CN110204509B - Benzothiadiazole-selenium nano complex and preparation method and application thereof - Google Patents

Benzothiadiazole-selenium nano complex and preparation method and application thereof Download PDF

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CN110204509B
CN110204509B CN201910406756.9A CN201910406756A CN110204509B CN 110204509 B CN110204509 B CN 110204509B CN 201910406756 A CN201910406756 A CN 201910406756A CN 110204509 B CN110204509 B CN 110204509B
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bth
selenium
benzothiadiazole
senps
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王光
朱世江
彭苗苗
陈卓盛
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South China Agricultural University
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00Protecting plants
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
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    • C07DHETEROCYCLIC COMPOUNDS
    • C07D285/00Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01Five-membered rings
    • C07D285/02Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/14Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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    • Y02A40/10Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture

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Abstract

The invention discloses a diazosulfide-selenium nano complex and a preparation method and application thereof. The diazosulfide-selenium nano complex is prepared by the following steps: respectively preparing a BTH aqueous solution A and a sodium selenite aqueous solution B; mixing the two solutions according to a certain proportion, adding ascorbic acid, fully mixing, and standing for reaction; and then carrying out low-speed centrifugation on the mixed solution, then taking the supernatant, carrying out low-temperature high-speed centrifugation, and collecting fluid-like precipitate to obtain the product. The BTH-SeNPs have good stability and dispersibility and are convenient to use; compared with the independent use of BTH, the BTH has better effect of preventing anthracnose, less dosage and lower cost; the method has the advantages of improving the disease resistance of vegetables, effectively preventing anthracnose, reducing the use of chemical pesticides and improving the food safety and economic value of the flowering Chinese cabbage.

