Rare earth functional material for preventing and treating cotton verticillium wilt as well as preparation method and application of rare earth functional material

Abstract

The invention provides a rare earth functional material for preventing and treating cotton verticillium wilt and a preparation method and application thereof.The rare earth functional material comprises an intermediate, a carrier and water according to the mass ratio of (4-6): (4-6): (18-25), and the intermediate comprises a rare earth lanthanum source compound, a medium and water according to the mass ratio of (7-15): (2-7): (78-89). The rare earth functional material LCP has a particularly strong inhibition effect on verticillium dahliae which is a pathogenic bacterium of cotton verticillium wilt, compared with a common pesticide thiophanate methyl in the market, the inhibition effect of the rare earth functional material LCP is obviously better than that of the pesticide thiophanate methyl, the toxic effect on plants is low, the material is expected to be applied to preparation of pesticides, and the application prospect is wide. The composition is used for controlling cotton verticillium wilt, increasing cotton yield in China and improving cotton quality.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticide preparations, and in particular relates to a rare earth functional material for preventing and controlling cotton verticillium wilt, and a preparation method and application thereof. Background Art

[0002] Verticillium wilt is a soil-borne fungal disease of cotton caused by Verticillium dahliae Kleb. It is widespread worldwide and is particularly severe in warm, humid regions. Verticillium wilt not only leads to a significant decline in cotton yield but also severely impacts cotton fiber quality, causing significant economic losses to the cotton industry. Due to the robust survival and wide host range of the cotton Verticillium wilt pathogen, traditional control methods such as crop rotation and deep plowing often fail to achieve optimal results. Therefore, chemical pesticides play a vital role in the control of cotton Verticillium wilt. However, the long-term and extensive use of chemical pesticides has also led to a series of problems, such as environmental pollution, pesticide residues, and increased resistance among pathogens. To address these issues, researchers have begun exploring safer and more effective pesticides for the control of cotton Verticillium wilt. On one hand, researchers are committed to developing new biopesticides, such as biological agents that use antagonistic microorganisms and biotoxins to inhibit the growth and reproduction of the pathogen. These biopesticides offer advantages such as high selectivity and environmental friendliness, and are expected to become an important tool for the future control of cotton Verticillium wilt. Meanwhile, researchers are also working to improve the efficiency and safety of chemical pesticides. For example, by improving pesticide formulations and optimizing application techniques, pesticide usage and residue levels can be reduced. Furthermore, efforts are underway to strengthen pesticide resistance monitoring and management to prevent pathogens from developing resistance. In addition to developing new pesticides, researchers are also focusing on integrating pesticides with other control measures. For example, combining pesticides with biological control and agronomic practices to form an integrated control system can improve effectiveness and reduce costs. In short, research on pesticides for cotton Verticillium wilt is a complex and urgent task. With the continuous advancement of science and technology and growing awareness of environmental protection, future research on pesticides for cotton Verticillium wilt will place greater emphasis on safety, effectiveness, and environmental friendliness. At the same time, governments and research institutions around the world are increasing their investment in supporting the research and development of pesticides for cotton Verticillium wilt to jointly address this global challenge. Summary of the Invention

[0003] In view of this, the present invention aims to overcome the defects in the prior art and proposes a rare earth functional material for preventing and treating cotton verticillium wilt, and a preparation method and application thereof.

[0004] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0005] In a first aspect, the present invention provides a rare earth functional material LCP for preventing and controlling cotton wilt, comprising an intermediate, a carrier and water in a mass ratio of (4-6): (4-6): (18-25), wherein the intermediate comprises a rare earth lanthanum source compound, a medium and water in a mass ratio of (7-15): (2-7): (78-89).

[0006] Preferably, the rare earth lanthanum source compound is selected from one or more of lanthanum chloride, lanthanum nitrate, lanthanum oxide, lanthanum citrate, and lanthanum sulfate.

[0007] Preferably, the medium is sodium sulfosalicylate.

[0008] Preferably, the carrier is 5,7-dichloro-8-hydroxyquinaldine.

[0009] Preferably, the preparation method of the intermediate comprises the following steps:

[0010] The rare earth lanthanum source compound and the medium are dissolved in water, and the mixture is reacted for 30-60 minutes at a temperature of 40-60° C. and a rotation speed of 500-1200 rpm to obtain the product.

