nano composite antibacterial agent and a preparation method and application thereof. Background Art

[0002] There are all kinds of bacteria in the environment, and we come into contact with them every day. Some harmless bacteria can establish beneficial relationships with their hosts, but there are still a large number of pathogenic strains in life, and thousands of people die from bacterial infections every year. These pathogenic bacteria can also seriously contaminate food, drinking water, and medical equipment, leading to infectious diseases such as foodborne diseases, urinary tract infections, and sexually transmitted diseases. What is more worrying is that some infectious diseases may further induce complications of bacterial infections. However, this kind of bacteria has strong adaptability and reproduces quickly. If no timely action is taken, it may cause a global disaster.

[0003] Compared with traditional antibacterial materials (such as antibiotics), nano antibacterial materials have many advantages, such as more stable performance and more significant effects. Nano antibacterial materials firstly affect the structure of bacteria by contacting with the bacterial surface (cell membrane, cell wall); at the same time, the metal elements in the materials will dissolve and react with the substances inside the cells, affecting their reproduction; in addition, nano materials can produce reactive oxygen species (ROS) through various catalytic effects, such as ·O -2 and ·OH, acting on intracellular substances by catalytic oxidation, thereby inactivating bacteria and achieving an antibacterial effect.

[0004] Prussian blue (PB) and Prussian blue analogs (PBAs) have a wide range of applications in catalysis, ion batteries, etc. due to their unique framework structure, three-dimensional pores, and the adjustability of metal ions. At the same time, PB has excellent biocompatibility, so it has great application potential in cancer treatment, antibacterial materials, etc. However, PB has many problems. Although it has certain antibacterial properties under H2O2 or near-infrared light irradiation as a nanozyme and infrared photothermal material, the performance is not ideal. In addition, PB was first used as a blue pigment. The dark color greatly reduces its application range. It is necessary to modify it to improve the broad-spectrum antibacterial properties of the material and reduce the restrictions of color on the application range. Summary of the invention

[0005] The object of the present invention is to provide a attapulgite-silver ion modified Prussian blue analogue (Ag + PB-APT) nanocomposite antibacterial agent and its preparation method and application are used to solve the problem of bacterial contamination, achieve good biocompatibility and excellent antibacterial performance, with low cost, safety and environmental protection.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A method for preparing an attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent comprises the following steps:

[0008] Step 1, weighing a certain mass of ferric chloride and attapulgite, dispersing the ferric chloride and attapulgite in a 1.0-5.0 mM citric acid aqueous solution to obtain solution A, stirring until the solution is uniformly dispersed, and ultrasonically dispersing for 15-30 minutes;

[0009] Step 2, weigh a certain amount of potassium ferrocyanide trihydrate, disperse the potassium ferrocyanide trihydrate in a 1.0-5.0 mM citric acid aqueous solution to obtain solution B, stir the two solutions to disperse them evenly, and perform ultrasonic dispersion for 15-30 minutes;

[0010] Step 3: Transfer the two solutions to a constant temperature water bath, add solution B dropwise to solution A, react at constant temperature for 2 to 10 minutes, transfer to room temperature, and continue stirring for 30 minutes;

[0011] Step 4: After the reaction is completed and the mixture is naturally cooled, the obtained sample is centrifuged, and the precipitated solid is washed and dried to obtain attapulgite-Prussian blue;

[0012] Step 5, weigh a certain mass of attapulgite-Prussian blue and silver nitrate, disperse the attapulgite-Prussian blue in deionized water and continue stirring, then add silver nitrate, stir for 2 hours, centrifuge, wash and dry the resulting composite material to obtain a nanocomposite antibacterial agent of attapulgite-silver ion modified Prussian blue analogue.

[0013] Furthermore, in the step 1, the amount of ferric chloride added is 4 to 16 g / L.

[0014] Furthermore, in the step 2, the amount of potassium ferrocyanide trihydrate added is 11 to 42 g / L.

[0015] Furthermore, in the step 5, the amount of attapulgite-Prussian blue added is 5 to 10 g / L.

[0016] Furthermore, in step five, the amount of silver nitrate added is 3.6-10 g / L.

[0017] A attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent prepared by any of the above preparation methods.

[0018] Furthermore, the modified Prussian blue analog nanoparticles are uniformly loaded on the surface of nanorod-shaped attapulgite, the length of the attapulgite is 200-500 nm, and the size of the Prussian blue analog nanoparticles is 5-50 nm.

[0019] An application of the above-mentioned attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent in the antibacterial field and biomedical treatment.

