CN113773525B

CN113773525B - Preparation method and application of molybdenum disulfide-loaded nano-silver antibacterial hydrogel

Info

Publication number: CN113773525B
Application number: CN202111097378.4A
Authority: CN
Inventors: 杨建军; 刘雷; 汪煜强; 吴庆云; 张建安; 吴明元; 刘久逸
Original assignee: Anhui University
Current assignee: Anhui University
Priority date: 2021-09-18
Filing date: 2021-09-18
Publication date: 2022-06-07
Anticipated expiration: 2041-09-18
Also published as: CN113773525A

Abstract

The invention discloses a preparation method and application of molybdenum disulfide-loaded nano-silver antibacterial hydrogel₂Mixing the solution; then the TA-MoS is added₂The mixed solution is mixed and reacted with acrylamide, ammonium persulfate, N' -methylene bisacrylamide and deionized water to obtain the product containing TA-MoS₂A polyacrylamide hydrogel; finally, the product will contain TA-MoS₂Placing polyacrylamide hydrogel in prepared AgNO₃And obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel in the solution. The TA adopted by the hydrogel prepared by the invention has a multi-benzene ring and polyphenol structure, can effectively disperse and stabilize the distribution of nano-silver, provides better antibacterial performance, has high sterilization efficiency, and does not need an additional reducing agent; meanwhile, the addition of the nano particles can effectively enhance the mechanical property and the heat resistance of the hydrogel, and the hydrogel is expected to be applied to the field of biomedicine as an antibacterial material.

Description

Preparation method and application of molybdenum disulfide-loaded nano-silver antibacterial hydrogel

Technical Field

The invention belongs to the field of biomedical materials and polymer chemistry, and particularly relates to a preparation method and application of a molybdenum disulfide-loaded nano silver antibacterial hydrogel.

Background

The antibacterial material has been widely used in daily life, and has a great contribution to the protection of the life and health of people. Common antibacterial agents include antibiotics, halogens, peroxides, quaternary ammonium salts, etc., however, these antibacterial materials are often associated with toxicity, drug resistance, non-sustainable use, low antibacterial efficiency, and lack of broad spectrum antibacterial activity during use. The silver nanoparticles can rapidly kill and inactivate bacteria after contacting with the bacteria, are an antibacterial material with broad-spectrum efficient sterilization performance, and are combined with hydrogel in order to enable the antibacterial performance of the antibacterial material to be better.

The hydrogel is a three-dimensional network structure, can absorb wound secretion in the aspect of wound treatment due to the special performance, can effectively promote wound healing due to the characteristic of similarity to extracellular matrix, has wide development and application prospects, and is widely applied to tissue engineering, medical engineering and sensing. However, the conventional hydrogel may have a reduced antibacterial effect during the application process due to its poor mechanical properties and easy fracture deformation. The molybdenum disulfide nanosheet layer has the characteristics similar to those of graphene, is a two-dimensional material, and can be used for enhancing the mechanical property, the heat resistance and the like of the material. Tannin is not only a natural compound with reducing performance and partial sterilizing performance, but also can effectively disperse and stabilize the distribution of silver nano particles due to the polyphenyl ring and polyphenol structure of the tannin, thereby providing better antibacterial performance.

Therefore, the hydrogel containing silver nanoparticles can be applied to the aspect of biological antibacterial materials, can be used as an excellent antibacterial dressing to cover the surface of a wound when the wound is treated, can protect the wound from bacterial infection, can keep the environment of the wound stable, is easy to exchange gas and has good biocompatibility.

Disclosure of Invention

The invention provides a preparation method and application of a molybdenum disulfide-loaded nano-silver antibacterial hydrogel, and aims to solve the technical problems of poor antibacterial performance of the hydrogel in the prior art and the like.

The preparation method of the molybdenum disulfide-loaded nano-silver antibacterial hydrogel comprises the steps of stripping molybdenum disulfide by tannic acid to obtain TA-MoS₂Mixing the solution; then the TA-MoS is added₂The mixed solution is mixed and reacted with acrylamide, ammonium persulfate, N' -methylene bisacrylamide and deionized water to obtain the product containing TA-MoS₂A polyacrylamide hydrogel; finally, the product will contain TA-MoS₂Placing polyacrylamide hydrogel in prepared AgNO₃And obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel in the solution.

