CN115428805B - Preparation method of graphene oxide-based composite antibacterial material and antibacterial solution - Google Patents

Preparation method of graphene oxide-based composite antibacterial material and antibacterial solution Download PDF

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CN115428805B
CN115428805B CN202211172168.1A CN202211172168A CN115428805B CN 115428805 B CN115428805 B CN 115428805B CN 202211172168 A CN202211172168 A CN 202211172168A CN 115428805 B CN115428805 B CN 115428805B
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陶永新
白迪
梁方维
黎珊
彭勇刚
汪媛
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Changzhou University
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Abstract

The invention relates to a preparation method of a graphene oxide-based composite antibacterial material and an antibacterial solution, which comprises the steps of firstly preparing Graphene Oxide (GO), uniformly mixing low-content GO after alkali treatment and beta-cyclodextrin copper (Cu 2 -beta-CD), regulating the acid to be neutral, dialyzing to obtain GO@Cu 2 -beta-CD composite material, freeze-drying, and adding PVP or SDS (surfactant) or vanillin (a food additive) after freeze-drying to obtain the composite antibacterial solution of graphene oxide. The three components are selected to effectively produce a synergistic effect, and the antibacterial effect on escherichia coli and staphylococcus aureus under the conditions of low content of GO and low concentration of Cu 2 -beta-CD is realized.

Description

Preparation method of graphene oxide-based composite antibacterial material and antibacterial solution
Technical Field
The invention belongs to the field of antibacterial materials, and particularly relates to a preparation method of a low-content graphene oxide composite antibacterial material, which can maintain good antibacterial performance under low-concentration beta-cyclodextrin copper.
Background
Graphene Oxide (GO) contains a large amount of oxygen-containing groups, has good water solubility and solution dispersibility, low cytotoxicity of GO and good biocompatibility. The high concentration GO (200 mug/mL-1000 mug/mL) has inhibiting effect on a plurality of harmful bacteria (staphylococcus aureus, escherichia coli, pseudomonas aeruginosa, pseudomonas syringae and fusarium oxysporum), and is a promising antibacterial material. However, the difference of the preparation methods can cause the difference of the GO performances, and the high-concentration GO is sticky, so that the application of the GO in antibiosis is limited. Beta-cyclodextrin copper is a cyclic complex formed by cyclodextrin and copper ions, has certain antibacterial capability, but has higher antibacterial concentration, and is the important point of research.
Patent CN201910875396 discloses that the cyclodextrin copper and polylysine complex has certain inhibitory effect on escherichia coli, staphylococcus aureus and bacillus subtilis. The compound is applied to textiles, emphasizes that the compound has water-resistance, has antibacterial performance after the textiles are washed, can improve the antibacterial capacity of cyclodextrin copper, and has no clear expression.
Patent CN202110867397.4 discloses that the combination of cyclodextrin copper and surfactant can significantly improve the inhibition effect on escherichia coli, staphylococcus aureus and candida albicans fungi. However, the concentration of copper element is higher (6.28X10 83mol/L),Cu2 -beta-CD concentration is 4000 mug/mL, and biosafety is relatively low. The inventor intensively researches on the basis that low content GO is alkalized, the carboxylic acid of GO becomes sodium salt, hydrogen bonds among GO are effectively destroyed, the GO is fully dispersed, then the GO is mixed with Cu 2 -beta-CD, high content Cu 2 -beta-CD can prevent the aggregation of GO sheets, then the GO sheets are adjusted to be neutral, the salt is removed by dialysis, the GO@Cu 2 -beta-CD is obtained by freeze drying, the freeze drying can keep the high dispersion state of GO, and the freeze drying solution is compounded with PVP or SDS as a surfactant or vanillin, so that the antibacterial effect on escherichia coli and staphylococcus aureus can be kept under the lower content of Cu 2 -beta-CD.
