CN111990408B - Nano antibacterial agent, preparation method and application thereof - Google Patents
Nano antibacterial agent, preparation method and application thereof Download PDFInfo
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- CN111990408B CN111990408B CN202010503873.XA CN202010503873A CN111990408B CN 111990408 B CN111990408 B CN 111990408B CN 202010503873 A CN202010503873 A CN 202010503873A CN 111990408 B CN111990408 B CN 111990408B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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Abstract
The invention discloses a nano antibacterial agent, a preparation method and application thereof, and belongs to the technical field of new agricultural materials. The preparation method comprises the steps of firstly acidifying HNTs, ultrasonically dispersing in ethanol, adding triethylamine and organosiloxane, carrying out constant-temperature heating reflux reaction, carrying out solid-liquid separation after the reaction is finished, washing, drying and sieving to obtain amino-modified HNTs, dispersing in deionized water, dropwise adding acetyl chloride to obtain acetylated HNTs, adding quaternary phosphonium salt, stirring, carrying out stirring reaction, and carrying out freeze-drying to obtain the nano antibacterial agent. The nano antibacterial agent has good inhibition and killing effects on fusarium oxysporum which is a pathogenic bacterium of banana vascular wilt.
Description
Technical Field
The invention relates to the technical field of new agricultural materials, in particular to a nano antibacterial agent, a preparation method and application thereof.
Background
Banana wilt, also known as banana Panama disease, yellow leaf disease, is a devastating fungal disease and a typical soil-borne disease of bananas caused by vascular bundle necrosis due to Fusarium oxysporum infection.
Due to the great harmfulness, the banana is applied for a long time in the planting process to prevent diseases from affecting the growth of plants. Although banana seedlings are disinfected, cultivation management is enhanced, intercropping, rotation and the like are carried out to inhibit the spread of disease conditions to a certain extent, the effect is not ideal from the current practical situation. In the aspect of chemical control, as the banana vascular wilt is a soil-borne vascular bundle disease, common chemical agents are almost ineffective. The quaternary phosphonium salt as a spectrum antibacterial drug has obvious antibacterial and bacteriostatic effects in the aspect of biomedicine. The salt of the quaternary ammonium salt and the elements in the same family has stronger electronegativity with the phosphorus element, so the antibacterial effect is more excellent. As a natural clay mineral material, the halloysite nanotube has a natural coiled tubular structure and strong adsorption capacity, the large length-diameter ratio and the small particle size of the halloysite nanotube can be absorbed by crops and transported in vivo, if the drug is directly adsorbed in the lumen of the halloysite nanotube, the loss of the drug in the using process still exists, and the action effect is not obvious. Therefore, it is necessary to develop a nano antibacterial agent having high antibacterial efficiency and stability.
Disclosure of Invention
The invention aims to develop a novel high-efficiency nano antibacterial agent for resisting banana vascular wilt, and provides a preparation method of the nano antibacterial agent for resisting banana vascular wilt.
In order to achieve the purpose, the invention provides the following scheme:
the first technical scheme is as follows:
the invention provides a nano antibacterial agent, which comprises Halloysite Nanotubes (HNTs) and quaternary phosphonium salt (NP).
As a further improvement of the invention, the halloysite nanotubes are modified by organic siloxane, and the surface of the halloysite nanotubes has amino groups. The halloysite nanotube has the length of 200nm, the inner diameter of 20nm and the outer diameter of 35 nm.
As a further development of the invention, the organosiloxane is 3-aminopropyltriethoxysilane (KH-550) or gamma-aminopropyltrimethoxysilane (KH 792).
As a further improvement of the invention, the quaternary phosphonium salt comprises one or more of trimethyl phosphonium bromide (chloride), triphenyl phosphonium chloride (bromide), tributyl phosphonium chloride (bromide), tricyclohexyl phosphonium bromide (chloride), 5-carboxypentyl triphenylphosphine bromide (chloride), 3-carboxyethyl triphenylphosphine bromide (chloride) and 2-carboxyethyl triphenylphosphine bromide (chloride).