[0020] Compared with the prior art, the present invention has the following technical effects:

[0021] The invention adopts a simple in-situ precipitation method and an electrochemical replacement method to synthesize a attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent. In the preparation process, natural nano-rod-shaped attapulgite mineral is used as a carrier, and the nano-particle Prussian blue is loaded on the attapulgite by an in-situ precipitation method, which effectively solves the agglomeration problem of Prussian blue nanomaterials and improves the antibacterial performance and commercial value of low-cost natural clay minerals. Ag + The introduction of the nanocomposite antibacterial agent causes silver ion dissolution after contact with bacteria. + It can interact with bacterial cell membranes and enter the interior of bacteria to cause metabolic disorders, thereby damaging the bacteria, improving the antibacterial activity of the nanocomposite material, improving the broad-spectrum antibacterial properties of the material, and forming a nanocomposite antibacterial agent with good biocompatibility and high cost performance.

[0022] (1) In the present invention, the nanomaterial dispersibility improved by the excellent aspect ratio of attapulgite and the silver ion dissolution effect jointly improve the antibacterial activity of the nanocomposite material, forming a nanocomposite antibacterial agent with good biocompatibility and excellent antibacterial performance.

[0023] (2) The nanocomposite antibacterial agent prepared by the present invention has excellent antibacterial performance, low price, safety and environmental protection, strong drug resistance and wide application range.

[0024] (3) The attapulgite-silver ion modified Prussian blue nanocomposite antibacterial agent prepared by the present invention can effectively kill pathogens such as Escherichia coli and Staphylococcus aureus, and its minimum inhibitory concentration (MIC) for Escherichia coli and Staphylococcus aureus is 8 μg / mL. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 From top to bottom are the attapulgite-silver ion modified Prussian blue analogue (Ag + XRD patterns of the nanocomposite antibacterial agent PB-APT), attapulgite-Prussian blue (PB-APT) prepared in Comparative Example 1, and attapulgite (APT);

[0026] Figure 2 TEM image of PB-APT nanocomposite;

[0027] Figure 3 Ag +TEM image of PB-APT nanocomposite antibacterial agent;

[0028] Figure 4 This is a photo of the colony growth of untreated Staphylococcus aureus;

[0029] Figure 5 This is a photo of the colony growth of Staphylococcus aureus after treatment with PB-APT nanomaterials under dark conditions;

[0030] Figure 6 Ag under dark conditions + Photo of colony growth of Staphylococcus aureus after treatment with PB-APT nanocomposite antimicrobial agent;

[0031] Figure 7 This is a photo of the colony growth of untreated E. coli;

[0032] Figure 8 Ag under dark conditions + Photo of the colony growth of Escherichia coli after treatment with PB-APT nanocomposite antibacterial agent. DETAILED DESCRIPTION

[0033] The specific contents of the present invention are further explained in detail below in conjunction with embodiments.

[0034] Example 1

[0035] First, 0.64g of ferric chloride and 1.68g of potassium ferrocyanide trihydrate were weighed respectively, and the ferric chloride was dispersed in 0.4g of attapulgite citric acid aqueous solution to obtain solution A; potassium ferrocyanide trihydrate was dispersed in citric acid aqueous solution (2mM) to obtain solution B, and the two solutions were stirred until they were evenly dispersed, and then ultrasonically dispersed for 15min; then, solution A was transferred to a 60°C constant temperature heating pot, and solution B was added dropwise to solution A, and the reaction was carried out at a constant temperature for 5min, and then the mixture was moved to room temperature and stirred for 30min; finally, after the reaction was completed and cooled naturally, the obtained sample was centrifuged, and the precipitated solid was washed and dried to obtain attapulgite-Prussian blue;

[0036] Weigh 0.25 g of attapulgite-Prussian blue and 0.17 g of silver nitrate respectively, disperse the attapulgite-Prussian blue in deionized water and continue stirring, then add silver nitrate and stir for 2 hours, centrifuge the obtained composite material, wash and dry to obtain a nanocomposite antibacterial agent of attapulgite-silver ion modified Prussian blue.

