CN115399179A - Application of polysaccharide-based cationic polymer in prevention and treatment of soil-borne diseases of agriculture and forestry - Google Patents

Application of polysaccharide-based cationic polymer in prevention and treatment of soil-borne diseases of agriculture and forestry Download PDF

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CN115399179A
CN115399179A CN202110584175.1A CN202110584175A CN115399179A CN 115399179 A CN115399179 A CN 115399179A CN 202110584175 A CN202110584175 A CN 202110584175A CN 115399179 A CN115399179 A CN 115399179A
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chloride
polysaccharide
bromide
based cationic
cationic polymer
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田卫国
季欣
温朝俊
张军
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M17/00—Apparatus for the destruction of vermin in soil or in foodstuffs
    • A01M17/002—Injection of toxic gases or fluids into the soil
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M17/00—Apparatus for the destruction of vermin in soil or in foodstuffs
    • A01M17/008—Destruction of vermin in foodstuffs
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom

Abstract

The invention discloses application of polysaccharide-based cationic polymer for preventing and treating soil-borne diseases of agriculture and forestry, wherein the polysaccharide-based cationic polymer is selected from polysaccharide or polysaccharide derivatives substituted by an acylating reagent. The polysaccharide-based cationic polymer can kill pathogenic bacteria of the blight in the soil-borne diseases of agriculture and forestry, fusarium oxysporum, fusarium solani and the like. The polysaccharide-based cationic polymer sterilization material has no biotoxicity, is biodegradable and is environment-friendly. And the polysaccharide polymer can be conveniently processed into various forms of materials such as aqueous solution, emulsion, microspheres and the like based on the natural hydrophilic property of the polysaccharide polymer, so that the polysaccharide polymer has important practical value.

Description

Application of polysaccharide-based cationic polymer in prevention and treatment of soil-borne diseases of agriculture and forestry
Technical Field
The invention belongs to the technical field of bio-based agricultural and forestry disease control materials, and particularly relates to application of polysaccharide-based cationic polymer for agricultural and forestry soil-borne disease control.
Background
The prevention and control of agricultural and forestry diseases are the key points for increasing both production and income of agriculture and forestry, and most of the current agricultural and forestry soil-borne diseases are caused by the transmission and infection of pathogenic microorganisms such as bacteria and fungi. Plant black rot caused by fusarium, phytophthora, pythium and the like is an important fungal soil-borne disease restricting crop production, and can damage plants such as broccoli, cabbage, radish and the like, thereby reducing the yield and quality of the plants. After the crops are infected by pathogenic bacteria, leaves and stems can turn yellow and fall off, root system rot is caused, and the plants can die seriously.
At present, the most direct and effective control method against bacterial and fungal infections is the spraying of pesticides containing antibiotics, which can control the spread of diseases relatively quickly. However, the long-term use of antibiotics can cause the appearance of drug-resistant bacteria and fungi, thereby causing the control effect of the original pesticide to be poor or even completely ineffective. In addition, most of the approved pesticides for preventing and treating bacterial and fungal infection are small molecular structures, and are difficult to adsorb for a long time in a complex soil environment, so that pathogenic bacteria hidden in the soil are difficult to contact and kill; meanwhile, a dispersing aid and the like are often needed to be stably dispersed in the solution, but the dispersing aid is diffused and lost in soil, so that side effects such as environmental pollution and the like are generated. Therefore, the development of the bactericide which has a lasting bactericidal effect, does not generate drug resistance, is environment-friendly and biodegradable is the development direction in the future.
Disclosure of Invention
In order to improve the technical problems, the invention provides application of polysaccharide-based cationic polymer used for preventing and treating soil-borne diseases of agriculture and forestry, wherein the polysaccharide-based cationic polymer is selected from polysaccharide or polysaccharide derivative substituted by acylating reagent.
According to the embodiment of the invention, the polysaccharide-based cationic polymer has better biocompatibility and chemical stability, and can kill at least one of phytophthora blight pathogenic bacteria, fusarium oxysporum, fusarium solani and the like in agricultural and forestry soil-borne diseases, so that the prevention and the treatment of the agricultural and forestry soil-borne diseases are realized.
