CN114773504A - Fluorine-containing macromolecular quaternary ammonium salt with two-block structure and preparation method and application thereof - Google Patents
Fluorine-containing macromolecular quaternary ammonium salt with two-block structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sterilization, and discloses fluorine-containing macromolecular quaternary ammonium salt with a two-block structure, and a preparation method and application thereof. The structural general formula of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is shown as formula 1:
wherein m and n are both positive integers, and m: n ═ 14 to 22: (6-32). The two-block junctionThe fluorine-containing macromolecular quaternary ammonium salt has good bacteriostatic effect, especially has the inhibitory effect on FOC4 spores in soil, reduces the influence on the microbial diversity of the soil, and is favorable for preventing and treating banana wilt.
Description
Technical Field
The invention belongs to the technical field of sterilization, and particularly relates to fluorine-containing macromolecular quaternary ammonium salt with a two-block structure, and a preparation method and application thereof.
Background
The pathogenic bacteria of the banana wilt disease are Fusarium oxysporum f.sp.cubense (FOC for short), the physiological race thereof is more differentiated, wherein the race 4 (FOC4 for short) has the greatest harm and the widest distribution, and becomes one of the greatest diseases harming the worldwide banana planting industry. The pathogenic bacteria have strong saprophytic capacity and can survive in soil for a long time in the form of dormant spores, and the occurrence of banana vascular wilt is positively correlated with the quantity of pathogenic bacteria FOC4 in the soil, so that the reduction of the quantity of the pathogenic bacteria in the soil is an important method for preventing and treating the banana vascular wilt.
Chemical control in the prior art is mainly divided into two types of methods: one is the use of chemical agents to inhibit the number of pathogenic bacteria in the soil. Although some small-molecule drugs screened out based on indoor toxicity measurement and potting test, such as prochloraz, propiconazole, thiophanate methyl and quintozene, have certain control effect on banana wilt, the control effect in practice is poor. The other type of the chemical fumigation method is called as 'soil disinfection', namely microorganisms in soil are completely killed by adopting a physical, chemical or biological method, such as soil heating, soil fumigation and the like, wherein fumigation of small-molecule chemical agents represented by dazomet (tetrahydro-3, 5-dimethyl-2H-1, 3, 5-thiadiazine-2-thione), calcium cyanamide (calcium cyanamide), chlorine dioxide and the like is the main method for field control at present; the method completely destroys microbial community structure in soil, so new organic matters need to be introduced to restore soil after treatment, which is not beneficial to the stability of soil ecosystem. Biological control and crop rotation, etc. are also difficult to implement effectively on a large scale due to high economic cost and incapability of continuous planting, limited by economic benefits, etc. Therefore, no method which is economically feasible and can effectively inhibit the FOC4 in the soil on the basis of keeping the microbial diversity in the soil as much as possible exists at present.
Therefore, it is highly desirable to provide a new bactericidal substance which has a good effect of killing FOC4 in soil and does not destroy the soil microbial ecosystem, thereby facilitating the control of banana wilt.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure, and the preparation method and the application thereof are provided by the invention, and the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure can well inhibit the activity of FOC4 spores in soil, reduce the influence on the microbial diversity of the soil, and is favorable for preventing and treating banana wilt.
The first aspect of the present invention provides a fluorine-containing macromolecular quaternary ammonium salt having a diblock structure.
Specifically, the structural general formula of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is shown as formula 1:
wherein m and n are both positive integers, and m: n ═ 14 to 22: (6-32).
More preferably, m: n ═ 18: (6-30).
Preferably, m is a positive integer between 14 and 22, and n is a positive integer between 6 and 32.
Preferably, m is an even number between 14 and 22, and n is an even number between 6 and 32.
Preferably, m is 18 and n is 6, 12, 18 or 30.
In formula 1, b represents that m and n marked repeating units are of a two-block structure.
Preferably, the molecular weight of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is 5-20kDa, and preferably 5-12 kDa.
The second aspect of the invention provides a preparation method of fluorine-containing macromolecular quaternary ammonium salt with a diblock structure.
Specifically, the preparation method of the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure comprises the following steps:
(1) mixing trifluoroethyl methacrylate, brominated ester, a catalyst, an auxiliary agent and an organic solvent, carrying out a first reaction in an inert gas atmosphere, adding dimethylaminoethyl methacrylate, and carrying out a second reaction to obtain an intermediate product;
(2) and (2) mixing the intermediate product prepared in the step (1), benzyl chloride and an organic solvent, and reacting in an inert gas atmosphere to prepare the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure.