The preparation method of the antibacterial hydrogel with the molybdenum disulfide loaded with the nano silver specifically comprises the following steps:

step 1: adding tannic acid and molybdenum disulfide into deionized water, uniformly stirring, placing in an ultrasonic cell crusher, setting ultrasonic time for 2-4h, ultrasonic power of 300-500W, and obtaining TA-MoS after ultrasonic processing₂Mixing the solution;

step 2: acrylamide, ammonium persulfate, N' -methylene-bisacrylamide, deionized water and TA-MoS obtained in step 1₂The mixed solution is added into a reactor under N₂Fully stirring under protection, then heating to 60-70 ℃ for reaction for 4-6h to obtain the product containing TA-MoS₂A polyacrylamide hydrogel; it is then purified in a reaction flask containing deionized water and soaked for 72 hours, during which the deionized water is replaced at regular intervals, typically 4-6 hours, in order to soak out the unreacted monomers.

And step 3: the purified product obtained in the step 2 contains TA-MoS₂The polyacrylamide hydrogel is completely frozen and dried at the temperature of-50 ℃, and then is placed in prepared AgNO₃In the aqueous solution, stirring at low speed of 200-500r/min at room temperature in the dark to fully swell the freeze-dried gel, taking out the freeze-dried gel, and washing residual AgNO on the surface by using deionized water₃And (4) obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel through solution.

Preferably, in the step 1, the mass ratio of the tannic acid to the molybdenum disulfide is 1: 1-3; TA-MoS₂The concentration of the mixed solution is 2-4 mg/mL.

Preferably, in step 2, 2.0g of acrylamide is added; the adding mass of the ammonium persulfate is 0.4-0.6% of the mass of the acrylamide; the adding mass of the N, N' -methylene bisacrylamide is 0.1-0.2% of the mass of the acrylamide; the adding mass of the deionized water is 1-10 times of that of the acrylamide; TA-MoS₂The mass of the acrylamide solution is 0.5-1.5% of the mass of the acrylamide solution.

Preferably, in step 3, AgNO₃The concentration of (b) is 40-60. mu.g/mL.

The molybdenum disulfide-loaded nano silver antibacterial hydrogel can be used for preparing wound dressings and antibacterial materials, and has excellent antibacterial performance.

Compared with the prior art, the invention has the beneficial effects that:

1. the tannin adopted by the hydrogel prepared by the invention has a multi-benzene-ring and polyphenol structure, can effectively disperse and stabilize the distribution of nano-silver, provides better antibacterial performance, has high sterilization efficiency, does not need an additional reducing agent, and is simple to operate.

2. The two-dimensional nanosheet structure is favorable for enhancing the flexibility of the hydrogel, and the silver nanoparticles can be well adsorbed by the special two-dimensional structure, so that the hydrogel has good antibacterial performance, has no drug resistance, and has a long-acting antibacterial effect.

3. The antibacterial hydrogel can be applied to wound dressings, daily antibacterial materials and the like.

Drawings

Fig. 1 is a graph showing the antibacterial effect of the hydrogels prepared in examples 1 to 4 and comparative examples 1 to 2 after contacting with s.

Fig. 2 is a graph of the inhibition circles of the hydrogels prepared in example 3 and comparative example 1 after 24h of culture in s.

FIG. 3 is a graph showing the reaction mechanism of stripping molybdenum disulfide from tannic acid and the dispersibility in water after stripping.

Detailed Description

The technical scheme of the invention is further analyzed and explained by combining specific examples.

Example 1:

1. adding 0.2g of tannic acid and 0.4g of molybdenum disulfide into a reaction flask filled with 300mL of deionized water solution, uniformly stirring, placing in an ultrasonic cell crusher, setting the ultrasonic time for 2h and the ultrasonic power for 300W, and obtaining TA-MoS with the concentration of 2mg/mL after the ultrasonic treatment is finished₂The solution was mixed.

2. 2.0g acrylamide, 0.48mL ammonium persulfate (20 mg/mL), 0.24mL N, N' -methylenebisacrylamide (10 mg/mL), 10g deionized water, and 2.5mL TA-MoS₂The mixed solution was added to a reaction flask under N₂The mixture is fully stirred under the condition of (1), and then is placed in a constant-temperature oven to react for 4 hours under the condition of controlling the reaction temperature to be 60 ℃ to obtain the product containing TA-MoS₂And (3) putting the polyacrylamide hydrogel into a reaction bottle filled with deionized water for purification, continuously soaking for 72 hours, and replacing the deionized water every 4 hours during the soaking period so as to soak out the monomers which do not participate in the reaction.