According to an embodiment of the invention, the polysaccharide or polysaccharide derivative is selected from one, two or more of starch, dextran, chitosan, chitin, alginic acid, cellulose or cellulose derivatives.
Illustratively, the starch is selected from at least one of amylopectin and amylose.
Illustratively, the cellulose is selected from at least one of microcrystalline cellulose, cotton pulp, wood pulp, bamboo pulp, cotton wool, bagasse, wood, and cellulose made from plant straw.
Illustratively, the cellulose derivative is selected from at least one of a substituent-containing cellulose ether and a substituent-containing cellulose ester; wherein the substituents are selected from C 1 -C 4 At least one of the alkyl groups, such as methyl, ethyl, propyl.
Illustratively, the cellulose ester is selected from at least one of cellulose acetate, cellulose propionate, cellulose butyrate, cellulose nitrate, and cellulose benzoate.
Illustratively, the cellulose ether is selected from at least one of methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose.
According to an embodiment of the invention, the acylating reagent is selected from at least one of an acid chloride or an acid bromide reagent.
Illustratively, the acid chloride reagent is selected from at least one of chloroacetyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride, 4-chlorobutyryl chloride, 5-chloropentanoyl chloride, 6-chlorohexanoyl chloride, m-chlorobenzoyl chloride, 5-chlorothiophene-2-sulfonyl chloride, 2-chlorobenzoyl chloride, 2-chlorophenylacetyl chloride, 2, 5-dichlorobenzenesulfonyl chloride, dichloroacetyl chloride, 3, 5-difluorobenzoyl chloride, 2, 6-difluorobenzoyl chlorobromoacetyl chloride, pentafluorobenzoyl chloride, 3-trifluoromethylbenzoyl chloride, 2-trifluoromethylbenzoyl chloride, 4-trifluoromethylbenzoyl chloride, 3-fluoro-4-bromobenzenesulfonyl chloride, 3-fluorobenzoyl chloride, 2-fluorobenzoyl chloride, 4-fluorophenylacetyl chloride, 6-bromohexanoyl chloride, p-bromobenzoyl chloride, 4-carboxybenzenesulfonyl chloride, 3-bromobenzoyl chloride, 4-bromobenzoyl chloride and 2-bromoethylsulfonyl chloride, preferably at least one of chloroacetyl chloride, 2-chloropropionyl chloride and chlorobutyroyl chloride.
Illustratively, the acyl bromide reagent is selected from at least one of bromoacetyl bromide, 2-bromopropionyl bromide, 3-bromopropionyl bromide, 4-bromobutyryl bromide, 5-bromovaleryl bromide, 6-bromohexanoyl bromide, 2-bromo-n-butanoyl bromide, p-bromobenzenesulfonyl bromide, 2, 3-dibromopropionyl bromide, 2, 4-dibromobutyryl bromide, p-bromomethylbenzoyl bromide, 4-bromobenzeneacetyl bromide, 3, 5-difluorobenzoyl bromide, 3-chloro-4-fluorobenzoyl bromide, 3-bromo-4-fluorobenzoyl bromide, 2,4, 5-trifluorobenzoyl bromide, and 3' -bromobenzeneacetyl bromide.
According to an embodiment of the invention, the degree of substitution of the acylating agent in the polysaccharide-based cationic polymer is 0.01 to 3, preferably 0.05 to 3, more preferably 0.1 to 3, exemplary 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.8, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.8, 2.0, 2.5, 3.0.
According to an embodiment of the present invention, the polysaccharide-based cationic polymer further includes a substituent group substituted with at least one of a tertiary amine compound and a tertiary phosphine compound.
Illustratively, the tertiary amine compound is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, N-dimethylethylamine, N, N-dimethylpropylamine, N-dimethylbutylamine, N-diethylmethylamine, N-diethylpropylamine, N-diethylbutylamine, N-dipropylmethylamine, N, N-dipropylethylamine, N-dipropylbutylamine, N-dibutylmethylamine, N-dibutylethylamine, N-dibutylpropylamine, N, at least one of N-dimethylcyclohexylamine, N-diethylcyclohexylamine, N-dipropylcyclohexylamine, N-diethylhydroxylamine and N-methylcyclohexylamine.