The second technical scheme is as follows:
the invention provides a preparation method of a nano antibacterial agent, which comprises the following steps:
s1, firstly, carrying out hydrochloric acid acidification on HNTs, wherein the concentration of the hydrochloric acid is 3 mol/L;
s2, dispersing the acidified HNTs in 95% ethanol by volume, and performing ultrasonic dispersion;
s3, adding triethylamine and organic siloxane, wherein the ratio of triethylamine to HNTs is 2-1: 1(mL/g), and the ratio of organic siloxane to HNTs is 5-2: 1 (mL/g);
s4, heating at constant temperature for reflux reaction for 24-48 h, preferably 48h, at the heating temperature of 80-85 ℃, preferably 80 ℃, after the reaction is finished, separating solid from liquid, washing with 95% ethanol by volume fraction, drying at the temperature of 60-70 ℃ in a vacuum drying oven, preferably drying at the temperature of 60 ℃, grinding and sieving, preferably sieving with a 300-mesh sieve, and obtaining amino modified HNTs (HNTs-NH) for later use;
s5, dispersing the amino modified HNTs prepared in S4 in deionized water, then dropwise adding acetyl chloride, reacting at room temperature, concentrating at 70-80 ℃, finally adding absolute ethyl alcohol into the concentrated solution for precipitation, then performing solid-liquid separation, washing with ethyl alcohol, and performing vacuum drying to obtain acetylated HNTs (HNTsNC) for later use;
s6, dispersing HNTsNC synthesized by S5 in dimethyl sulfoxide, adding quaternary phosphonium salt and stirring, wherein the molar ratio of the quaternary phosphonium salt to the HNTsNC is 3:1, stirring and reacting at 60-70 ℃ for 24-36h, performing the whole reaction process under the protection of nitrogen, precipitating with acetone after the reaction is finished, collecting precipitate, washing with acetone, performing Soxhlet extraction with acetone to remove unreacted quaternary phosphonium salt, wherein the Soxhlet extraction time is 24h, and finally performing freeze-drying on the product to obtain the nano antibacterial agent.
As a further improvement of the invention, the ratio of HNTs to hydrochloric acid in S1 is 1: 20-25 (g/mL).
As a further improvement of the invention, the ratio of HNTs to ethanol in S2 is 1: 50-100 (g/mL).
As a further improvement of the present invention, the molar ratio of acetyl chloride to HNTs in S5 is 2:1, wherein the halloysite nanotubes are calculated based on amino groups in their molecular structure.
The third technical scheme is as follows:
the invention provides application of the nano antibacterial agent in resisting banana vascular wilt.
The invention discloses the following technical effects:
the quaternary phosphonium salt is grafted on the halloysite nanotube to form a new nano antibacterial agent, and the novel nano antibacterial agent has good inhibition and killing effects on fusarium oxysporum of banana wilt. The main bacteriostatic mechanism comprises two aspects: on one hand, the tubular structure of the halloysite nanotube has stronger adsorption capacity, in addition, the surface of the pathogen has negative charges, and the quaternary phosphonium salt nano antibacterial agent has positive charges and can be better adsorbed with the pathogen in an electrostatic way, so that the cell structure of the pathogen is damaged; on the other hand, the nano antibacterial agent mainly plays a role in the crop body, the nano antibacterial agent is applied to the roots or injected into the stems, and the antibacterial agent is transmitted and transported in the plant body through plant vascular bundles, plant conduits and xylem. The blight bacteria just attack the vascular bundles, and the antibacterial agent can effectively inhibit or kill the blight bacteria in the transportation process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 shows the antibacterial effect of a grafted triphenylphosphine bromide nano antibacterial agent;
FIG. 2 shows the antibacterial effect of the grafted tricyclohexyl phosphine chloride nano antibacterial agent;