Preferably, in the step (1), the catalyst is cuprous salt; further preferably, the catalyst is cuprous salt formed by halogen and cuprous; more preferably, the catalyst is CuBr.
Preferably, the bromo ester in step (1) is ethyl 2-bromoisobutyrate (abbreviated to EtBriB).
Preferably, in the step (1), the auxiliary agent comprises N, N', N ", N ″ -pentamethyldivinyltriamine (PMDETA for short).
Preferably, in step (1), the inert gas comprises nitrogen or a noble gas.
Preferably, in the step (1), the reaction is stopped when the second reaction is performed for a certain period of time and then exposed to air. The intermediate product can be separated and purified and is light yellow transparent oily liquid.
Preferably, the separation and purification process of the intermediate product is as follows: performing rotary evaporation treatment on a mixture formed after the reaction to remove most of the organic solvent, then adding an acetone solvent, adding neutral alumina, stirring until the solution is changed from green to colorless, then filtering out powder, and finally performing rotary evaporation on the solvent and unreacted substances (monomers) to obtain a purified intermediate product; or removing most of organic solvent by rotary evaporation, dissolving the reacted system with acetone, performing suction filtration by a diaphragm pump to remove CuBr in the reacted system through a neutral alumina chromatographic column, and rotary evaporation of the obtained eluent at 70 ℃ to remove unreacted substances (monomers or auxiliaries) to obtain an intermediate product.
Preferably, in step (1), the organic solvent is toluene and/or ethanol.
Preferably, in the step (1), the volume of the organic solvent is 1 to 10 times, preferably 2 to 8 times of the total volume of the trifluoroethyl methacrylate and the bromo-ester.
Preferably, in step (1), the catalyst is pretreated and washed 3 to 10 times with acetic acid and methanol, respectively.
Preferably, in the step (1), the molar ratio of the brominated ester to the catalyst to the auxiliary agent is 1: (0.8-2): (0.8-2); preferably 1: 1.5: 1.5.
preferably, in the step (1), the temperature of the first reaction is 45-55 ℃, and the reaction time is 1-10 hours; preferably, the reaction temperature is 48-50 ℃ and the reaction time is 2-3 hours.
Preferably, in the step (1), the temperature of the second reaction is 45-55 ℃, and the reaction time is 4-8 hours; preferably, the reaction temperature is 48-50 ℃, and the reaction time is 4-8 hours.
Preferably, in the step (1), the mass ratio of trifluoroethyl methacrylate to dimethylaminoethyl methacrylate is 1-5: 3. the trifluoroethyl methacrylate and the dimethylaminoethyl methacrylate are subjected to reduced pressure distillation before use to remove polymerization inhibitor impurities.
Preferably, in the step (2), the mass of the organic solvent is 2 to 5 times, preferably 3 to 4 times that of the intermediate product prepared in the step (1).
Preferably, in the step (2), the reaction temperature is 45-55 ℃, and the reaction time is 20-50 hours; preferably, the reaction temperature is 48-50 ℃, and the reaction time is 24-48 hours.
Preferably, in the step (2), the molar ratio of the intermediate product prepared in the step (1) to benzyl chloride is 1 (3-8); preferably 1: 5.
preferably, in the step (2), after the reaction is finished, the product is purified, and the purification process is as follows: distilling out most of solvent under reduced pressure, adding a large amount of anhydrous ether to precipitate the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure, pouring out supernatant, repeating for 2-5 times, and drying in a vacuum oven at 40-50 ℃ to obtain the purified fluorine-containing macromolecular quaternary ammonium salt with the two-block structure.
The molecular weight of the product can be controlled by controlling the amount of each reaction raw material.
The third aspect of the invention provides application of fluorine-containing macromolecular quaternary ammonium salt with a diblock structure.
The invention relates to application of fluorine-containing macromolecular quaternary ammonium salt with a two-block structure in preventing and treating banana wilt.
Preferably, the use is in inhibition of FOC 4.
An antibacterial agent comprising the fluorine-containing macromolecular quaternary ammonium salt having a diblock structure.