Illustratively, the tertiary phosphine compound is selected from at least one of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, dimethylethylphosphine, dimethylpropylphosphine, dimethylbutylphosphine, diethylmethylphosphine, diethylpropylphosphine, diethylbutylphosphine, dipropylmethylphosphine, dipropylethylphosphine, dipropylbutylphosphine, dibutylmethylphosphine, dibutylethylphosphine, dibutylpropylphosphine, dimethylphenylphosphine, diethylphenylphosphine, dipropylphosphine, dibutylphosphine and triphenylphosphine, preferably from trimethylphosphine.
According to an embodiment of the present invention, in the polysaccharide-based cationic polymer, the degree of substitution of the substituent group by at least one of the tertiary amine-based compound and the tertiary phosphine-based compound is 0.01 to 3, preferably 0.05 to 3, more preferably 0.1 to 3, and exemplified by 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.8, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.8, 2.0, 2.5, and 3.0.
According to an embodiment of the present invention, the polysaccharide-based cationic polymer is prepared by a preparation method comprising the steps of: polysaccharide or polysaccharide derivative and acylating reagent are used as raw materials to react to prepare the polysaccharide-based cationic polymer.
According to an embodiment of the present invention, the raw material further comprises at least one compound of a tertiary amine compound and a tertiary phosphine compound.
According to an embodiment of the invention, the polysaccharide or polysaccharide derivative, acylating agent and compound may be mixed in the form of a solution thereof; alternatively, the polysaccharide or polysaccharide derivative, the acylating agent, and the compound are sequentially added to a solvent and mixed. For example, a solution of a polysaccharide or polysaccharide derivative is prepared, and then an acylating agent and a compound are sequentially added to the solution to obtain a mixed solution.
According to an embodiment of the invention, in the reaction, the mass ratio of the polysaccharide or polysaccharide derivative to the acylating agent is 1; preferably 1; more preferably 1.
According to an embodiment of the present invention, in the reaction, the mass ratio of the polysaccharide or polysaccharide derivative to the compound is 1; preferably 1; more preferably 1.
According to an embodiment of the present invention, the solvent is selected from at least one of N, N-dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), tetrahydrofuran (THF), acetone, chloroform, pyridine, N-methylpyrrolidone, and ionic liquids.
According to an embodiment of the present invention, when the polysaccharide or polysaccharide derivative is selected from cellulose, starch, chitosan, chitin, and the like, the solvent is preferably an ionic liquid; when the polysaccharide or polysaccharide derivative is selected from cellulose derivatives, the solvent is preferably at least one of DMSO, DMF, DMAc, THF, acetone, chloroform, N-methylpyrrolidone, and pyridine.
Preferably, the ionic liquid is an organic molten salt which is formed by imidazole or pyridine type cations and anions and has a melting point lower than 100 ℃, and can dissolve polysaccharides such as cellulose, starch, chitosan and chitin.
The invention can use mixed ionic liquid to dissolve cellulose, starch, chitosan, chitin and other polysaccharides, wherein: the mixed ionic liquids can be all the ionic liquids capable of dissolving the polysaccharides such as cellulose, starch, chitosan, chitin and the like, and can also be the mixture of the ionic liquids capable of dissolving the polysaccharides such as cellulose, starch, chitosan, chitin and the like and the ionic liquids incapable of dissolving the polysaccharides such as cellulose, starch, chitosan, chitin and the like.
Illustratively, the cation of the ionic liquid is selected from any one of the following: 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-allyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, N-ethylpyridinium cation, N-butylpyridinium cation, N-N-hexylpyridinium cation. The cation is particularly preferably any one of the following: 1-ethyl-3-methylimidazolium cation, 1-allyl-3-methylimidazolium cation and 1-butyl-3-methylimidazolium cation.
Illustratively, the anion of the ionic liquid is selected from any one of the following: chloride, bromide, formate, acetate, propionate, butyrate, and methyl phosphate ions. More preferably, the anion is selected from any one of the following: chloride, formate, acetate and methyl phosphate ions.