[0011] In a second aspect, the present invention provides a method for preparing the rare earth functional material LCP for preventing and treating cotton Verticillium wilt, comprising the following steps:

[0012] The intermediate and the carrier are mixed evenly and added to a hydrothermal reactor. Water is then added to the reactor. After mixing evenly, the mixture is reacted at 100-150°C for 2-4 hours. Finally, the mixture is dried to obtain the rare earth functional material LCP.

[0013] In a third aspect, the present invention also provides the use of the rare earth functional material LCP in the preparation of a biocontrol agent for inhibiting Verticillium dahliae.

[0014] In a fourth aspect, the present invention also provides the use of the rare earth functional material LCP in preventing and treating cotton Verticillium wilt.

[0015] Preferably, the pathogen of cotton Verticillium wilt is Verticillium dahliae.

[0016] Among all the components of the rare earth functional material LCP of the present invention, the reasonable ratio of rare earth elements and media can effectively stimulate the bactericidal effect of the carrier, so that it has sufficient bactericidal strength to achieve an inhibitory effect on stubborn bacteria such as Verticillium dahliae. At the same time, the rare earth elements and media are plant immune inducers that can "stimulate" the plant's own immune system to resist diseases. This formula treats both the symptoms and the root cause.

[0017] The rare earth functional material LCP of the present application can penetrate into plant tissues through leaf epidermis and be absorbed by root system and transported to stem and leaf parts when sprayed on the surface of plants, and can be uniformly distributed in all parts of the plant, forming continuous protection to the newly formed tender tissues, and especially having inhibiting hyphal splitting effect on the mycelium invading into the subcutaneous layer of the plant, thereby achieving the effect of eradicating pathogenic bacteria.

[0018] Compared with the prior art, the present application has the following advantages:

[0019] The rare earth functional material LCP has particularly strong inhibiting effect on the pathogenic bacteria of cotton verticillium wilt, i.e. verticillium dahliae, and has low toxicity to plants, and is expected to be applied to the preparation of pesticides to prevent and control cotton verticillium wilt and improve cotton yield and quality. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 SEM electron microscope photos of LCP1 prepared in Example 1;

[0021] Figure 2 Antibacterial effects of LCP materials on verticillium dahliae in different embodiments;

[0022] Figure 3 Antibacterial effects of LCP materials on verticillium dahliae under different storage conditions;

[0023] Figure 4 Toxicity detection results of LCP materials on cotton seedlings;

[0024] Figure 5 pH of LCP material solution. DETAILED DESCRIPTION

[0025] The embodiments of the present application are described in detail below. The embodiments described below are exemplary and are only used to explain the present application, and cannot be understood as a limitation of the present application.

[0026] In this text, unless otherwise defined, all technical and scientific terms used herein have the same meaning as understood by those skilled in the art to which the present application belongs.

[0027] In this text, in the case of describing a value as a range, it should be understood that such disclosure includes the disclosure of all possible sub-ranges within the range, and the specific numerical values falling within the range, regardless of whether the specific numerical values or specific sub-ranges are explicitly indicated.

[0028] In this text, as long as there is no special limitation, the term "a plurality of" or the like refers to more than two or equal to two in quantity. For example, "one or more" means one or more than two.

[0029] In this document, the terms “preferably” and “more preferably” are only used to describe implementation methods or examples with better effects. It should be understood that they do not limit the scope of protection of the present invention.

[0030] In this document, the word "further" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0031] In this article, the term "and / or" is used to describe the association relationship between objects, indicating that three relationships can exist. For example, A and / or B means: A or B, or A and B.

[0032] As used herein, the term "about" means + / - 10%, preferably + / - 5%, more preferably + / - 1% of the specified value.

[0033] In this document, the terms “include,” “including,” “have,” “contain,” etc. are open-ended terms, meaning including but not limited to.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention.

[0035] The present invention will be described in detail below with reference to the embodiments.