FIG. 3 shows the antibacterial effect of the grafted tributyl phosphonium chloride nano antibacterial agent.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
S1, firstly, acidifying 10g of HNTs with hydrochloric acid, wherein the concentration of the hydrochloric acid is 3mol/L, and the addition amount of the hydrochloric acid is 200 mL;
s2, dispersing the acidified HNTs in 500mL of ethanol with volume fraction of 95%, and performing ultrasonic dispersion for 0.5 h;
s3, then adding 20mL of triethylamine and 30mL of 3-aminopropyltriethoxysilane;
s4, heating at a constant temperature for reflux reaction for 24 hours, wherein the heating temperature is 80 ℃, after the reaction is finished, separating solid from liquid, washing with 95% ethanol by volume fraction, drying in a vacuum drying oven at 60 ℃, and grinding and sieving with a 300-mesh sieve to obtain amino-modified HNTs (HNTs-NH) for later use;
s5, dispersing 0.17g of amino-modified HNTs-NH (the concentration is 10mmol based on the amino in the halloysite nanotube molecular structure) prepared in S4 in 100mL of deionized water, then dropwise adding 2mL of acetyl chloride (the concentration is 20mmol), reacting at room temperature for 12h, then concentrating at 70 ℃, finally adding 200mL of absolute ethyl alcohol into the concentrated solution for precipitation, then carrying out solid-liquid separation, washing with ethyl alcohol, and carrying out vacuum drying to obtain acetylated HNTs (HNTsNC) for later use;
s6, dispersing 0.15g (2mmol) of acetylated HNTsNC synthesized by S5 in 50mL of dimethyl sulfoxide, adding triphenylphosphine bromide (6mmol) and stirring, stirring at 60 ℃ for reaction for 24h, carrying out the whole reaction process under the protection of nitrogen, precipitating with acetone after the reaction is finished, collecting the precipitate, washing with acetone, carrying out Soxhlet extraction with acetone to remove unreacted quaternary phosphonium salt, wherein the Soxhlet extraction time is 24h, and freeze-drying the final product for 24h to obtain the nano antibacterial agent.
Antimicrobial Activity test
(1) Picking bacterial colonies of banana vascular wilt disease (fusarium oxysporum) by using an inoculating loop, carrying out shake culture at 37 ℃ for 12 hours in 20-30mL sterilized nutrient broth, and washing for 3-5 times by using PBS (phosphate buffer solution) with the pH value of 6 to remove the nutrient solution. The original bacterial solution was diluted with PBS buffer solution until OD was about 0.2 (λ is absorbance at 600 nm). Sucking 0.5mL of the diluent into 4.5mLPBS to obtain diluted bacterial liquid diluted by 1 time, and continuously diluting until 10-3 of the diluted bacterial suspension.
(2) Weighing nutrient agar in a conical flask of 1000mL, adding deionized water, preparing a solid culture medium with the concentration of 3.3% (w/v), weighing an antibacterial agent, respectively dissolving the antibacterial agent in deionized water with the pH of 6 to prepare antibacterial agents with different concentrations, and placing the antibacterial agents in an autoclave for sterilization at 120 ℃ for 15 min.
(3) The antimicrobial agents (0.1,0.5,1.0mg/mL) prepared in this example were added to 10 of the above-mentioned concentrations-3Diluting the bacterial suspension, incubating for 24 hours, respectively and uniformly coating 100 mu L of bacterial liquid on the surface of a sterilized solid agar culture medium, and incubating for 24 hours in a constant-temperature incubator at 37 ℃. Then calculating the bacteriostasis rate according to the following formula
Bacteriostatic rate (%) - (1-D)a/Db)*100
Note: daRepresents the growth diameter of the test sample hyphae; dbThe growth diameter of the control hyphae is shown.
The results are shown in FIG. 1.
Antibacterial activity experiments show that compared with HNTs control groups, the grafted triphenylphosphine bromide nano antibacterial agent has obvious antibacterial effect, wherein the antibacterial effect with the concentration of 1.0mg/mL is the best, and the antibacterial rate reaches 89.63%.