According to an embodiment of the present invention, the above solvents may be used alone or in combination.
According to an embodiment of the invention, the polysaccharide or polysaccharide derivative is present in the solution in a concentration of 0.2-15% by mass, such as 0.5-7%, exemplarily 0.2%, 0.5%, 1%, 2%, 5%, 7%, 10%, 15%.
According to an embodiment of the invention, the temperature of the reaction is 0 to 150 ℃, exemplary 0 ℃, 25 ℃,40 ℃,60 ℃,80 ℃, 100 ℃, 120 ℃, 150 ℃. Further, the reaction time is 0.5 to 72 hours, and is exemplified by 0.5h, 1h, 5h, 12h, 24h, 36h, 48h, 72h.
According to an embodiment of the present invention, the method of preparing the polysaccharide-based cationic polymer further comprises: after the reaction is finished, carrying out solid-liquid separation, washing, drying and the like on the reaction product.
For example, the solid-liquid separation may be dialysis. In another example, the solvent used for dialysis is at least one of water or alcohol. Preferably, the alcohol is selected from at least one of methanol, ethanol, propanol and isopropanol.
According to an embodiment of the present invention, the method for preparing the polysaccharide-based cationic polymer comprises the steps of:
1) Dissolving polysaccharide or polysaccharide derivative in solvent, adding acylating agent and compound, and reacting at 0-150 deg.C for 0.5-72h.
2) And dialyzing the reaction solution, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
The invention also provides a sterilizing material which comprises the polysaccharide-based cationic polymer.
According to the embodiment of the invention, the sterilization material has better biocompatibility and chemical stability, and can kill pathogenic bacteria of the blight disease, fusarium oxysporum, fusarium solani and the like in the soil-borne diseases of agriculture and forestry.
According to an embodiment of the invention, the concentration of the biocidal material is between 50. Mu.g/mL and 1g/mL, preferably between 500. Mu.g/mL and 5mg/mL, exemplary being 50. Mu.g/mL, 60. Mu.g/mL, 75. Mu.g/mL, 100. Mu.g/mL, 200. Mu.g/mL, 500. Mu.g/mL, 1mg/mL, 2mg/mL, 5mg/mL, 10mg/mL, 1g/mL.
The invention also provides application of the sterilization material in agriculture and forestry diseases and food spoilage prevention and treatment caused by propagation and infection of pathogenic microorganisms such as bacteria and fungi.
Illustratively, in the black rot of plants caused by phytophthora blight pathogens, fusarium oxysporum, fusarium solani, and the like.
The invention also provides a method for preventing and treating the agricultural and forestry diseases, which comprises the steps of contacting the sterilization material with agricultural and forestry crops which are easy to cause the agricultural and forestry diseases by the transmission and infection of pathogenic microorganisms such as bacteria and fungi;
or contacting the above-mentioned bactericidal material with food which is susceptible to putrefaction caused by the propagation and infection of pathogenic microorganisms such as bacteria and fungi;
alternatively, the bactericidal material is brought into contact with an environment in which diseases are easily caused by the spread and infection of pathogenic microorganisms such as bacteria and fungi.