Disclosure of Invention
The invention aims to solve the problems that: in order to improve the antibacterial performance of the graphene oxide composite material or reduce the minimum antibacterial concentration, the invention provides a preparation method based on the graphene oxide composite antibacterial material, which is characterized in that graphene oxide and beta-cyclodextrin copper are compounded, and then a surfactant PVP or SDS or a food additive vanillin is added for compounding, so that the antibacterial effect on gram-positive bacteria staphylococcus aureus and gram-negative bacteria escherichia coli is remarkably improved. On the premise of ensuring the antibacterial effect, the copper content in the composite material is reduced, and the biological safety of the material is improved.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the graphene oxide-based composite antibacterial material comprises the following steps of:
(1) Modified Hummers method for preparing graphene oxide: weighing 0.1g of graphite into a three-neck flask, and slowly adding 0.6g of potassium permanganate under the stirring condition; 1.33mL of H 3PO4 and 12mL of H 2SO4 were removed and added to the three-necked flask, and the mixture was stirred at 50℃for 12 hours. A glass of distilled water (20 mL) was frozen and the ice was placed in a 100mL beaker. 1mLH 2O2 was measured and added to the beaker. The solution was slowly poured into a beaker and stirred continuously for 12h. Distilled water was added to 100mL. And standing and layering water changing until the solution is neutral. And (5) centrifugally drying to obtain the Graphene Oxide (GO).
(2) Preparation of copper beta-cyclodextrin (Cu 2 -beta-CD): firstly preparing a solution containing 0.5mol/L NaOH and 0.02mol/L beta-cyclodextrin, then adding 0.04mol/L CuSO 4·5H2 O solution into the solution to quickly form Cu (OH) 2 blue precipitate, stirring for 24 hours at room temperature, and filtering out Cu (OH) 2 solid particles by suction; and then absolute ethyl alcohol is added into the filtrate, when blue precipitation gradually appears in the solution, the solution is kept stand for 48 hours and then filtered, the obtained blue precipitation solid is washed by ethyl alcohol and a small amount of distilled water, and vacuum drying is carried out at room temperature, so that blue solid powder is the beta-cyclodextrin copper (Cu 2 -beta-CD).
Further, the volume ratio of the solution containing NaOH and beta-cyclodextrin to the CuSO 4·5H2 O solution and the absolute ethanol is 10:15:200.
(3) Dissolving graphene oxide in water, performing ultrasonic treatment until the graphene oxide is uniformly dispersed, adding a NaOH solution under a stirring state to adjust the pH value to 10-14, adding beta-cyclodextrin copper, performing ultrasonic treatment until the graphene oxide is uniformly dispersed, and performing slow stirring for 8 hours at a speed of 100-200 r/min. After the reaction is finished, hydrochloric acid solution is used for neutralization, and the pH value of the solution is regulated to 6.8-7.0. And (3) dialyzing with a 14kDa dialysis bag to remove the generated NaCl, and freeze-drying the solution to obtain the GO@Cu 2 -beta-CD composite material.
The mass relation between the graphene oxide and the cyclodextrin copper is GO: cu 2 -CD was 1:100-200.
(4) Freeze-drying the GO@Cu 2 -beta-CD composite material in water, performing ultrasonic oscillation, gradually dissolving, and then adding a surfactant PVP or SDS or a food additive vanillin to obtain the composite antibacterial solution.
The addition amount of the surfactant is 0.1% -1% of the mass of the GO@Cu 2 -beta-CD dissolving solution;
The antibacterial performance of the graphene oxide composite antibacterial solution is determined by adopting a method for quantitative antibacterial test of suspension in WS/T650-2019 antibacterial and antibacterial effect evaluation method.
The technical scheme can be seen that: the GO@Cu 2 -beta-CD can reach the effects of 99% of escherichia coli and 99% of staphylococcus aureus at the concentration of 300 mug/mL. The GO@Cu 2 -beta-CD composite freeze-dried can generate obvious synergistic effect after being compounded with a surfactant PVP or SDS or a food additive vanillin, and compared with the components of the formula, the inhibition effect on escherichia coli and staphylococcus aureus is obviously enhanced. 0.3% PVP is added under the condition of adding a surfactant, and 150 mug/mLGO@Cu 2 -beta-CD is added; 0.3% SDS was added at 10. Mu.g/mL GO@Cu 2 -beta-CD; 1% vanillin is added, and the content of the vanillin in 100 mug/mL GO@Cu 2 -beta-CD can reach 99% for both escherichia coli and staphylococcus aureus. Under the condition of adding a surfactant, the GO@Cu 2 -beta-CD further has a strong antibacterial effect on escherichia coli and staphylococcus aureus at a lower concentration, so that the copper element content is reduced, and the biological safety is improved.
The beneficial effects of the invention are as follows: the low-content GO (without increasing the viscosity of the solution) is realized by using the high-biosafety surfactant PVP or SDS or the food additive vanillin and the GO@Cu 2 -beta-CD to be compounded and freeze-dried, the low-concentration Cu 2 -beta-CD has good antibacterial performance, the copper element content in the composite antibacterial material is greatly reduced, and the biosafety of the material can be improved.