[0036] Example 1 Synthesis of rare earth functional material LCP1:

[0037] 7 parts of lanthanum chloride and 2 parts of sodium sulfosalicylate are dissolved in 89 parts of water, mixed and reacted at a temperature of 40°C and a rotation speed of 500 rpm for 30 minutes to prepare an intermediate. Take 40 parts of the intermediate and 40 parts of 5,7-dichloro-8-hydroxyquinaldine, mix them well and add them to a hydrothermal reactor, then add 250 parts of water to the reactor, mix them evenly and place them at 100°C for 2 hours, and finally dry them to obtain the rare earth functional material LCP1 (hereinafter referred to as LCP1). The electron microscope scanning photo of the prepared rare earth functional material LCP1 is shown as follows: Figure 1 shown.

[0038] Example 2 Synthesis of rare earth functional material LCP2:

[0039] 15 parts of lanthanum nitrate and 7 parts of sodium sulfosalicylate were dissolved in 78 parts of water and reacted at 60°C and 1200 rpm for 60 minutes to prepare an intermediate. 60 parts of the intermediate was mixed with 60 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 180 parts of water was then added to the reactor, mixed thoroughly, and allowed to react at 150°C for 4 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP2 (hereinafter referred to as LCP2).

[0040] Example 3 Synthesis of rare earth functional material LCP3:

[0041] 12 parts of lanthanum oxide and 5 parts of sodium sulfosalicylate were dissolved in 83 parts of water and reacted at 50°C and 800 rpm for 40 minutes to prepare an intermediate. 50 parts of the intermediate was mixed with 50 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 210 parts of water were then added to the reactor, mixed thoroughly, and allowed to react at 120°C for 3 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP3 (hereinafter referred to as LCP3).

[0042] Example 4 Synthesis of rare earth functional material LCP4:

[0043] 15 parts of lanthanum citrate and 2 parts of sodium sulfosalicylate were dissolved in 83 parts of water and reacted at 40°C and 1000 rpm for 50 minutes to prepare an intermediate. 45 parts of the intermediate was mixed with 55 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 210 parts of water were then added to the reactor, mixed thoroughly, and allowed to react at 140°C for 4 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP4 (hereinafter referred to as LCP4).

[0044] Example 5 Synthesis of rare earth functional material LCP5:

[0045] 7 parts of lanthanum sulfate and 7 parts of sodium sulfosalicylate were dissolved in 86 parts of water and reacted at 50°C and 700 rpm for 40 minutes to prepare an intermediate. 60 parts of the intermediate was mixed with 40 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 230 parts of water were then added to the reactor, mixed thoroughly, and allowed to react at 140°C for 2 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP5 (hereinafter referred to as LCP5).

[0046] Comparative Example 1 Synthesis of rare earth functional material LCP6:

[0047] 20 parts of lanthanum oxide and 5 parts of sodium sulfosalicylate were dissolved in 83 parts of water and reacted at 50°C and 800 rpm for 40 minutes to prepare an intermediate. 50 parts of the intermediate was mixed with 50 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 210 parts of water were then added to the reactor, mixed thoroughly, and allowed to react at 120°C for 3 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP6 ​​(hereinafter referred to as LCP6).

[0048] Comparative Example 2 Synthesis of rare earth functional material LCP7:

[0049] 12 parts of lanthanum oxide and 10 parts of sodium sulfosalicylate were dissolved in 83 parts of water and reacted at 50°C and 800 rpm for 40 minutes to prepare an intermediate. 50 parts of the intermediate was mixed with 50 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 210 parts of water were then added to the reactor, mixed thoroughly, and allowed to react at 120°C for 3 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP7 (hereinafter referred to as LCP7).

[0050] Comparative Example 3 Synthesis of rare earth functional material LCP8:

[0051] 12 parts of lanthanum oxide and 5 parts of sodium sulfosalicylate were dissolved in 83 parts of water and reacted at 50°C and 800 rpm for 40 minutes to prepare an intermediate. 30 parts of the intermediate was mixed with 50 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 210 parts of water were then added to the reactor, mixed thoroughly, and allowed to react at 120°C for 3 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP8 (hereinafter referred to as LCP8).

[0052] Comparative Example 4: Synthesis of rare earth functional material LCP9:

[0053] 12 parts of lanthanum oxide and 5 parts of sodium sulfosalicylate were dissolved in 83 parts of water and reacted at 50°C and 800 rpm for 40 minutes to prepare an intermediate. 50 parts of the intermediate was mixed with 30 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 210 parts of water were then added to the reactor, mixed thoroughly, and allowed to react at 120°C for 3 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP9 (hereinafter referred to as LCP9).