The invention has the advantages of
Compared with a micromolecular structure, the macromolecular polymer has the characteristics of large molecular weight and various structures, and the chemical stability, the thermal stability and the biological toxicity of the macromolecular polymer are superior to those of micromolecules. The action mechanism of the cationic antibacterial polymer is mainly divided into two mechanisms: one is through electrostatic interaction, such as the cell membrane surface of gram-positive bacteria and gram-negative bacteria is electronegative, and the cationic antibacterial polymer can be combined with the electronegative cell membrane surface through the interaction force between charges and further reacts with proteins in cells and the like to destroy the normal life activities of the cells; the second is that through ion exchange, cations of the cationic antibacterial polymer can exchange with metal cations such as calcium and magnesium of the microbial cell membrane to destroy the potential balance on the surface of the cell membrane and finally cause the damage of the microbial cell membrane. Based on the above, the inventors of the present invention propose a polysaccharide-based cationic antibacterial polymer based on a water-soluble modified polysaccharide modified by a small-molecule antibacterial agent, specifically:
(1) According to the invention, the micromolecular antibacterial agent is modified on the polysaccharide macromolecule through homogeneous chemical modification, so that the antibacterial activity of the antibacterial agent is effectively improved, meanwhile, the natural hydrophilicity of the polysaccharide macromolecule is utilized, the affinity with microorganisms is improved, the adhesion of a cationic antibacterial polymer in plant soil can be enhanced, and an excellent antibacterial effect is shown. The polysaccharide polymer is also innovatively applied to prevention and treatment of agricultural and forestry diseases, so that the problems of poor chemical stability and thermal stability of the traditional small-molecule pesticide are solved, and the polysaccharide polymer has good biodegradability due to the natural biobased nature, so that the polysaccharide polymer belongs to an environment-friendly new material for prevention and treatment of agricultural and forestry diseases, particularly has an excellent protection effect on plant black rot in agriculture, and has a potential very important application prospect.
(2) The polysaccharide-based strong cationic antibacterial polymer can kill pathogenic bacteria of the blight in the soil-borne diseases of agriculture and forestry, fusarium oxysporum, fusarium solani and the like. The sterilization material has no biotoxicity, is biodegradable and is environment-friendly. And due to the characteristics of the polymer, the material can be conveniently processed into various forms of materials such as aqueous solution, emulsion, microspheres and the like, and has important practical value.
Drawings
In FIG. 1, (a) and (b) are FTIR patterns of the bactericidal material obtained in example 1, 1 H-NMR chart.
Fig. 2 shows the results of the bactericidal test of the bactericidal material of example 1 against the pathogen Pseudomonas syringae pv. Phaseolicola.
FIG. 3 shows the results of the minimum inhibitory concentration test of the bactericidal material of example 1 against Fusarium oxysporum.
FIG. 4 shows the results of the minimum bactericidal concentration test of the bactericidal material of example 1 against Fusarium oxysporum.
FIG. 5 shows the results of the minimum inhibitory concentration test of the bactericidal material in example 1 against Fusarium solani.
FIG. 6 shows the results of the minimum bactericidal concentration test of the bactericidal material of example 1 against Fusarium solani.
FIG. 7 is a photograph showing the bactericidal material of example 1 before and after the treatment of the meat-rich black rot.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose was weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved with vigorous stirring at 80 ℃ for 2h. Then 7.6g of 2-chloropropionyl chloride was added and reacted at 40 ℃ for 6 hours. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 3.64g of tributylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 2
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of cotton pulp was weighed out and added to 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved at 80 ℃ with vigorous stirring for 2h. Then 7.6g of 2-chloropropionyl chloride was added and reacted at 40 ℃ for 6 hours. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 3.64g of tributylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 3
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose is weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved for 2h at 80 ℃ with vigorous stirring. Then 7.6g of 2-chloropropionyl chloride was added and reacted at 40 ℃ for 6 hours. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of cellulose derivative was weighed and dissolved in 10mL of DMF, and 4.7g of triphenylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 4
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose was weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved with vigorous stirring at 80 ℃ for 2h. 6.77g of chloroacetyl chloride are subsequently added and reacted for 6h at 40 ℃. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 3.64g of tributylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 5
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of cotton pulp was weighed out and added to 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved at 80 ℃ with vigorous stirring for 2h. 6.77g of chloroacetyl chloride are subsequently added and reacted for 6h at 40 ℃. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 3.64g of tributylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 6
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose was weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved with vigorous stirring at 80 ℃ for 2h. 6.77g of chloroacetyl chloride are subsequently added and reacted for 6h at 40 ℃. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 4.7g of triphenylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 7
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose was weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved with vigorous stirring at 80 ℃ for 2h. Then, 8.45g of chlorobutyryl chloride was added thereto, and the reaction was carried out at 40 ℃ for 6 hours. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 4.7g of triphenylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 8
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose was weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved with vigorous stirring at 80 ℃ for 2h. Then, 8.45g of chlorobutyryl chloride was added thereto, and the reaction was carried out at 40 ℃ for 6 hours. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder.