Detailed Description
Weighing 0.1g of graphite into a three-neck flask, and slowly adding 0.6g of potassium permanganate under the stirring condition; 1.33mL of H 3PO4 and 12mL of H 2SO4 were removed and added to the three-necked flask, and the mixture was stirred at 50℃for 12 hours. A glass of distilled water (20 mL) was frozen and the ice was placed in a 250mL beaker. 1mLH 2O2 was measured and added to the beaker. The solution was slowly poured into a beaker and stirred continuously for 12h. Distilled water was added to 100mL. And standing and layering water changing until the solution is neutral. And (5) centrifugally drying to obtain the Graphene Oxide (GO).
Preparing beta-cyclodextrin copper: firstly, preparing 10mL of solution containing 0.5mol/L NaOH and 0.02mol/L beta-cyclodextrin, then adding 15mL of 0.04mol/L CuSO 4·5H2 O solution into the solution to quickly form Cu (OH) 2 blue precipitate, stirring for 24 hours at room temperature, and then suction-filtering to remove Cu (OH) 2 solid particles; and then adding 200mL of absolute ethyl alcohol into the filtrate, standing for 48 hours, filtering the solution when blue precipitation gradually appears in the solution, washing the obtained blue precipitation solid with ethyl alcohol and a small amount of distilled water, and vacuum drying at room temperature to obtain blue solid powder, namely beta-cyclodextrin copper (Cu 2 -beta-CD).
Preparing a graphene oxide and beta-cyclodextrin copper composite material: dissolving 5mg of graphene oxide in 10mL of water, carrying out ultrasonic treatment until the graphene oxide is uniformly dispersed, adding a NaOH solution under a stirring state to adjust the pH value to 11, adding 0.7g of beta-cyclodextrin copper, carrying out ultrasonic treatment until the graphene oxide is uniformly dispersed, and carrying out slow stirring for 8 hours. After the reaction is finished, hydrochloric acid solution is used for neutralization, and the pH value of the solution is regulated to 6.8-7.0. And (3) dialyzing with a 14kDa dialysis bag to remove the generated NaCl, and freeze-drying the solution to obtain the GO@Cu 2 -beta-CD composite material.
All examples and comparative examples were subjected to the determination of the bacteriostasis rate of the materials according to the quantitative bacteriostasis test method for suspensions in WS/T650-2019, method for evaluation of antibacterial and bacteriostatic Effect.
Example 1: 100. Mu.g/mLGO@Cu 2 -beta-CD compound solution containing 0.3% PVP was prepared.
Firstly, preparing 5mL of 100 mug/mLGO@Cu 2 -beta-CD freeze-dried solution, adding 0.015g of PVP into the solution, and uniformly mixing to obtain GO@Cu 2 -beta-CD compound solution containing 0.3% of PVP.
Example 2: preparation of 150. Mu.g/mL GO@Cu 2 -beta-CD Compound solution containing 0.3% PVP
Firstly, preparing 5mL of 150 mug/mLGO@Cu 2 -beta-CD freeze-dried solution, adding 0.015g of PVP into the solution, and uniformly mixing to obtain GO@Cu 2 -beta-CD compound solution containing 0.3% of PVP.
Example 3: a5. Mu.g/mLGO@Cu 2 -. Beta. -CD complex solution containing 0.3% SDS was prepared.
Firstly, 5mL of 5 mug/mLGO@Cu 2 -beta-CD freeze-dried solution is prepared, 0.015gSDS is added into the solution, and the GO@Cu 2 -beta-CD compound solution containing 0.3% SDS is obtained after uniform mixing.
Example 4: 10 mug/mL GO@Cu 2 -beta-CD compound solution containing 0.3% SDS was prepared.
Firstly, preparing 5mL of 10 mug/mLGO@Cu 2 -beta-CD freeze-dried solution, adding 0.015gSDS into the solution, and uniformly mixing to obtain GO@Cu 2 -beta-CD compound solution containing 0.3% SDS.
Example 5: a50. Mu.g/mLGO@Cu 2 -. Beta. -CD compound solution containing 0.1% vanillin was prepared.
Firstly, preparing 5mL of 50 mug/mL of the GO@Cu 2 -beta-CD freeze-dried solution prepared by the method, adding 0.005g of vanillin into the solution, and uniformly mixing to obtain the GO@Cu 2 -beta-CD compound solution containing 0.1% of vanillin.