[0037] Example 2

[0038] First, 0.64g of ferric chloride and 1.68g of potassium ferrocyanide trihydrate were weighed respectively, and the ferric chloride was dispersed in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, and potassium ferrocyanide trihydrate was dispersed in citric acid aqueous solution (2mM) to obtain solution B, and the two solutions were stirred until they were evenly dispersed, and then ultrasonically dispersed for 30min; then, solution A was transferred to a 60°C constant temperature heating pot, and solution B was added dropwise to solution A, and the reaction was carried out at a constant temperature for 5min, and then the solution was moved to room temperature and stirred for 30min; finally, after the reaction was completed and cooled naturally, the obtained sample was centrifuged, and the precipitated solid was washed and dried to obtain attapulgite-Prussian blue;

[0039] Weigh 0.25 g of attapulgite-copper-iron Prussian blue and 0.34 g of silver nitrate respectively, disperse the attapulgite-Prussian blue in deionized water and continue stirring, then add silver nitrate and stir for 2 hours, centrifuge the obtained composite material, wash and dry to obtain a nanocomposite antibacterial agent of attapulgite-silver ion modified Prussian blue.

[0040] Example 3

[0041] First, 0.32g of ferric chloride and 0.84g of potassium ferrocyanide trihydrate were weighed respectively, and the ferric chloride was dispersed in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, and potassium ferrocyanide trihydrate was dispersed in citric acid aqueous solution (2mM) to obtain solution B, and the two solutions were stirred until they were evenly dispersed, and then ultrasonically dispersed for 30min; then, solution A was transferred to a 60°C constant temperature heating pot, and solution B was added dropwise to solution A, and the reaction was carried out at a constant temperature for 5min, and then the solution was moved to room temperature and stirred for 30min; finally, after the reaction was completed and cooled naturally, the obtained sample was centrifuged, and the precipitated solid was washed and dried to obtain attapulgite-Prussian blue;

[0042] Weigh 0.25 g of attapulgite-Prussian blue and 0.25 g of silver nitrate respectively, disperse the attapulgite-Prussian blue in deionized water and continue stirring, then add silver nitrate and stir for 2 hours, centrifuge the obtained composite material, wash and dry to obtain a nanocomposite antibacterial agent of attapulgite-silver ion modified Prussian blue.

[0043] Example 4

[0044] Step 1: First, weigh 0.32g of ferric chloride and 0.84g of potassium ferrocyanide trihydrate, respectively, disperse the ferric chloride in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, disperse potassium ferrocyanide trihydrate in citric acid aqueous solution (2mM) to obtain solution B, stir until the two solutions are evenly dispersed, and then ultrasonically disperse for 30 minutes; then, transfer solution A to a 60°C constant temperature heating pot, add solution B dropwise to solution A, react at a constant temperature for 5 minutes, move to room temperature, and continue stirring for 30 minutes; finally, after the reaction is completed and cooled naturally, the obtained sample is centrifuged, and the precipitated solid is washed and dried to obtain attapulgite-Prussian blue;

[0045] Step 2: Weigh 0.25g of attapulgite-Prussian blue and 0.51g of silver nitrate respectively, disperse the attapulgite-copper-iron Prussian blue in deionized water and continue stirring, then add silver nitrate and stir for 2h, centrifuge, wash and dry the obtained composite material to obtain a nanocomposite antibacterial agent of attapulgite-silver ion modified Prussian blue.

[0046] Comparative Example 1

[0047] Step 1: First, weigh 0.64g of ferric chloride and 1.68g of potassium ferrocyanide trihydrate, respectively, disperse the ferric chloride in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, disperse potassium ferrocyanide trihydrate in citric acid aqueous solution (2mM) to obtain solution B, stir until the two solutions are evenly dispersed, and then ultrasonically disperse for 15min; then, transfer solution A to a 60°C constant temperature heating pot, add solution B dropwise to solution A, react at a constant temperature for 2 to 10min, move to room temperature, and continue stirring for 30min; finally, after the reaction is completed and cooled naturally, the obtained sample is centrifuged, and the precipitated solid is washed and dried to obtain attapulgite-Prussian blue;

[0048] Figures 1 to 8 Ag + Characterization results of PB-APT nanocomposite antibacterial agent. Figure 1 From top to bottom, the Ag prepared in Example 1 + XRD patterns of PB-APT nanocomposite antibacterial agent, PB-APT prepared in Comparative Example 1, and APT. Figure 1 The two attapulgite composites clearly showed the diffraction peaks of attapulgite, which matched those of pure APT. In addition, the XRD patterns of PB-APT nanocomposite antibacterial agent showed obvious PB characteristic peaks (JCPDS 01-0239). + The PB-APT spectrum also contains a strong diffraction peak of silver Prussian blue analogue, indicating that Ag + Successful preparation of PB-APT nanocomposite antibacterial agent.