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 3.64g of tributylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 9
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose is weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved for 2h at 80 ℃ with vigorous stirring. Then, 8.45g of chlorobutyryl chloride was added thereto, and the reaction was carried out at 40 ℃ for 6 hours. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 1.37g of trimethylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 10
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose was weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved with vigorous stirring at 80 ℃ for 2h. 7.6g of 2-chloropropionyl chloride are subsequently added and reacted for 6h at 40 ℃. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 1.37g of trimethylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 11
The preparation of polysaccharide-based cationic polymer with bactericidal effect comprises the following steps:
(1) 1.62g of microcrystalline cellulose was weighed into 50g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid and dissolved with vigorous stirring at 80 ℃ for 2h. 6.77g of chloroacetyl chloride are subsequently added and reacted for 6h at 40 ℃. After the reaction is finished, adding the reaction solution into ethanol, and precipitating, washing and drying to obtain cellulose derivative solid powder;
(2) 0.4g of the cellulose derivative was weighed out and dissolved in 10mL of DMF, and 1.37g of trimethylphosphine was added thereto, followed by reaction at 60 ℃ for 24 hours. After the reaction is finished, dialyzing the reaction solution for 5 days by using water or ethanol, and drying to obtain the polysaccharide-based cationic polymer with the bactericidal effect.
Example 12
Structural characterization of the biocidal material of example 1.
Using FTIR and 1 the chemical structure of the bactericidal material prepared in example 1 of the present invention was characterized by H-NMR, and the results are shown in fig. 1 (a) and (b), respectively.
As shown in FIG. 1 (a), 3500cm in FTIR spectrum -1 Stretching vibration attributed to O-H; 300-2700cm -1 Characteristic peaks ascribed to the methyl and methylene groups of tributylphosphine; 1730cm -1 The characteristic peak is assigned to C = O and is a new ester group formed after modification of 2-chloropropionyl chloride with microcrystalline cellulose.
As shown in figure 1 (b) of the drawings, 1 in the H-NMR spectrum, characteristic peaks ascribed to tributylphosphine appeared at 2.3ppm,1.4ppm, 0.9ppm; 5.5-2.5ppm is microcrystalline cellulose skeleton peak and characteristic peak of methylene in 2-chloropropionyl chloride. The degree of substitution of 2-chloropropionyl chloride was calculated to be 1.6 and the degree of substitution of tributylphosphine was calculated to be 1.1.
Example 13
The bactericidal material in example 1 was tested for bactericidal activity against Pseudomonas syringae pv. Phaseolicola.
80 mu L of polysaccharide-based cationic polymer solutions with different concentrations are respectively mixed with 20 mu L of bacterial liquid (OD = 0.5) of pathogenic bacteria of the epidemic disease (Pseudomonas syringae pv. Phaseolicola) in a 96-well plate uniformly, and the bacterial liquid is diluted 10000 times by PBS after dark culture for 30 min. Then, 100. Mu.L of the diluted solution was applied evenly on NB medium and cultured at 28 ℃ for 24 hours to count the colonies. As shown in figure 2, when the concentration of the polysaccharide-based cationic polymer bactericidal material reaches 1 mug/mL, the pathogenic bacteria of the phytophthora blight can be completely killed. According to the table, the minimum inhibitory concentration of the polysaccharide-based cationic polymer prepared by the invention to pathogenic bacteria of the epidemic disease is 1 microgram/mL.
Example 14
The biocidal material of example 1 was tested for minimum inhibitory concentration against fusarium oxysporum.
Adding polysaccharide-based cationic polymer solution with different concentrations into liquid culture medium (composed of glucose 20g, potato 200g, agar 20g, and water 1L), and mixing with 10 6 CFU/mL Fusarium oxysporum spore suspension is mixed uniformly, cultured in an incubator at 28 ℃ for 8h, and then the spore germination condition is observed by a microscope. As shown in FIG. 3, the spores in the blank control group after PBS treatment clearly grew and hyphae were formed. When the concentration of the polysaccharide-based cationic polymer solution reaches 50 mu g/mL or more, no germination of spores occurs. The minimum inhibitory concentration of the polysaccharide-based cationic polymer prepared by the method on Fusarium oxysporum is 50 mu g/mL.