3. Purifying the purified product containing TA-MoS₂Placing the polyacrylamide hydrogel in a freeze dryer, completely freeze-drying at about-50 ℃, and placing the polyacrylamide hydrogel in the prepared AgNO₃Stirring at 300r/min in a low speed and dark room temperature in the aqueous solution (the concentration is 50mg/mL) to completely swell the freeze-dried gel, and washing residual AgNO on the surface by deionized water after taking out₃And (4) obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel through solution.

Example 2:

1. mixing 0.2g tannic acid and 0.4g diAdding molybdenum sulfide into a reaction bottle filled with 300mL of deionized water solution, uniformly stirring, placing in an ultrasonic cell crusher, setting the ultrasonic time for 2h, setting the ultrasonic power to be 300W, and obtaining the TA-MoS with the concentration of 2mg/mL after the ultrasonic treatment is finished₂The solution was mixed.

2. 2.0g of acrylamide, 0.48mL of ammonium persulfate (at a concentration of 20mg/mL), 0.24mL of N, N' -methylenebisacrylamide (at a concentration of 10mg/mL), 7.5g of deionized water, and 5mL of TA-MoS₂The mixed solution is added into a reaction flask under N₂The mixture is fully stirred under the condition of (1), and then is placed in a constant-temperature oven to react for 4 hours under the condition of controlling the reaction temperature to be 60 ℃ to obtain the product containing TA-MoS₂And (3) putting the polyacrylamide hydrogel into a reaction bottle filled with deionized water for purification, continuously soaking for 72 hours, and replacing the deionized water every 4 hours during the soaking period so as to soak out the monomers which do not participate in the reaction.

3. Purifying the purified product containing TA-MoS₂Placing the polyacrylamide hydrogel in a freeze dryer, completely freeze-drying at about-50 ℃, and placing the polyacrylamide hydrogel in prepared AgNO₃The freeze-dried gel is completely swelled by stirring the freeze-dried gel at low speed of 300r/min in a low-speed dark room temperature in the aqueous solution (the concentration is 50mg/mL), and the AgNO remained on the surface of the freeze-dried gel is washed by deionized water after the freeze-dried gel is taken out₃And (4) obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel through solution.

Example 3:

1. adding 0.2g of tannic acid and 0.4g of molybdenum disulfide into a reaction bottle filled with 300mL of deionized water solution, uniformly stirring, placing in an ultrasonic cell crusher, setting ultrasonic time for 2h, wherein the ultrasonic power is 300W, and obtaining TA-MoS with the concentration of 2mg/mL after ultrasonic treatment₂The solution was mixed.

2. 2.0g of acrylamide, 0.48mL of ammonium persulfate (concentration of 20mg/mL), 0.24mL of N, N' -methylenebisacrylamide (concentration of 10mg/mL), 2.5g of deionized water, and 10mL of TA-MoS₂The mixed solution was added to a reaction flask under N₂The mixture is fully stirred under the condition of (1), and then is placed in a constant-temperature oven to react for 4 hours under the condition of controlling the reaction temperature to be 60 ℃ to obtain the product containing TA-MoS₂The polyacrylamide hydrogel is put into a reaction bottle filled with deionized water for purification, and is continuously soaked for 72 hoursAnd h, replacing the deionized water every 4h during the soaking period so as to soak out the monomers which do not participate in the reaction.

3. Purifying the purified product containing TA-MoS₂Placing the polyacrylamide hydrogel in a freeze dryer, completely freeze-drying at about-50 ℃, and placing the polyacrylamide hydrogel in the prepared AgNO₃The freeze-dried gel is completely swelled by stirring the freeze-dried gel at low speed of 300r/min in a low-speed dark room temperature in the aqueous solution (the concentration is 50mg/mL), and the AgNO remained on the surface of the freeze-dried gel is washed by deionized water after the freeze-dried gel is taken out₃And (4) obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel through solution.

Example 4:

1. adding 0.2g of tannic acid and 0.6g of molybdenum disulfide into a reaction flask filled with 400mL of deionized water solution, uniformly stirring, placing in an ultrasonic cell crusher, setting the ultrasonic time for 3h, wherein the ultrasonic power is 400W, and obtaining TA-MoS with the concentration of 2mg/mL after the ultrasonic treatment₂The solution was mixed.