Example 2
S1, firstly, acidifying 10g of HNTs with hydrochloric acid, wherein the concentration of the hydrochloric acid is 3mol/L, and the addition amount of the hydrochloric acid is 200 mL;
s2, dispersing the acidified HNTs in 500mL of ethanol with volume fraction of 95%, and performing ultrasonic dispersion for 0.5 h;
s3, then adding 20mL of triethylamine and 30mL of 3-aminopropyltriethoxysilane;
s4, heating at a constant temperature for reflux reaction for 24 hours, wherein the heating temperature is 80 ℃, after the reaction is finished, separating solid from liquid, washing with 95% ethanol by volume fraction, drying in a vacuum drying oven at 60 ℃, and grinding and sieving with a 300-mesh sieve to obtain amino-modified HNTs for later use;
s5, dispersing 0.17g of amino-modified HNTs-NH (the concentration is 10mmol based on the amino in the halloysite nanotube molecular structure) prepared in S4 in 100mL of deionized water, then dropwise adding 2mL of acetyl chloride (the concentration is 20mmol), reacting at room temperature for 12h, then concentrating at 70 ℃, finally adding 200mL of absolute ethyl alcohol into the concentrated solution for precipitation, then carrying out solid-liquid separation, washing with ethyl alcohol, and carrying out vacuum drying to obtain acetylated HNTs (HNTsNC) for later use;
s6, dispersing 0.15g (2mmol) of acetylated HNTsNC synthesized by S5 in 50mL of dimethyl sulfoxide, adding tricyclohexyl phosphine chloride, stirring at 60 ℃ for reaction for 24h, performing the whole reaction process under the protection of nitrogen, precipitating with acetone after the reaction is finished, collecting the precipitate, washing with acetone, performing Soxhlet extraction with acetone to remove unreacted quaternary phosphonium salt, wherein the Soxhlet extraction time is 24h, and freeze-drying the final product for 24h to obtain the nano antibacterial agent.
Antimicrobial Activity test
(1) Picking bacterial colonies of banana vascular wilt disease (fusarium oxysporum) by using an inoculating loop, carrying out shake culture at 37 ℃ for 12 hours in 20-30mL sterilized nutrient broth, and washing for 3-5 times by using PBS (phosphate buffer solution) with the pH value of 6 to remove the nutrient solution. The original bacterial solution was diluted with PBS buffer solution until OD was about 0.2 (λ is absorbance at 600 nm). Sucking 0.5mL of the diluent into 4.5mLPBS to obtain diluted bacterial liquid diluted by 1 time, and continuously diluting until 10-3 of the diluted bacterial suspension.
(2) Weighing nutrient agar in a conical flask of 1000mL, adding deionized water, preparing a solid culture medium with the concentration of 3.3% (w/v), weighing an antibacterial agent, respectively dissolving the antibacterial agent in deionized water with the pH of 6 to prepare antibacterial agents with different concentrations, and placing the antibacterial agents in an autoclave for sterilization at 120 ℃ for 15 min.
(3) The antimicrobial agents (0.1,0.5,1.0mg/mL) prepared in this example were added to 10 of the above-mentioned concentrations-3Diluting the bacterial suspension, incubating for 24 hr, respectively and uniformly coating 100 μ L of bacterial liquid on the surface of sterilized solid agar culture medium, and coatingThe mixture is placed in a constant temperature incubator at 37 ℃ for 24 hours. Then calculating the bacteriostasis rate according to the following formula
Bacteriostatic rate (%) - (1-D)a/Db)*100
Note: daRepresents the growth diameter of the test sample hyphae; dbThe growth diameter of the control hyphae is shown.
The results are shown in FIG. 2.
Antibacterial activity experiments show that compared with HNTs control groups, the grafted tricyclohexylphosphine chloride nano antibacterial agent has obvious antibacterial effect, wherein the antibacterial effect with the concentration of 1.0mg/mL is the best, and the antibacterial rate reaches 80.93%.
Example 3
S1, firstly, acidifying 10g of HNTs with hydrochloric acid, wherein the concentration of the hydrochloric acid is 3mol/L, and the addition amount of the hydrochloric acid is 200 mL;
s2, dispersing the acidified HNTs in 500mL of ethanol with volume fraction of 95%, and performing ultrasonic dispersion for 0.5 h;
s3, then adding 20mL of triethylamine and 30mL of 3-aminopropyltriethoxysilane;
s4, heating at a constant temperature for reflux reaction for 24 hours, wherein the heating temperature is 80 ℃, after the reaction is finished, separating solid from liquid, washing with 95% ethanol by volume fraction, drying in a vacuum drying oven at 60 ℃, and grinding and sieving with a 300-mesh sieve to obtain amino-modified HNTs for later use;
s5, dispersing 0.17g of amino-modified HNTs-NH (the concentration is 10mmol based on the amino in the halloysite nanotube molecular structure) prepared in S4 in 100mL of deionized water, then dropwise adding 2mL of acetyl chloride (the concentration is 20mmol), reacting at room temperature for 12h, then concentrating at 70 ℃, finally adding 200mL of absolute ethyl alcohol into the concentrated solution for precipitation, then carrying out solid-liquid separation, washing with ethyl alcohol, and drying in vacuum to obtain acetylated HNTs for later use;
s6, dispersing 0.15g (2mmol) of acetylated HNTsNC synthesized by S5 in 50mL of dimethyl sulfoxide, adding tributyl phosphine chloride, stirring at 60 ℃ for reaction for 24h, performing the whole reaction process under the protection of nitrogen, precipitating with acetone after the reaction is finished, collecting the precipitate, washing with acetone, performing Soxhlet extraction with acetone for removing unreacted quaternary phosphonium salt, wherein the Soxhlet extraction time is 24h, and freeze-drying the final product for 24h to obtain the nano antibacterial agent.