Example 15
The bactericidal material of example 1 was tested for minimum bactericidal concentration against fusarium oxysporum.
Spores at the concentration of the non-germination treatments in example 14 were transferred onto PDA medium and cultured at 28 ℃ for 5 days. As shown in FIG. 4, when the concentration of the polysaccharide-based cationic polymer solution reached 75. Mu.g/mL or more, no hypha growth was observed. The minimum bactericidal concentration of the polysaccharide-based cationic polymer prepared according to the present invention against Fusarium oxysporum was 75. Mu.g/mL.
Example 16
The germicidal material of example 1 was tested for minimum inhibitory concentration against fusarium solani.
The test method was the same as in example 14. As shown in FIG. 5, the spores in the blank control group after PBS treatment clearly grew and hyphae were formed. When the concentration of the polysaccharide-based cationic polymer solution reaches 40 mu g/mL or more, spores do not germinate. The minimum inhibitory concentration of the polysaccharide-based cationic polymer prepared by the method on Fusarium solani is 40 mug/mL.
Example 17
The germicidal material of example 1 was tested for minimum germicidal concentration against fusarium solani.
The test method was the same as in example 15. As shown in FIG. 6, when the concentration of the polysaccharide-based cationic polymer solution was 60. Mu.g/mL or more, no hypha growth was observed. The minimum bactericidal concentration of polysaccharide-based cationic polymer prepared according to the present invention against Fusarium solani was 60 μ g/mL.
Example 18
FIG. 7 is a photograph of the fungicidal material of example 1 before and after the treatment of succulent black rot.
The bactericidal material prepared in example 1 was sprayed onto the fleshy foliage (the leaf core and leaf of the fleshy foliage which are infected with black rot become black and rotten) at a concentration of 2mg/mL, and the mixture was exposed to sunlight, and the growth of the plants was observed and recorded on time. The results are shown in FIG. 7, which shows that: after treatment, the rotting degree of succulent rootstalks is greatly relieved, and plants can grow normally.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. Use of polysaccharide-based cationic polymers for the control of soil-borne diseases in agriculture and forestry, characterized in that the polysaccharide-based cationic polymers are selected from acylated agent substituted polysaccharides or polysaccharide derivatives.
2. Use according to claim 1, wherein the polysaccharide or polysaccharide derivative is selected from one, two or more of starch, dextran, chitosan, chitin, alginic acid, cellulose or cellulose derivatives.
3. Use according to claim 1 or 2, wherein the acylating reagent is selected from at least one of an acid chloride or an acid bromide reagent.
Preferably, the acid chloride reagent is selected from at least one of chloroacetyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride, 4-chlorobutyryl chloride, 5-chlorovaleryl chloride, 6-chlorohexanoyl chloride, m-chlorobenzoyl chloride, 5-chlorothiophene-2-sulfonyl chloride, 2-chlorobenzoyl chloride, 2-chlorophenylacetyl chloride, 2, 5-dichlorobenzenesulfonyl chloride, dichloroacetyl chloride, 3, 5-difluorobenzoyl chloride, 2, 6-difluorobenzoyl chlorobromoacetyl chloride, pentafluorobenzoyl chloride, 3-trifluoromethylbenzoyl chloride, 2-trifluoromethylbenzoyl chloride, 4-trifluoromethylbenzoyl chloride, 3-fluoro-4-bromobenzenesulfonyl chloride, 3-fluorobenzoyl chloride, 2-fluorobenzoyl chloride, 4-fluorobenzoyl chloride, 6-bromohexanoyl chloride, p-bromobenzoyl chloride, 4-carboxybenzoyl chloride, 3-bromobenzoyl chloride, 4-bromobenzoyl chloride and 2-bromoethylsulfonyl chloride, preferably at least one of chloroacetyl chloride, 2-chloropropionyl chloride and 2-bromobutyroyl chloride.