2. 2.0g acrylamide, 0.48mL ammonium persulfate (20 mg/mL), 0.24mL N, N' -methylenebisacrylamide (10 mg/mL), 2.5g deionized water, and 10mL TA-MoS₂The mixed solution was added to a reaction flask under N₂The mixture is fully stirred under the condition of (1), and then is placed in a constant-temperature oven to react for 4 hours under the condition of controlling the reaction temperature to be 60 ℃ to obtain the product containing TA-MoS₂And (3) putting the polyacrylamide hydrogel into a reaction bottle filled with deionized water for purification, continuously soaking for 72 hours, and replacing the deionized water every 4 hours during the soaking period so as to soak out the monomers which do not participate in the reaction.

3. Purifying the purified product containing TA-MoS₂Placing the polyacrylamide hydrogel in a freeze dryer, completely freeze-drying at about-50 ℃, and placing the polyacrylamide hydrogel in the prepared AgNO₃The freeze-dried gel is stirred in the aqueous solution (the concentration is 50mg/mL) at 300r/min at a low-speed light-shielding room temperature to completely swell the freeze-dried gel, and the AgNO remained on the surface of the freeze-dried gel is washed by deionized water after the freeze-dried gel is taken out₃And (4) obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel through solution.

Comparative example 1:

1. 0.2g of tannic acid and 0.4g of molybdenum disulfide were added to a reaction flask containing 300mL of deionized water solution and stirred uniformlyPlacing the mixture in an ultrasonic cell crusher after the mixture is homogenized, setting the ultrasonic time for 2h, setting the ultrasonic power to be 300W, and obtaining TA-MoS with the concentration of 2mg/mL after the ultrasonic is finished₂The solution was mixed.

2. 2.0g of acrylamide, 0.48mL of ammonium persulfate (at a concentration of 20mg/mL), 0.24mL of N, N' -methylenebisacrylamide (at a concentration of 10mg/mL), 12.5g of deionized water, and 0mL of TA-MoS₂The mixed solution was added to a reaction flask under N₂The monomer is placed in a constant temperature oven after being fully stirred under the condition of (1), the reaction temperature is controlled to be 60 ℃, the reaction is carried out for 4 hours, then the reaction bottle is placed in a reaction bottle filled with deionized water for purification, the soaking is carried out for 72 hours continuously, and the deionized water is replaced every 4 hours during the soaking period, so that the monomer which does not participate in the reaction is soaked out.

3. Placing the purified hydrogel in a freeze dryer, freeze-drying at-50 deg.C, and placing in AgNO₃The freeze-dried gel is completely swelled by stirring the freeze-dried gel at low speed of 300r/min in a low-speed dark room temperature in the aqueous solution (the concentration is 50mg/mL), and the AgNO remained on the surface of the freeze-dried gel is washed by deionized water after the freeze-dried gel is taken out₃And (5) obtaining the pure polyacrylamide hydrogel through solution.

Comparative example 2:

1. adding 0.4g of molybdenum disulfide into a reaction flask filled with 200mL of deionized water solution, uniformly stirring, placing in an ultrasonic cell crusher, setting the ultrasonic time for 2h, setting the ultrasonic power to 300W, and obtaining MoS with the concentration of 2mg/mL after the ultrasonic treatment is finished₂And (3) solution.

2. 2.0g of acrylamide, 0.48mL of ammonium persulfate (at a concentration of 20mg/mL), 0.24mL of N, N' -methylenebisacrylamide (at a concentration of 10mg/mL), 10g of deionized water, 2.5mL of MoS₂The mixed solution was added to a reaction flask under N₂The monomer is placed in a constant temperature oven after being fully stirred under the condition of (1), the reaction temperature is controlled to be 60 ℃, the reaction is carried out for 4 hours, then the reaction bottle is placed in a reaction bottle filled with deionized water for purification, the soaking is carried out for 72 hours continuously, and the deionized water is replaced every 4 hours during the soaking period, so that the monomer which does not participate in the reaction is soaked out.

3. Placing the purified hydrogel in a freeze dryer, freeze-drying at-50 deg.C, and placing in AgNO₃Is dissolved in waterStirring at 300r/min at low speed in dark room temperature in the solution (concentration is 50mg/mL) to make the freeze-dried gel fully swell, taking out, washing residual AgNO on the surface with deionized water₃And (4) obtaining the antibacterial hydrogel containing molybdenum disulfide by using the solution.

The antibacterial performance test is carried out on the molybdenum disulfide-loaded nano silver antibacterial hydrogel obtained in the example 1-3 and the pure polyacrylamide hydrogel obtained in the comparative example 1, the antibacterial performance of a sample is represented by a plate colony counting method by referring to the GB/T21866-2008 standard, staphylococcus aureus (S.aureus) and escherichia coli (E.coil) are selected as strains, and two common bacteria are selected and used for representing gram-negative bacteria and gram-positive bacteria respectively in the antibacterial test.