Antimicrobial Activity test
(1) Picking bacterial colonies of banana vascular wilt disease (fusarium oxysporum) by using an inoculating loop, carrying out shake culture at 37 ℃ for 12 hours in 20-30mL sterilized nutrient broth, and washing for 3-5 times by using PBS (phosphate buffer solution) with the pH value of 6 to remove the nutrient solution. The original bacterial solution was diluted with PBS buffer solution until OD was about 0.2 (λ is absorbance at 600 nm). Sucking 0.5mL of the diluent into 4.5mLPBS to obtain diluted bacterial liquid diluted by 1 time, and continuously diluting until 10-3 of the diluted bacterial suspension.
(2) Weighing nutrient agar in a conical flask of 1000mL, adding deionized water, preparing a solid culture medium with the concentration of 3.3% (w/v), weighing an antibacterial agent, respectively dissolving the antibacterial agent in deionized water with the pH of 6 to prepare antibacterial agents with different concentrations, and placing the antibacterial agents in an autoclave for sterilization at 120 ℃ for 15 min.
(3) The antimicrobial agents (0.1,0.5,1.0mg/mL) prepared in this example were added to 10 above-3Diluting the bacterial suspension, incubating for 24 hours, respectively and uniformly coating 100 mu L of bacterial liquid on the surface of a sterilized solid agar culture medium, and incubating for 24 hours in a constant-temperature incubator at 37 ℃. Then calculating the bacteriostasis rate according to the following formula
Bacteriostatic rate (%) - (1-D)a/Db)*100
Note: daRepresents the growth diameter of the test sample hyphae; dbThe growth diameter of the control hyphae is shown.
The results are shown in FIG. 3.
Antibacterial activity experiments show that compared with HNTs control groups, the grafted tributyl phosphine chloride nano antibacterial agent has obvious antibacterial effect, wherein the antibacterial effect with the concentration of 1.0mg/mL is the best, and the antibacterial rate reaches 88.54%.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A nano antibacterial agent is characterized by comprising halloysite nanotubes and quaternary phosphonium salt;
the halloysite nanotube is modified by triethylamine and 3-aminopropyltriethoxysilane, and the surface of the halloysite nanotube is provided with amino groups;
the preparation method of the nano antibacterial agent comprises the following steps:
s1, firstly, carrying out hydrochloric acid acidification on the halloysite nanotube, wherein the concentration of the hydrochloric acid is 3 mol/L;
s2, dispersing the acidified halloysite nanotubes in 95% ethanol by volume, and performing ultrasonic dispersion;
s3, adding triethylamine and organic siloxane, wherein the ratio of the triethylamine to the halloysite nanotube is 2-1: 1(mL/g), and the ratio of the organic siloxane to the halloysite nanotube is 5-2: 1 (mL/g);
s4, heating at constant temperature for reflux reaction for 24-48 h, wherein the heating temperature is 80-85 ℃, after the reaction is finished, separating solid from liquid, washing with 95% ethanol by volume fraction, drying in a vacuum drying oven, grinding and sieving to obtain the amino modified halloysite nanotube for later use;
s5, dispersing the amino-modified halloysite nanotube prepared in the step S4 in deionized water, then dropwise adding acetyl chloride, reacting at room temperature, then concentrating, finally adding absolute ethyl alcohol into a concentrated solution for precipitation, then performing solid-liquid separation, washing with ethyl alcohol, and performing vacuum drying to obtain an acetylated halloysite nanotube for later use;
s6, dispersing the acetylated halloysite nanotubes synthesized by S5 in dimethyl sulfoxide, adding quaternary phosphonium salt, stirring for reaction, performing the whole reaction process under the protection of nitrogen, precipitating with acetone after the reaction is finished, collecting precipitate, washing with acetone, performing Soxhlet extraction with acetone to remove unreacted quaternary phosphonium salt, wherein the Soxhlet extraction time is 24 hours, and freeze-drying the final product to obtain the nano antibacterial agent.