Example 6: a50. Mu.g/mLGO@Cu 2 -. Beta. -CD compound solution containing 1% vanillin was prepared.
Firstly, preparing 5mL of 50 mug/mLGO@Cu 2 -beta-CD freeze-dried solution, adding 0.05g of vanillin into the solution, and uniformly mixing to obtain GO@Cu 2 -beta-CD compound solution containing 1% of vanillin.
Example 7: 100 μg/mL GO@Cu 2 -beta-CD compound solution containing 1% vanillin is prepared.
Firstly, preparing 5mL of 100 mug/mLGO@Cu 2 -beta-CD freeze-dried solution, adding 0.05g of vanillin into the solution, and uniformly mixing to obtain the GO@Cu 2 -beta-CD compound solution containing 1% of vanillin.
Example 8: GO@Cu 2 -beta-CD compound solution
5ML of 200 mug/mL GO@Cu 2 -beta-CD freeze-dried solution is prepared, namely the GO@Cu 2 -beta-CD compound solution.
Example 9: GO@Cu 2 -beta-CD compound solution
5ML of the GO@Cu 2 -beta-CD freeze-dried solution with the concentration of 300 mug/mL is prepared, and the GO@Cu 2 -beta-CD compound solution is obtained.
TABLE 1 antibacterial Rate of various materials with surfactant added to different strains
Different surfactants have different effects on GO@Cu 2 -beta-CD, 0.3% PVP is added, and 150 mug/mLGO@Cu 2 -beta-CD is added; 0.3% SDS was added at 10. Mu.g/mL GO@Cu 2 -beta-CD; 1% vanillin is added, and the ratio of GO@Cu 2 -beta-CD to Escherichia coli and Staphylococcus aureus is up to 99% at 100 mug/mL; the effect of the escherichia coli of >99% and the staphylococcus aureus of >99% can be achieved at 300 mug/mL without adding the surfactant GO@Cu 2 -beta-CD. The addition amount of the surfactant is 0.1% -1%, and the GO@Cu 2 -beta-CD further has a strong antibacterial effect on escherichia coli and staphylococcus aureus under a very low concentration, so that the copper element content is reduced, and the biosafety is improved.
Comparative example 1: GO and Cu 2 -beta-CD (1:140) mixed solution
0.011Mg of graphene oxide, 1.489mg of beta-cyclodextrin copper are weighed out and dissolved in 5mL of sterile water. And (3) uniformly mixing by ultrasonic to obtain the mixed solution of GO and Cu 2 -beta-CD (1:140).
Comparative example 2: GO solution
5ML of a 300. Mu.g/mL GO solution was prepared.
Comparative example 3: cu 2 -beta-CD solution
5ML of a 600. Mu.g/mL Cu 2 -. Beta. -CD solution was prepared to obtain a Cu 2 -. Beta. -CD solution.
Comparative example 4: GO solution containing 0.3% PVP
Firstly preparing 5mL of 100 mug/mL GO solution, adding 0.015g of PVP into the solution, and uniformly mixing to obtain GO solution containing 0.3% PVP
Comparative example 5: GO solution containing 0.3% SDS
Firstly preparing 5mL of 5 mug/mL GO solution, adding 0.015gSDS to the solution, and uniformly mixing to obtain GO solution containing 0.3% SDS
Comparative example 6: cu 2 -beta-CD solution containing 0.3% PVP
Firstly preparing 5mL of 100 mug/mLCu 2 -beta-CD solution, adding 0.015g PVP into the solution, uniformly mixing to obtain Cu 2 -beta-CD solution containing 0.3% PVP
Comparative example 7: cu 2 -beta-CD solution containing 0.3% SDS
Firstly preparing 5mL of 5 mug/mLCu 2 -beta-CD solution, adding 0.015gSDS into the solution, uniformly mixing to obtain Cu 2 -beta-CD solution containing 0.3% SDS
Comparative example 8:0.3% PVP solution
0.015G PVP was weighed into 5mL sterile water to give 5mL of 0.3% PVP solution.
Comparative example 9:0.3% SDS solution
0.015G of SDS was weighed into 5mL of sterile water to prepare 5mL of a 0.3% SDS solution.