Preferably, the acyl bromide reagent is selected from at least one of bromoacetyl bromide, 2-bromopropionyl bromide, 3-bromopropionyl bromide, 4-bromobutyryl bromide, 5-bromovaleryl bromide, 6-bromohexanoyl bromide, 2-bromo-n-butanoyl bromide, p-bromobenzenesulfonyl bromide, 2, 3-dibromopropionyl bromide, 2, 4-dibromobutyryl bromide, p-bromomethylbenzoyl bromide, 4-bromobenzeneacetyl bromide, 3, 5-difluorobenzoyl bromide, 3-chloro-4-fluorobenzoyl bromide, 3-bromo-4-fluorobenzoyl bromide, 2,4, 5-trifluorobenzoyl bromide, and 3' -bromobenzeneacetyl bromide.
4. Use according to any one of claims 1 to 3, wherein the polysaccharide-based cationic polymer has a degree of substitution of the acylating agent in the range of 0.01 to 3, preferably 0.05 to 3, more preferably 0.1 to 3.
5. The use according to any one of claims 1 to 4, wherein the polysaccharide-based cationic polymer further comprises a substituent group substituted with at least one of a tertiary amine compound and a tertiary phosphine compound.
Preferably, the tertiary amine compound is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, N-dimethylethylamine, N, N-dimethylpropylamine, N-dimethylbutylamine, N-diethylmethylamine, N-diethylpropylamine, N-diethylbutylamine, N-dipropylmethylamine, N, N-dipropylethylamine, N-dipropylbutylamine, N-dibutylmethylamine, N-dibutylethylamine, N-dibutylpropylamine, N, at least one of N-dimethylcyclohexylamine, N-diethylcyclohexylamine, N-dipropylcyclohexylamine, N-diethylhydroxylamine and N-methylcyclohexylamine.
Preferably, the tertiary phosphine compound is selected from at least one of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, dimethylethylphosphine, dimethylpropylphosphine, dimethylbutylphosphine, diethylmethylphosphine, diethylpropylphosphine, diethylbutylphosphine, dipropylmethylphosphine, dipropylethylphosphine, dipropylbutylphosphine, dibutylmethylphosphine, dibutylethylphosphine, dibutylpropylphosphine, dimethylphenylphosphine, diethylphenylphosphine, dipropylphosphine, dibutylphosphine and triphenylphosphine, preferably from trimethylphosphine.
6. The use according to claim 5, wherein the polysaccharide-based cationic polymer has a degree of substitution of a substituent group substituted with at least one of a tertiary amine compound and a tertiary phosphine compound of 0.01 to 3, preferably 0.05 to 3, and more preferably 0.1 to 3.
7. Use according to any one of claims 1 to 4, wherein the polysaccharide-based cationic polymer is prepared by a preparation method comprising the steps of: polysaccharide or polysaccharide derivative and acylating reagent are used as raw materials to react to prepare the polysaccharide-based cationic polymer.
Preferably, the raw material further comprises at least one compound of tertiary amine compounds and tertiary phosphine compounds.
8. An antimicrobial material comprising the polysaccharide-based cationic polymer of any one of claims 1 to 7.
9. The use of the fungicidal material according to claim 8 for the prevention and control of agricultural and forestry diseases and food spoilage caused by the spread and infection of pathogenic microorganisms such as bacteria and fungi.
Preferably, the plant black rot disease caused by at least one of the pathogens of phytophthora blight, fusarium oxysporum and fusarium solani.
10. A method for controlling an agricultural or forestry disease, which comprises contacting the fungicidal material according to claim 8 with an agricultural or forestry crop susceptible to an agricultural or forestry disease caused by the spread and infection of pathogenic microorganisms such as bacteria and fungi;
alternatively, the fungicidal material according to claim 8 is contacted with foodstuffs which are susceptible to putrefaction caused by propagation and infection of pathogenic microorganisms such as bacteria and fungi;
alternatively, the fungicidal material according to claim 8 is brought into contact with an environment susceptible to diseases caused by the spread and infection of pathogenic microorganisms such as bacteria and fungi.
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