[0054] Comparative Example 5 Synthesis of rare earth functional material LCP10:

[0055] 5 parts of sodium sulfosalicylate were dissolved in 83 parts of water and reacted at 50°C and 800 rpm for 40 minutes to prepare an intermediate. 50 parts of the intermediate were mixed with 50 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 210 parts of water were then added to the reactor, mixed thoroughly, and allowed to react at 120°C for 3 hours. Finally, the functional material LCP10 (hereinafter referred to as LCP10) was obtained by drying.

[0056] Comparative Example 6 Synthesis of rare earth functional material LCP11:

[0057] 12 parts of lanthanum oxide was dissolved in 83 parts of water and reacted at 50°C and 800 rpm for 40 minutes to prepare an intermediate. 50 parts of the intermediate was mixed with 50 parts of 5,7-dichloro-8-hydroxyquinaldine and added to a hydrothermal reactor. 210 parts of water was then added to the reactor, mixed thoroughly, and allowed to react at 120°C for 3 hours. Finally, the mixture was dried to obtain the rare earth functional material LCP11 (hereinafter referred to as LCP11).

[0058] Experimental Example 1 Detection of the effect against Verticillium dahliae

[0059] The Verticillium dahliae was inoculated on a PDA culture medium plate, and then placed in a constant temperature incubator and cultured at 27°C for 14 days. After the Verticillium dahliae strains grew well, a plate full of Verticillium dahliae pathogenic hyphae was selected, and a Verticillium dahliae block with a diameter of 8 mm was dug out with a puncher or a sterile 1mL pipette tip. The Verticillium dahliae block was placed in the center of the PDA plate, and a small piece of circular filter paper was placed 1.5 cm away from the center of the block. 5uL (concentration 0.2%) of the test material LCP1-LCP12 solution was added to the filter paper. At the same time, a group of PDA plates with only Verticillium dahliae blocks and no liquid was added was set as a negative control. Each experiment was set up in parallel with 3 groups, and cultured in a dark environment at 27°C for 17 days. After 17 days, the colony diameter of the Verticillium dahliae was taken out and measured. The colony diameter of the control group was compared to calculate the inhibitory effect of the rare earth material on Verticillium dahliae.

[0060] The experimental results are as follows Figure 2 As shown, when the material concentration is 0.2%, the antibacterial effect of LCP1-LCP5 on Verticillium dahliae is 100%, and the Verticillium dahliae cake has almost no growth, while LCP6-11 has no inhibitory effect on Verticillium dahliae, and the growth rate of Verticillium dahliae is almost the same as that of the control group.

[0061] Experimental Example 2 Detection of the duration of the effect against Verticillium dahliae

[0062] After the preparation of the material LCP1, it was placed and stored at room temperature. After 2 months, 4 months, 6 months, 8 months, and 10 months, the resistance to Verticillium dahliae was tested. The detection method was the same as that of Experimental Example 1 to verify the effective storage period of the material LCP under natural conditions.

[0063] The experimental results are as follows Figure 3 As shown, after 2, 4, 6, 8, and 10 months of storage at room temperature, the material maintained a 100% inhibitory effect on Verticillium dahliae, with no Verticillium dahliae growth on the experimental plates. This indicates that the material has a relatively stable structure and shelf life, which is beneficial for subsequent production and storage.

[0064] Experimental Example 3: Toxic Effects of Cotton (Appearance)

[0065] Plant safety testing was conducted using a 0.2% concentration of LCP1. Three cotton seedlings were selected, each of which was roughly the same size and height. To simulate field conditions, all seedlings were placed outdoors, protected from sunlight, temperature, and rainfall. Under these conditions, a 0.2% solution of each material was placed in an agricultural sprayer. Foliar application was completed by spraying the cotton seedling once in each of the four directions, centered at a distance of 0.5 meters. Three additional cotton seedlings were sprayed with distilled water daily and once weekly for four weeks. Plant height, main stem diameter, and leaf health were recorded weekly. Yellowing, wilting, and lodging were observed to determine if the solution had any toxic effects on the cotton seedlings.