Comparative example 10: GO solution containing 0.1% vanillin solution
Firstly preparing 5mL of 50 mug/mL GO solution, adding 0.005g of vanillin into the solution, and uniformly mixing to obtain the GO solution containing 0.1% of vanillin
Comparative example 11: GO solution containing 1% vanillin
Firstly preparing 5mL of 50 mug/mL GO solution, adding 0.05g of vanillin into the solution, and uniformly mixing to obtain the GO solution containing 1% vanillin
Comparative example 12: cu 2 -beta-CD solution containing 0.1% vanillin solution
Firstly preparing 5mL of 50 mug/mLCu 2 -beta-CD solution, adding 0.005g of vanillin into the solution, and uniformly mixing to obtain Cu 2 -beta-CD solution containing 0.1% of vanillin
Comparative example 13: cu 2 -beta-CD solution containing 1% vanillin solution
Firstly preparing 5mL of 50 mug/mLCu 2 -beta-CD solution, adding 0.05g of vanillin into the solution, and uniformly mixing to obtain Cu 2 -beta-CD solution containing 1% vanillin
Comparative example 14:0.1% vanillin solution
0.005G of vanillin was weighed into 5mL of sterile water to give 5mL of a 0.1% vanillin solution.
Comparative example 15:1% vanillin solution
0.05G of vanillin was weighed into 5mL of sterile water to give 5mL of a 1% vanillin solution.
Comparative example 16: GO@Cu 2 -beta-CD compound solution
5ML of 50 mug/mLGO@Cu 2 -beta-CD freeze-dried solution is prepared, namely the GO@Cu 2 -beta-CD compound solution.
Table 2 bacteriostasis rates of each comparative example material on different strains
As can be seen from the data in Table 2, the GO@Cu 2 -beta-CD solution added with PVP, SDS or vanillin in the examples has significantly improved antibacterial performance compared with the single-component GO and Cu 2 -beta-CD, 300 μg/mL GO@Cu 2 -beta-CD composite material in the comparative examples, and has superior antibacterial performance compared with the GO and Cu 2 -beta-CD composite (1:140).
Further analysis of the data in comparative example 16 of Table 2 shows a significant decrease in the bacteriostatic properties of 50. Mu.g/mLGO@Cu 2 -. Beta. -CD. Compared with the dosage of Cu 2 -beta-CD in the patent CN202110867397.4 (4 mg/mL, namely 4000 mug/mL), the content of copper element in 300 mug/mLGO@Cu 2 -beta-CD is obviously reduced. Adding PVP, SDS or vanillin into the components, and on the premise of keeping the antibacterial performance, reducing the minimum antibacterial concentration of GO@Cu 2 -beta-CD to 100 mug/mL, and reducing the concentration of GO@Cu 2 -beta-CD to 5 mug/mL after adding SDS; after vanillin is added, the concentration of GO@Cu 2 -beta-CD is reduced to 50 mug/mL, and the minimum inhibitory concentration of GO@Cu 2 -beta-CD on escherichia coli and staphylococcus aureus can be obviously reduced by the third component. Realizes good antibacterial performance to escherichia coli and staphylococcus aureus under the conditions of low content of GO and low concentration of Cu 2 -beta-CD, greatly reduces the content of copper elements in the composite material and obviously improves the biosafety.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention are shown and described, and are directed to various modifications, e.g., broadening of the third component, which are intended to be included within the scope of the present invention.

Claims (2)

1. A preparation method of an antibacterial solution based on graphene oxide composite antibacterial material is characterized by comprising the following steps: the antibacterial material is prepared from Graphene Oxide (GO) and Cu 2 -beta-CD;
dissolving graphene oxide in water, performing ultrasonic treatment until the graphene oxide is uniformly dispersed, adjusting the pH value of a NaOH solution to 10-14 under a stirring state, adding Cu 2 -beta-CD, performing ultrasonic treatment on the composite material until the graphene oxide is uniformly dispersed, uniformly stirring, neutralizing with an acid solution after fully mixing, removing generated NaCl by dialysis with a dialysis bag, and performing freeze-drying on the solution to obtain a GO@Cu 2 -beta-CD antibacterial material; the mass ratio of GO to Cu 2 -beta-CD is 1:100-200 parts;
Dispersing the GO@Cu 2 -beta-CD composite material in water by ultrasonic vibration, and adding a surfactant to obtain a bacteriostatic solution; the surfactant is one or more of polyvinylpyrrolidone, sodium dodecyl sulfate and vanillin; the addition amount of the surfactant is 0.1% -1% of the mass of the antibacterial solution.
2. The preparation method of the antibacterial solution based on the graphene oxide composite antibacterial material, which is disclosed in claim 1, is characterized in that: the concentration of GO@Cu 2 -beta-CD in the antibacterial solution is more than 10 mug/mL.
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