[0049] Figure 2 This is the TEM photo of PB-APT prepared in Comparative Example 1. Figure 3 The Ag prepared in Example 1 + TEM images of PB-APT, from Figure 2 and Figure 3 It can be seen that the natural mineral clay attapulgite has a nanorod-like structure with a length of 200-500nm and a width of about 5nm. It has a very large aspect ratio. It can be observed that there are a large number of nanoparticles on it, and they are relatively uniform. Combined with the XRD test results, it can be seen that they are PB nanoparticles. Figure 3 It can be observed that different from Figure 2 The nanoparticles are AgPB nanoparticles, which further illustrates that Ag + Successful preparation of PB-APT nanocomposite antibacterial agent.

[0050] Figure 4 This is a photo of the colony growth of untreated Staphylococcus aureus; Figure 5 This is a photo of the colony growth of Staphylococcus aureus after treatment with PB-APT nanomaterials under dark conditions; Figure 6 Ag in dark conditions + Photo of colony growth of Staphylococcus aureus after treatment with PB-APT nanocomposite antibacterial agent; Figure 4 Compared with the blank control group, Figure 5 8μg / ml PB-APT had a certain inhibitory effect on Staphylococcus aureus colonies. Figure 6 8μg / ml Ag + No colonies appeared in the culture of Staphylococcus aureus solution after 10 min of PB-APT treatment; Figure 7 This is a photo of the colony growth of untreated E. coli; Figure 8 Ag under dark conditions + Photo of the colony growth of Escherichia coli after treatment with PB-APT nanocomposite antibacterial agent; it can be observed that the same Ag at 8μg / ml + After 10 min of PB-APT treatment, no E. coli colonies appeared on the culture dish.

[0051] The above-mentioned examples show that the prepared Ag + PB-APT material has a large number of active sites that come into contact with bacteria, exhibiting enhanced broad-spectrum antibacterial activity. It has excellent antibacterial properties without the need for near-infrared light and H2O2 catalysis. Its preparation process is simple, low-cost, and conducive to its application in environmental and medical fields.

[0052] To sum up, the above are only preferred specific implementation modes of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and inventive concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent, characterized in that: The following steps are involved: Step 1, weighing a certain mass of ferric chloride and attapulgite, dispersing the ferric chloride and attapulgite in a 1.0-5.0 mM citric acid aqueous solution to obtain solution A, stirring until the solution is uniformly dispersed, and ultrasonically dispersing for 15-30 minutes; Step 2, weigh a certain amount of potassium ferrocyanide trihydrate, disperse the potassium ferrocyanide trihydrate in a 1.0-5.0 mM citric acid aqueous solution to obtain solution B, stir the two solutions to disperse them evenly, and perform ultrasonic dispersion for 15-30 minutes; Step 3: Transfer the two solutions to a constant temperature water bath, add solution B dropwise to solution A, react at constant temperature for 2 to 10 minutes, transfer to room temperature, and continue stirring for 30 minutes; Step 4: After the reaction is completed and the mixture is naturally cooled, the obtained sample is centrifuged, and the precipitated solid is washed and dried to obtain attapulgite-Prussian blue; Step 5, weigh a certain mass of attapulgite-Prussian blue and silver nitrate, disperse the attapulgite-Prussian blue in deionized water and continue stirring, then add silver nitrate, stir for 2 hours, centrifuge, wash and dry the resulting composite material to obtain a nanocomposite antibacterial agent of attapulgite-silver ion modified Prussian blue analogue.

2. The method for preparing the attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent according to claim 1, characterized in that: In the step 1, the amount of ferric chloride added is 4-16 g / L.

3. The method for preparing the attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent according to claim 1, characterized in that: The amount of potassium ferrocyanide trihydrate added in step 2 is 11-42 g / L.

4. The method for preparing the attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent according to claim 1, characterized in that: In the step 5, the amount of attapulgite-Prussian blue added is 5-10 g / L.

5. The method for preparing the attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent according to claim 1, characterized in that: The amount of silver nitrate added in step 5 is 3.6-10 g / L.

6. An attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent prepared by the preparation method according to any one of claims 1 to 5.

7. The attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent according to claim 6, characterized in that: The modified Prussian blue analog nanoparticles are uniformly loaded on the surface of nanorod-shaped attapulgite, the length of the attapulgite is 200-500nm, and the size of the Prussian blue analog nanoparticles is 5-50nm.

8. An application of the attapulgite-silver ion modified Prussian blue analog nanocomposite antibacterial agent as claimed in claim 6 in the field of antibacterial and biomedical treatment.

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