Compared with the prior art, the invention has the following beneficial effects:
(1) the fluorine-containing macromolecular quaternary ammonium salt with the diblock scale structure has a good antibacterial effect, particularly has an inhibitory effect on FOC4 spores in soil, reduces the influence on the microbial diversity of the soil, and is beneficial to preventing and treating banana wilt. The fluorine-containing macromolecular quaternary ammonium salt with the diblock structure can be effectively adsorbed in soil and is not easy to migrate, so that FOC4 spores in the soil can be effectively inhibited for a long time.
(2) The preparation method provided by the invention has the advantages that the process is simple and convenient, two steps are adopted, no by-product is generated in the reaction process, a pure product can be efficiently and conveniently obtained, in addition, atom transfer living radical polymerization is adopted in the synthesis process, the product structure and the molecular weight can be controlled through the feeding sequence and the feeding ratio of each reaction, and the controllability on the prepared product is strong.
Drawings
FIG. 1 is an infrared spectrum of an intermediate product and a product obtained in example 1 of the present invention and comparative example 1;
FIG. 2 is a NMR chart of an intermediate obtained in example 1 of the present invention;
FIG. 3 is a NMR chart of the product obtained in example 1 of the present invention;
FIG. 4 is a graph of the critical micelle concentration of the products obtained in examples 1-4 of the present invention and comparative example 1;
FIG. 5 is a Zeta potential diagram for the products of inventive examples 1-4, comparative example 1;
FIG. 6 is a schematic diagram showing the particle size distribution of the products obtained in examples 1 to 4 of the present invention and comparative example 1;
FIG. 7 is a graph showing the antibacterial effects of the products obtained in examples 1 to 4 of the present invention and comparative example 1;
FIG. 8 is a graph showing the saturation adsorption amounts in soil of the products obtained in examples 1 to 4 of the present invention and comparative example 1;
FIG. 9 is a graph of the migration performance in soil for the products of examples 1-4 of the present invention, comparative example 1;
FIG. 10 shows the effect of the products obtained in example 1 and comparative example 1 of the present invention on the diversity of soil microorganisms.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are, unless otherwise specified, either commercially available from conventional sources or can be obtained by known methods.
The general structural formula of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is shown as formula 1:
wherein m is 18, and n is 6, 12, 18 or 30.
In formula 1, b represents that m and n marked repeating units are of a two-block structure.
The molecular weight of the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure is 5-20kDa
The preparation method of the fluorine-containing macromolecular quaternary ammonium salt with the diblock structure comprises the following steps:
(1) mixing trifluoroethyl methacrylate, brominated ester, a catalyst, an auxiliary agent and an organic solvent, carrying out a first reaction in an inert gas (nitrogen) atmosphere, adding dimethylaminoethyl methacrylate, and carrying out a second reaction to obtain an intermediate product;
(2) and (2) mixing the intermediate product prepared in the step (1), benzyl chloride and an organic solvent, and reacting in an inert gas atmosphere to prepare the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure.
In the step (1), the catalyst is CuBr; the bromo-ester is ethyl 2-bromoisobutyrate (EtBriB for short); the auxiliary agent comprises N, N, N' -pentamethyl divinyl triamine (PMDETA for short); the inert gas is nitrogen; the intermediate product can be separated and purified and is light yellow transparent oily liquid.
In the step (1), the temperature of the first reaction is 45-55 ℃, and the reaction time is 1-10 hours; the temperature of the second reaction is 45-55 ℃, and the reaction time is 4-8 hours.
In the step (2), the reaction temperature is 45-55 ℃, and the reaction time is 20-50 hours.