2. The nano-antibacterial agent as claimed in claim 1, wherein the quaternary phosphonium salt comprises one or more of trimethyl phosphonium bromide (chloride), triphenyl phosphonium chloride (bromide), tributyl phosphonium chloride (bromide), tricyclohexyl phosphonium bromide (chloride), 5-carboxypentyl phosphonium bromide (chloride), 3-carboxyethyl triphenyl phosphonium bromide (chloride), and 2-carboxyethyl triphenyl phosphonium bromide (chloride).
3. A method for preparing a nano antibacterial agent as claimed in any one of claims 1 to 2, comprising the steps of:
s1, firstly, carrying out hydrochloric acid acidification on the halloysite nanotube, wherein the concentration of the hydrochloric acid is 3 mol/L;
s2, dispersing the acidified halloysite nanotubes in 95% ethanol by volume, and performing ultrasonic dispersion;
s3, adding triethylamine and organic siloxane, wherein the ratio of the triethylamine to the halloysite nanotube is 2-1: 1(mL/g), and the ratio of the organic siloxane to the halloysite nanotube is 5-2: 1 (mL/g);
s4, heating at constant temperature for reflux reaction for 24-48 h, wherein the heating temperature is 80-85 ℃, after the reaction is finished, separating solid from liquid, washing with 95% ethanol by volume fraction, drying in a vacuum drying oven, grinding and sieving to obtain the amino modified halloysite nanotube for later use;
s5, dispersing the amino-modified halloysite nanotube prepared in the step S4 in deionized water, then dropwise adding acetyl chloride, reacting at room temperature, then concentrating, finally adding absolute ethyl alcohol into a concentrated solution for precipitation, then performing solid-liquid separation, washing with ethyl alcohol, and performing vacuum drying to obtain an acetylated halloysite nanotube for later use;
s6, dispersing the acetylated halloysite nanotubes synthesized by S5 in dimethyl sulfoxide, adding quaternary phosphonium salt, stirring for reaction, performing the whole reaction process under the protection of nitrogen, precipitating with acetone after the reaction is finished, collecting precipitate, washing with acetone, performing Soxhlet extraction with acetone to remove unreacted quaternary phosphonium salt, wherein the Soxhlet extraction time is 24 hours, and freeze-drying the final product to obtain the nano antibacterial agent.
4. The method for preparing a nano antibacterial agent according to claim 3, wherein the ratio of the halloysite nanotubes to the hydrochloric acid in S1 is 1: 20-25 (g/mL).
5. The method for preparing a nano antibacterial agent according to claim 3, wherein the ratio of the halloysite nanotubes to ethanol in S2 is 1: 50-100 (g/mL).
6. The method for preparing nano antibacterial agent according to claim 3, wherein the molar ratio of acetyl chloride to halloysite nanotubes in S5 is 2: 1.
7. Use of the nano antibacterial agent as claimed in any one of claims 1-2 in resisting banana vascular wilt.
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| CN102250347A (en) * | 2011-05-04 | 2011-11-23 | 中国地质大学（武汉） | Preparation method of chelating type ion exchange resin with natural halloysite nanotube (HNT) as matrix |
| CN104119704A (en) * | 2013-04-27 | 2014-10-29 | 中国科学院化学研究所 | Surface modification treatment method of halloysite nanotube |
| CN109619100A (en) * | 2018-12-07 | 2019-04-16 | 国际竹藤中心 | A kind of halloysite nanotubes/quaternary ammonium salt composite antibacterial particle and its preparation method and application |
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