Table 1 shows the antibacterial ratio of the hydrogels of the examples and comparative examples obtained according to FIG. 1 after 2 hours of contact with S.aureus and E.coil

Bacterial strain	Antibacterial ratio/%)
								Comparative example 1	Comparative example 2	Example 1	Example 2	Example 3	Example 4
S.aureus	―	48.6	86.60	98.80	99.99	98.60
							E.coil	―	45.4	82.20	98.50	99.99	98.20

From the above table, it can be seen that the pure polyacrylamide hydrogel prepared in comparative example 1 does not contain an antibacterial material and has no antibacterial property; the antibacterial rates of the antibacterial hydrogel containing molybdenum disulfide prepared in comparative example 2 to s.aureus and e.coil were 48.6% and 45.4%, which are due to the nano MoS₂The material has oxidation capacity, and can cause larger oxidation stress on bacteria; the antibacterial rates of the molybdenum disulfide nano-silver loaded antibacterial hydrogel prepared in the example 1 on S.aureus and E.coil are 86.60% and 82.20%, the antibacterial rates of the example 2 on S.aureus and E.coil are 98.80% and 98.50%, the antibacterial rates of the example 3 on S.aureus and E.coil are 99.99% and 99.99%, and the antibacterial rates of the example 4 on S.aureus and E.coil are 98.60% and 98.20%, which shows that the water prepared by the method isThe gel has excellent antibacterial effect, and is expected to be applied to the field of biomedicine as an antibacterial material such as wound dressing, daily antibacterial material and the like.

The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. A preparation method of molybdenum disulfide loaded nano-silver antibacterial hydrogel is characterized by comprising the following steps:

firstly, stripping molybdenum disulfide by tannic acid to obtain TA-MoS₂Mixing the solution; then the TA-MoS is added₂The mixed solution is mixed and reacted with acrylamide, ammonium persulfate, N' -methylene bisacrylamide and deionized water to obtain the product containing TA-MoS₂A polyacrylamide hydrogel; finally, the product will contain TA-MoS₂Placing polyacrylamide hydrogel in prepared AgNO₃And obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel in the solution.

2. The method of claim 1, comprising the steps of:

step 1: adding tannic acid and molybdenum disulfide into deionized water, uniformly stirring, placing in an ultrasonic cell crusher, setting the ultrasonic time to be 2-4h and the ultrasonic power to be 300-500W, and obtaining TA-MoS after the ultrasonic is finished₂Mixing the solution;

step 2: acrylamide, ammonium persulfate, N' -methylene bisacrylamide, deionized water and TA-MoS obtained in step 1₂The mixed solution is added into a reactor under N₂Fully stirring under protection, then heating to 60-70 ℃ for reaction for 4-6h to obtain the product containing TA-MoS₂Purifying the polyacrylamide hydrogel in a reaction bottle filled with deionized water, and continuously soaking for 72 h;

and step 3: the purified product obtained in the step 2 contains TA-MoS₂Polyacrylamide hydrogels at-50 deg.CFreeze-drying completely, and placing in AgNO₃Stirring at room temperature at low speed of 200-₃And (4) obtaining the molybdenum disulfide loaded nano silver antibacterial hydrogel through solution.

3. The method of claim 2, wherein:

in the step 1, the mass ratio of the tannic acid to the molybdenum disulfide is 1: 1-3; TA-MoS₂The concentration of the mixed solution is 2-4 mg/mL.

4. The method of claim 2, wherein:

in the step 2, the adding mass of the ammonium persulfate is 0.4-0.6% of that of the acrylamide; the adding mass of the N, N' -methylene bisacrylamide is 0.1-0.2% of the mass of the acrylamide; the adding mass of the deionized water is 1-10 times of that of the acrylamide; TA-MoS₂The mass of the acrylamide solution is 0.5-1.5% of the mass of the acrylamide solution.

5. The method of claim 2, wherein:

in step 3, AgNO₃The concentration of (b) is 40-60. mu.g/mL.

6. The application of the antibacterial hydrogel with the molybdenum disulfide and the nano silver loaded prepared by the method according to any one of claims 1 to 5 is characterized in that: the molybdenum disulfide-loaded nano silver antibacterial hydrogel is used for preparing wound dressings and antibacterial materials.