The equation for the above reaction is shown below:
comparative example 1: preparation of fluorine-containing quaternary ammonium salt product
The preparation method of the fluorine-containing quaternary ammonium salt product comprises the following steps:
(1) 1.08g of CuBr is weighed into a 250mL eggplant-shaped bottle with stirring magnetons, 40g of toluene and 40g of ethanol were added to the reaction system, and 1.3g of 1.3g N, N, N' -Pentamethyldiethylenetriamine (PMDETA) and 0.975g of ethyl 2-bromoisobutyrate (EtBriB) were added to the reaction system, and the reaction system was charged with nitrogen gas three times, stirred under an oil bath pan at 50 ℃ and stirred, then 15g of dimethylaminoethyl methacrylate (recorded as DMAEMA) is added, after 5 hours of reaction at 50 ℃, and (3) exposing the reaction product to air to stop the reaction, removing most of the organic solvent by rotary evaporation, dissolving the reacted system by using 100mL of acetone, performing suction filtration by using a diaphragm pump to remove CuBr in the reacted system by using a neutral alumina chromatographic column, and performing rotary evaporation on the obtained eluent at 70 ℃ to remove unreacted substances (monomers or auxiliaries) to obtain an intermediate product (marked as PDMAEMA, and referred to as D for short).3)；
(2) 10g of D from step (1)3Dissolving the mixture in 40g of toluene/ethanol (mass ratio is 1: 1) mixed organic solvent, filling the mixture into 150mL eggplant-shaped bottles with stirring magnetons, flushing nitrogen into a reaction system for three times, placing the bottle in an oil bath kettle at 50 ℃, injecting 2.11g of benzyl chloride into the reaction system, carrying out heat preservation reaction for 24 hours, carrying out rotary evaporation at 70 ℃ to remove most of toluene and ethanol organic solvent in the reacted system, adding 100mL of diethyl ether after the rotary evaporation is finished, precipitating and separating a final product from the toluene/ethanol organic solvent by utilizing solubility difference to obtain a yellow flocculent product, repeatedly washing the product with diethyl ether for three 3 times, filtering, placing the product in a vacuum oven at 60 ℃ for drying for 48 hours to obtain a fluorine-containing quaternary ammonium salt product (marked as PDMAEMA-BC Q for short for PDMAEMA-BC Q)5)。
Comparative example 1 the reaction equation for the fluorinated quaternary ammonium salt product is as follows:
example 1: preparation of fluorine-containing macromolecular quaternary ammonium salt with diblock structure
The structural formula of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is shown as formula 1:
wherein m is 18 and n is 6.
The preparation method of the fluorine-containing macromolecular quaternary ammonium salt with the diblock structure comprises the following steps:
(1) weighing 1.08g of CuBr into a 250mL eggplant-shaped bottle with a stirring magneton, adding 40g of toluene and 40g of ethanol mixed organic solvent, adding 1.3g of 1.3g N, N, N' -pentamethyl divinyl triamine (PMDETA) and 0.975g of ethyl 2-bromoisobutyrate (EtBriB) into a reaction system, filling nitrogen into the reaction system for three times, placing the reaction system under a 50 ℃ oil bath kettle for stirring, then adding 5g of trifluoroethyl methacrylate (DMAFMA), carrying out a first reaction at 50 ℃ for 2.5 hours, then adding 15g of dimethylaminoethyl methacrylate (DMAEMA), carrying out a second reaction at 50 ℃ for 4 hours, and then adding 15g of dimethylaminoethyl methacrylate (DMAEMA)Exposing the mixture to air to stop reaction, removing most of organic solvent by rotary evaporation, dissolving the reacted system with 100mL of acetone, performing suction filtration by using a diaphragm pump to remove CuBr in the reacted system through a neutral alumina chromatographic column, performing rotary evaporation on the obtained eluent at 70 ℃ to remove unreacted substances (monomers or auxiliaries) to obtain an intermediate product (marked as F)1-b-D3)；
(2) Dissolving 10g of the intermediate product prepared in the step (1) in 40g of toluene/ethanol (mass ratio is 1: 1) mixed organic solvent, loading the mixture into a 150mL eggplant-shaped bottle with stirring magnetons, flushing and absorbing nitrogen for three times in a reaction system, placing the bottle in an oil bath kettle at 50 ℃, injecting 2.11g of benzyl chloride into the reaction system, preserving heat for reacting for 24 hours, performing rotary evaporation at 70 ℃ to remove most of toluene and ethanol organic solvent in the reacted system, adding 100mL of diethyl ether after the rotary evaporation is finished, precipitating and separating a final product from the toluene/ethanol organic solvent by utilizing solubility difference to obtain a yellow flocculent product, repeatedly washing the product with diethyl ether for three times 3 times, filtering, and placing the product in a vacuum oven at 60 ℃ for drying for 48 hours to obtain a fluorine-containing macromolecular quaternary ammonium salt (marked as PFDMS-MAPDEMA-BC, F) with a two-block structure for short1-b-Q5)。
FIG. 1 is an infrared spectrum of an intermediate product and a product obtained in example 1 and comparative example 1 of the present invention; FIG. 2 shows the NMR spectrum of the intermediate obtained in example 1 of the present invention (for clarity of FIG. 2, intermediate F is shown)1-b-D3A, b, a ', b', c, d, e, f in fig. 2 are labels for hydrogen at different positions); FIG. 2 shows the results obtained for intermediate F1-b-D3Placing in CDCl3As measured in deuterated chloroform. FIG. 3 is a NMR chart of the product obtained in example 1 of the present invention (for clarity of FIG. 3, product F is shown)1-b-Q5A, b, a ', b', c, d, e, f, g, h in fig. 3 are labels for hydrogen at different positions); FIG. 3 shows the results obtained by subjecting the product F1-b-Q5Measured in deuterated methanol (notation of b in FIGS. 2-3 for hydrogen at different positions and b in the intermediate or product formula preparedThe thinking is that, b for a different position hydrogen is a label for a different position hydrogen, and b in the intermediate or product formula is expressed to mean that the repeating units of m and n labels are in a diblock structure).