[0066] Table 1 Various indicators of cotton seedlings

[0067] control group Leaf width (cm) Leaf height (cm) Experimental group Leaf width (cm) Leaf height (cm) Week 1 8.4 2.1 Week 1 8.3 2.2 Week 2 10.2 3.4 Week 2 10.5 3.4 Week 3 12.5 4.7 Week 3 12.8 4.6 Week 4 15.2 5.9 Week 4 14.9 5.8

[0068] Cotton seedling status Figure 4 As shown in Table 1, the various indicators of cotton showed no yellowing, wilting or lodging of leaves, and there was no obvious difference in the thickness of leaves and main stem diameters, indicating that rare earth pesticides at this concentration had no obvious toxic effect on cotton.

[0069] Experimental Example 4: Acidity and Alkalinity Detection

[0070] Pesticides that are too acidic or too alkaline can harm crops. Improper soil pH can hinder crop absorption of nutrients, leading to stunted growth and poor development, which in turn affects crop yield and quality. For example, overly acidic soil can increase the toxicity of ions like aluminum and manganese, hindering the release of phosphorus. Overly alkaline soil, on the other hand, can reduce the effectiveness of elements like calcium, magnesium, boron, and silicon, and can immobilize phosphorus, hindering crop absorption. Therefore, when using pesticides, care should be taken to control pH to protect crop growth. To prevent this, we test the pH of rare earth material solutions. Specifically, we prepare a saturated solution, a 200-fold dilution, and a 500-fold dilution of the rare earth material and then measure the pH of the solution using a pH meter.

[0071] The experimental results are as follows Figure 5 As shown, experiments have found that the pH values ​​of the rare earth material in saturated solution, 200-fold diluted solution and 500-fold diluted solution are close to neutral, and the harm to crops and soil is relatively small, making it more suitable for the preparation of pesticides for preventing and controlling cotton wilt.

[0072] In summary, the present invention proposes a rare earth functional material LCP for controlling Verticillium wilt in cotton. This material effectively inhibits the growth and reproduction of the pathogenic bacteria that causes Verticillium wilt in cotton. It features a simple production process, easy storage, a neutral pH, a long-lasting efficacy, and low toxicity to cotton plants. This material is expected to be applied in the preparation of pesticides for controlling Verticillium wilt in cotton, increasing cotton yields and improving cotton quality in my country.

[0073] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A rare earth functional material LCP for preventing and treating cotton Verticillium wilt, characterized by: The invention comprises an intermediate, a carrier and water in a mass ratio of (4-6): (4-6): (18-25), wherein the intermediate comprises a rare earth lanthanum source compound, a medium and water in a mass ratio of (7-15): (2-7): (78-89).

2. The rare earth functional material LCP for preventing and treating cotton Verticillium wilt according to claim 1, characterized in that: The rare earth lanthanum source compound is selected from one or more of lanthanum chloride, lanthanum nitrate, lanthanum oxide, lanthanum citrate, and lanthanum sulfate.

3. The rare earth functional material LCP for preventing and treating cotton Verticillium wilt according to claim 1, characterized in that: The medium is sodium sulfosalicylate.

4. The rare earth functional material LCP for preventing and treating cotton Verticillium wilt according to claim 1, characterized in that: The carrier is 5,7-dichloro-8-hydroxyquinaldine.

5. The rare earth functional material LCP for preventing and treating cotton Verticillium wilt according to claim 1, characterized in that: The preparation method of the intermediate comprises the following steps: The rare earth lanthanum source compound and the medium are dissolved in water, and the mixture is reacted for 30-60 minutes at a temperature of 40-60° C. and a rotation speed of 500-1200 rpm to obtain the product.

6. The method for preparing the rare earth functional material LCP for preventing and treating cotton Verticillium wilt according to any one of claims 1 to 5, characterized in that: The steps include: The intermediate and the carrier are mixed evenly and added to a hydrothermal reactor. Water is then added to the reactor. After mixing evenly, the mixture is reacted at 100-150°C for 2-4 hours. Finally, the mixture is dried to obtain the rare earth functional material LCP.

7. Use of the rare earth functional material LCP according to any one of claims 1 to 5 in the preparation of a biocontrol agent for inhibiting Verticillium dahliae.

8. Use of the rare earth functional material LCP according to any one of claims 1 to 5 in preventing and treating cotton Verticillium wilt.

9. The use according to claim 1, characterized in that: The pathogen of cotton verticillium wilt is Verticillium dahliae.

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