From the results shown in FIGS. 1 to 3, it can be seen that the product obtained in this example 1 has the formula shown in FIG. 1.
Example 2: preparation of fluorine-containing macromolecular quaternary ammonium salt with diblock structure
The structural formula of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is shown as formula 1:
wherein m is 18 and n is 12.
Example 2 differs from example 1 in that in example 210 g of trifluoroethyl methacrylate (described as DMAFMA) are added and the first reaction time is 4 hours, the procedure is the same as in example 1. Obtaining the fluorine-containing macromolecular quaternary ammonium salt (F for short) with a two-block structure2-b-Q5)。
Example 3: preparation of fluorine-containing macromolecular quaternary ammonium salt with diblock structure
The structural formula of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is shown as formula 1:
wherein m is 18 and n is 18.
Example 3 differs from example 1 in that in example 3 15g of trifluoroethyl methacrylate (described as DMAFMA) are added and the first reaction time is 6 hours, the procedure is the same as in example 1. Obtaining the fluorine-containing macromolecular quaternary ammonium salt (F for short) with a two-block structure3-b-Q5)。
Example 4: preparation of fluorine-containing macromolecular quaternary ammonium salt with two-block structure
The structural formula of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is shown as formula 1:
wherein m is 18 and n is 30.
Example 4 differs from example 1 in that in example 4 25g of trifluoroethyl methacrylate (designated DMAFMA) are added, the first reaction time is 10 hours and the procedure is the same as in example 1. Obtaining the fluorine-containing macromolecular quaternary ammonium salt (F for short) with a two-block structure5-b-Q5)。
Performance testing of products
1. Critical micelle concentration, Zeta potential (electromotive potential), particle size distribution, migration ability in soil performance test of products prepared in examples and comparative examples
FIG. 4 is a graph of the critical micelle concentration of the products obtained in examples 1-4 of the present invention and comparative example 1; FIG. 5 is a Zeta potential diagram for the products of inventive examples 1-4, comparative example 1; FIG. 6 is a graph showing the particle size distribution of the products obtained in examples 1 to 4 of the present invention and comparative example 1.
The products obtained in examples 1 to 4 of fig. 4 all showed a tendency of decreasing critical micelle concentration with increasing hydrophobicity.
The results in FIG. 5 show that the Zeta potential of the products obtained in examples 1-4 increases with increasing hydrophobicity, the Zeta potential of the micelles formed increases, and the dynamic stability of the micelles increases.
FIG. 6 the products obtained in examples 1 to 4 had larger particle sizes than the product obtained in comparative example 1, and the molecular weight increased with the increase of the hydrophobic segment, and the particle sizes of the products obtained in examples were increased.
2. Test of antibacterial Effect
The inhibition of the four bacteria/fungi by the products prepared in the examples was evaluated with reference to dodecyl dimethyl benzyl ammonium chloride (benzalkonium chloride, BC), escherichia coli (e.coli) as a representative of gram-negative bacteria, staphylococcus albus (s.albus) as a representative of gram-positive bacteria, candida albicans (c.albicans) as a representative of pathogenic fungi, and fusarium oxysporum cubeba specialization No. 4 physiorace (FOC4) as a representative of plant pathogenic fungi. The bacteriostatic experiment is briefly described as follows:
diluting the bacterial or fungal suspension cultured in the culture medium to 105CFU/mL, then 100. mu.L of the bacterial or fungal suspension and 100. mu.L of each of the solutions of the fluorine-containing macromolecular quaternary ammonium salt having a diblock structure prepared in examples and the product prepared in comparative example 1 at different concentrations were mixed and transferred to a 96-well plate. In addition, a culture medium was used as a control group instead of the fluorine-containing macromolecular quaternary ammonium salt solution having a diblock structure, then, the 96-well plate was incubated at 28 ℃ (fungi) or 37 ℃ (bacteria) for an appropriate number of days, and then 10 μ L of a solution of 2,3, 5-triphenyltetrazolium chloride (TTC) having a mass concentration of 5% was added to each well of the 96-well plate, and incubated at an appropriate temperature in the dark for 2 hours. The Minimum Inhibitory Concentration (MIC) value is the lowest concentration at which there is no visible bacterial or fungal growth, i.e. the lowest concentration at which TTC is not stained red. Then 100 μ L of the mixture in 96-well plates at or above MIC values was transferred to the medium for 48 hours of culture. The Minimum Fungicidal Concentration (MFC) or Minimum Bactericidal Concentration (MBC) value is the lowest concentration at which less than 5 colonies formation was observed, and the results are shown in fig. 7.
FIG. 7 is a graph showing the antibacterial effects of the products obtained in examples 1 to 4 of the present invention and comparative example 1; as can be seen from FIG. 7 (the ordinate in FIG. 7 indicates MIC or MFC (or MBC) values for bacteria or fungi corresponding to examples 1-4, comparative example 1), the products (F) produced by examples 1-4 of the present invention1-b-Q5、F2-b-Q5、F3-b-Q5、F5-b-Q5) Has good inhibitory effect on Escherichia coli (E.coli), Staphylococcus albus (S.albus), Candida albicans (C.albicans) and FOC 4. Wherein F1-b-Q5The minimal inhibitory concentration of FOC4 was comparable to Benzalkonium Chloride (BC), indicating F1-b-Q5Has good inhibition effect on FOC 4.
3. Testing of interaction characteristics with soil
And (3) testing the adsorption performance: examples 1 to 4 and comparative example 1 were prepared respectivelyAnd BC (benzalkonium chloride) with 0.01mol/L CaCl2The solutions are respectively prepared into 400mg/L, 100mL of the solutions are respectively put into 250mL conical flasks, 1g of sterilized soil is added, the rubber stoppers are sealed, the conical flasks are placed in a constant-temperature shaking incubator to shake at 25 ℃ and 200r/min, the conical flasks are placed in the constant-temperature shaking incubator, the initial time is 0, 1mL of upper-layer turbid liquid is respectively taken out at 1.5, 2,3,5, 10, 15, 20, 30, 40, 60, 80, 100, 120, 160, 210, 300, 600 and 720min, 1mL of deionized water is added, the upper-layer turbid liquid is centrifuged for 3min in a centrifuge of 8000r/min after the liquid taking is finished, the absorbance of the upper-layer clear liquid is measured by using an ultraviolet spectrophotometer, the adsorption content of the products prepared in examples 1-4 in the soil is calculated according to a standard curve and a formula, and the result is shown in FIG. 8.
FIG. 8 is a graph showing the saturation adsorption amount in soil of the products obtained in examples 1 to 4 of the present invention and comparative example 1; as can be seen from fig. 8, the products obtained in examples 1 to 4 of the present invention are easily adsorbed in soil, and the saturated adsorption amount in soil increases with increasing hydrophobicity (the fluorine-containing structure corresponds to hydrophobicity), the molecular weight increases, and the molecular chain growth tends to increase.
And (3) testing the migration performance: respectively preparing the products prepared in the embodiments 1 to 4 and BC (benzalkonium chloride) into 400mg/mL solutions, respectively dropwise adding 100mL of the solutions into leaching devices with different column thicknesses at a certain leaching speed (1-2 drops/second, which is equivalent to the actual heavy storm level), continuously dropwise adding deionized water at the same speed after the solution is dropwise added, observing the leaching condition, collecting the column leachate, collecting every 100mL of the column leachate until 500mL is collected, centrifuging 1mL of the column leachate at the rotating speed of 5000r/min for 5 minutes after the leachate collection is completed, testing the absorbance by using an ultraviolet spectrophotometer, and calculating the solution concentration, wherein the result is shown in FIG. 9.
In fig. 9, the ordinate represents "percentage of eluvial quaternary ammonium salt", and the products obtained in examples and comparative examples are quaternary ammonium salts, and for simplification of description, the ordinate represents "percentage of eluvial quaternary ammonium salt", which indicates that the products obtained in examples 1 to 4 have poor migration ability in soil and are not easily eluted by rain water.
4. Toxicity test on Zebra fish
Acute oral toxicity test of fish: refer to GB/T31270.12-2014 chemical pesticide environmental safety evaluation test guidelines-part 12: acute toxicity test of fish (Zebra fish test) by semi-static test method, which tests the acute toxicity of the products (called to be tested) prepared in examples 1-4 and comparative example 1 and benzalkonium chloride in water solution to Zebra fish, and comprises the following steps: determining the approximate toxic concentration range of the drug to the zebra fish through a pre-experiment, then accurately setting a series of gradient concentrations of the drug according to a certain interval, putting 7 zebra fish into each group of concentration gradients, replacing the drug liquid every day, keeping the other experiment conditions the same as the domestication environment, recording the growth condition of the zebra fish at 96h, and calculating the toxicity Level (LC) of the products prepared in the examples 1-4 and the comparative example 1 to the zebra fish50) The results are shown in Table 1.
Environmental toxicity test of drug-containing soil: 10g of fresh experimental soil, the products (which can be called as the drug to be tested) prepared in examples 1-4 and comparative example 1 and benzalkonium chloride are respectively prepared into 1000mL of drug-containing soil suspension, a group of drug-free soil suspension control groups are arranged at the same time, the soil suspension control groups are stirred by a glass rod and then are kept stand for 12h, 7 zebra fish are placed into each group of soil suspension after the upper layer of the solution is clear, the new soil suspension is changed every day, other experimental conditions are the same as the domestication environment, the growth condition of the zebra fish at 96h is recorded, the toxicity level of the drug to the zebra fish after soil adsorption is calculated, and the result is shown in Table 1.
Testing the toxicity of the leaching solution of the soil containing the medicine: the experimental soil, the products (which can be called as the medicine to be tested) prepared in the examples 1-4 and the comparative example 1 and benzalkonium chloride are respectively stirred and mixed uniformly, and then filled into a soil column, deionized water is dripped into the soil column eluviation device at a certain eluviation speed to wash the medicine in the soil column so as to simulate the actual washing condition of rainwater on the medicine in the soil, the eluviation condition is observed, the eluviation liquid of the soil column is collected to obtain eluviation liquid medicines of 100mg/L, 50mg/L, 20mg/L and 10mg/L, then the toxicity test of the zebra fish is carried out, the influence of the infiltration of the medicine into underground water along with rainwater on the toxicity of the zebra fish in the actual production and application is simulated, and the results are shown in the table 1.
TABLE 1
As can be seen from Table 1, the products obtained in examples 1 to 4 of the present invention exhibited low toxicity after interaction with soil.
4. Testing for impact on soil microbial diversity
Weighing 1g of fresh soil, the product prepared in example 1 and comparative example 1 and Benzalkonium Chloride (BC) medicine into a sterile centrifuge tube, supplementing a certain amount of sterile water to enable the water-soil mass ratio of a soil solution system to be 1:1, setting a group of deionized water control group (marked as CK), placing the prepared soil medicine liquid system into a constant-temperature shaking incubator to be cultured for 2 days under the condition of 28 ℃ and 200rpm, taking 0.5mL of upper-layer solution after the culture is finished, placing the upper-layer solution into a 1mL centrifuge tube, centrifuging the upper-layer solution for 3 minutes in a 5000r/min centrifuge, and then carrying out a series of dilution on the upper-layer solution. 100 mul of the diluted culture solution was applied to prepared Bengal red medium, beef extract peptone medium and modified Gow's medium by using a pipette gun to culture fungi, bacteria and actinomycetes in soil, and after culturing for a certain number of days in a constant temperature incubator at 28 ℃, colonies of the fungi, bacteria and actinomycetes grown in the plate medium were counted and compared with the number of colonies in a soil system to which the products prepared in example 1 and comparative example 1 were not added, thereby evaluating the influence of the products prepared in example 1 and comparative example 1 on microorganisms in the soil system.
FIG. 10 shows the effect of the products of example 1 and comparative example 1 on the diversity of soil microorganisms; in FIG. 10, (a), (b), and (c) represent the effects of the products obtained in example 1 and comparative example 1, and benzalkonium chloride on the amounts of bacteria, actinomycetes, and fungi, respectively. As can be seen from FIG. 10, Benzalkonium Chloride (BC) completely kills microorganisms in soil almost indiscriminately, whereas the product obtained in example 1 of the present invention had a lesser effect on the abundance of typical microbial communities in soil, with a reduced abundance of fungal communities and an increased abundance of bacterial and actinomycete communities, suggesting that soil to which the product obtained in example 1 was applied is more conducive to the planting of banana plants.
5. Pot experiment
Sterile and non-drug, sterile and drug test groups are arranged in the pot culture test process, 5 repeated groups are repeated under each concentration, and the specific operation is as follows: 10g of matrix soil is added into each of 100 parts of experimental soil samples, 90 parts of the experimental soil samples are taken and mixed with the product (called drug) solution prepared in a certain concentration comparative example 1 and example 1 uniformly, and then the mixture is filled into an experimental flowerpot with the upper caliber of 12cm, the lower caliber of 10cm and the height of 10cm, 10 parts of each concentration component (5 pots are inoculated in each concentration when FOC4 is inoculated subsequently), and the rest 10 groups of experimental soil samples are mixed with 150mL of deionized water uniformly to be set as a drug-free control group (marked as CK). Selecting banana seedlings with consistent root system and leaf growth vigor, transplanting the banana seedlings into the prepared potted soil environment, culturing for 14 days, and inoculating 2 multiplied by 10 pots of 5 pots of the banana seedlings under each concentration gradient of the aseptic medicinal group and the aseptic medicinal group after the banana seedlings adapt to the growth environment6FOC4 spore bacteria suspension of each g soil, continuously culturing for a certain number of days and counting the infection condition of the banana seedlings, and the results are shown in Table 2.
TABLE 2
Table 2 shows the influence of the products obtained in comparative example 1 and example 1 on the growth parameters of banana seedlings, EC50sRepresents the drug concentration at which the product prepared in comparative example 1 and example 1 inhibited FOC4 in soil to 50%. As can be seen from the results of table 2: products obtained in comparative example 1 and example 1 without inoculating FOC4The influence on the growth of banana seedlings is small; after the inoculation of FOC4, the product prepared in example 1 greatly reduces the concentration of FOC4 in soil through interaction with pathogenic bacteria in the soil, the banana seedling disease condition is better, the growth condition of the banana seedling obtains obvious effect along with the increase of the content of the applied medicine, and when the application amount of the product prepared in example 1 reaches 4 times of EC50sNamely, when the soil is about 1.2mg/g, the disease index of banana seedlings is reduced to the first level (the infection degree is about 11%), which indicates that the product prepared in the example 1 has positive prevention and treatment effects in the prevention and treatment process of banana vascular wilt infection.
Claims (10)
1. The general structural formula of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is shown as formula 1:
wherein m and n are both positive integers, and m: n ═ 14 to 22: (6-32).
2. The fluorine-containing macromolecular quaternary ammonium salt with a diblock structure according to claim 1, wherein m to n is 18: (6-30).
3. The fluorine-containing macromolecular quaternary ammonium salt having a diblock structure according to claim 1, wherein m is 18, and n is 6, 12, 18 or 30.
4. The fluorine-containing macromolecular quaternary ammonium salt with a diblock structure according to claim 1, wherein the molecular weight of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure is 5-20 kDa.
5. The method for preparing fluorine-containing macromolecular quaternary ammonium salt having a diblock structure according to any one of claims 1 to 4, comprising the steps of:
(1) mixing trifluoroethyl methacrylate, brominated ester, a catalyst, an auxiliary agent and an organic solvent, carrying out a first reaction in an inert gas atmosphere, adding dimethylaminoethyl methacrylate, and carrying out a second reaction to obtain an intermediate product;
(2) and (2) mixing the intermediate product prepared in the step (1), benzyl chloride and an organic solvent, and reacting in an inert gas atmosphere to prepare the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure.
6. The method according to claim 5, wherein in the step (1), the temperature of the first reaction is 45 to 55 ℃ and the reaction time is 1 to 10 hours.
7. The method according to claim 5, wherein in the step (1), the temperature of the second reaction is 45 to 55 ℃ and the reaction time is 4 to 8 hours.
8. The preparation method according to claim 5, wherein in the step (1), the mass ratio of trifluoroethyl methacrylate to dimethylaminoethyl methacrylate is 1-5: 3.
9. the use of the fluorine-containing macromolecular quaternary ammonium salt with a diblock structure according to any one of claims 1-4 for controlling banana wilt.
10. An antibacterial agent comprising the fluorine-containing macromolecular quaternary ammonium salt having a diblock structure according to any one of claims 1 to 4.
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