Description

Benzothiadiazole-selenium nano complex and preparation method and application thereof
Technical Field
The invention relates to the technical field of fruit and vegetable disease resistance, and in particular relates to a diazosulfide-selenium nano complex and a preparation method and application thereof.
Background
The flowering cabbage (Brassica campestris L.ssp. chinensis var. utilis Tsen et Lee), also called a flowering cabbage, is a special vegetable in southern areas of China, and is an important vegetable crop with the largest cultivation area and annual production supply in Guangdong province. The vegetable beverage has unique flavor and high nutritive value, is deeply loved by people and is praised as the crown of vegetable. The flowering Chinese cabbage is suitable for internal marketing, can be exported for earning foreign exchange, and has important economic value. Anthracnose is one of the most common and serious diseases during the cultivation of the flowering cabbage, is particularly easy to occur under high-temperature and high-humidity climatic conditions in southern areas of China, and seriously affects the yield and quality of the flowering cabbage, so that the flowering cabbage loses edible value and commodity value.
The most effective method for controlling anthracnose of cabbage at present is to apply a chemical bactericide, but the anthracnose of cabbage in southern areas of China has the drug resistance of different degrees due to the long-term use of the chemical bactericide. The problems of environmental pollution, pesticide residue and the increase of drug resistance of pathogenic bacteria have caused common concerns of consumers, and the use of the pesticide is increasingly limited. Therefore, the research and development of a method for safely, efficiently and effectively preventing and controlling anthracnose of the flowering cabbage and reducing the cultivation loss of the flowering cabbage are urgently needed. Has important significance for increasing economic benefit of vegetable farmers, promoting healthy development of vegetable heart industry and improving competitiveness of the vegetable heart exported international market.
In recent years, the disease resistance induction technology has become a hotspot of research on crop disease control, is considered to be the most promising method for controlling crop diseases by replacing chemical agents, and opens up wide prospects for controlling vegetable diseases. The principle is that the defense reaction or immune resistance reaction of the plant is utilized, and the Systemic Acquired Resistance (SAR) of the plant is improved by using the resistance inducer, so that the occurrence and the development of crop diseases are reduced. The use of the resistance inducer can lead the flowering cabbage to obtain favorable growth conditions in the field, is beneficial to improving the quality and the stress resistance of the flowering cabbage, has the advantages of high efficiency, low toxicity, broad spectrum and the like, is harmless to the environment, and is safe to people and livestock. Therefore, the research and development of novel plant resistance inducer is more and more paid attention to by people, the technology is favorable for reducing the use of chemical bactericide for crops, and the food quality safety of agricultural products is improved.
Diazosulfide (BTH) is a salicylic acid functional analogue, and when applied with exogenous BTH, the BTH can induce plants to generate systemic acquired resistance and improve the resistance of crops to pathogenic microorganisms, while the BTH does not have the activity of inhibiting the growth of the microorganisms. However, no research report on the application of BTH in the prevention and control of anthracnose of cabbage heart is found. In addition, the BTH aqueous solution is unstable in character, is easy to precipitate and is not favorable for uniform spraying in production and application. In addition, due to the reasons of high price of BTH, extremely high use cost and the like, BTH has a larger bottleneck problem in the application and popularization process of preventing and controlling diseases of the flowering cabbage.
Selenium (Se) is one of essential trace elements for human body, is a composition of various enzymes in human body, has various biological activity functions, and plays roles in resisting diseases, delaying aging, enhancing immunity and the like in life. The intake of selenium in human beings comes from food, and the insufficient intake of selenium easily causes diseases and causes human healthBecomes a great threat. Selenium is distributed in geological structures such as soil, rock and the like in nature and exists in selenium compounds with various forms, and the valence state of the selenium compound is Se6+、Se4+、Se2+、Se0And Se2-And the like. Inorganic selenium such as selenate and selenite, which is the main soluble selenium in soil; the organic selenium in the plant, such as selenoprotein, seleno amino acid, selenium polysaccharide and the like, is the result of the plant absorbing and converting inorganic selenium in soil into organic selenium through a physiological metabolic pathway.
The nano-selenium is a reduced selenium monomer, has extremely small particle size and is easy to be absorbed and utilized by passive plants and human bodies. Moreover, nano-selenium has the lowest chemical toxicity compared with inorganic selenium and organic selenium. Selenium has various physiological functions on plants, including improving the oxidation resistance of the plants, delaying aging and the like. Research shows that the shelf life of fruits such as pears, jujubes, strawberries, peaches and the like can be effectively prolonged by spraying inorganic selenium with proper concentration. In addition, the inorganic selenium treatment before picking effectively maintains the picked quality of vegetables such as lettuce, broccoli, tomato and the like, and prolongs the storage and transportation time of the vegetables. However, the selenium is rarely used for controlling the disease resistance of vegetables, and the inorganic selenium has high toxicity, so the selenium is easy to poison crops and is difficult to popularize and apply. The nano-selenium has obvious advantages due to low toxicity and high absorption efficiency, but no research report is found for the prevention and control of vegetable diseases by using the nano-selenium at present.
Disclosure of Invention
The invention aims to provide a benzothiadiazole-selenium nano complex, and a preparation method and application thereof. According to the invention, the BTH is used as a template to synthesize the benzothiadiazole-selenium nano complex for the first time, the benzothiadiazole-selenium nano complex is a nano particle with the particle size of 30-100nm, is good in stability and dispersibility, is easy to be absorbed by plants, can effectively improve the disease resistance of the heart of a vegetable, reduce the incidence rate of anthracnose disease of the heart of a vegetable, improve the quality and safety of the heart of a vegetable, improve the yield and economic value of the heart of a vegetable, and has a good application effect in disease prevention and control of other similar vegetables.
The invention also aims to provide a preparation method of the benzothiadiazole-selenium nano complex.
The invention further aims to provide application of the benzothiadiazole-selenium nano complex.
The above object of the present invention is achieved by the following scheme:
a diazosulfide-selenium nano complex is prepared by the following steps: preparing an aqueous solution A and an aqueous solution B of sodium selenite of 1,2, 3-benzothiadiazole-7-thioformic acid S-methyl ester (BTH) respectively; uniformly mixing the two solutions to ensure that the final concentration range of BTH in the mixed solution is 1-100 mg/L and the final concentration range of sodium selenite is 1-1000 mg/L; then adding ascorbic acid, uniformly mixing and standing; and then centrifuging the mixed solution at a low speed of 500-2000 rpm for 2-10 min, taking the supernatant, centrifuging the supernatant at a high speed of 10000-15000 rpm for 10-30 min at 4-20 ℃, and collecting the precipitate, namely the benzothiadiazole-selenium nano complex (BTH-SenPs).
In the preparation process of BTH-SeNPs, after the reaction is finished, in order to efficiently and high-quality collect the BTH-SeNPs, low-speed centrifugation is firstly carried out, and then high-speed centrifugation is carried out, wherein the rotation speed of the low-speed centrifugation is 500-2000 rpm, and the centrifugation within the rotation speed range can well remove insoluble substances in liquid, such as BTH which does not participate in the reaction; then high-speed centrifugation is carried out, so that BTH-SeNPs particles can be collected, and impurities such as ascorbic acid in the BTH-SeNPs are removed, so that the high-efficiency and high-quality recovery of the BTH-SeNPs is realized; when the rotation speed of the high-speed centrifugation is too high, BTH-SeNPs can be recovered, but the BTH-SeNPs are easy to aggregate and agglomerate, and the solubility of the BTH-SeNPs is influenced.
The diazosulfide-selenium nano complex (BTH-SeNPs) is nano particles, the particle size is 30-100nm, the nano particles are beneficial to absorption and conversion of leaf surfaces, and the utilization efficiency of the leaf surfaces to medicaments is improved; compared with the independent use of BTH, the BTH-SeNPs have better effect of preventing anthracnose, less dosage, lower cost (lower cost of nano selenium compared with BTH), better stability and dispersibility and more convenient use.
Preferably, the final concentration of the S-methyl 1,2, 3-benzothiadiazole-7-thiocarbamate in the mixed solution is 40-80 mg/L, and the final concentration of the sodium selenite is 50-200 mg/L.
More preferably, the final concentration of the S-methyl 1,2, 3-benzothiadiazole-7-thiocarbamate in the mixed solution is 75mg/L, and the final concentration of the sodium selenite in the mixed solution is 75 mg/L.
Preferably, the ascorbic acid is L-ascorbic acid; the molar mass ratio of the ascorbic acid to the sodium selenite is 3-10: 1.
More preferably, the molar mass ratio of ascorbic acid to sodium selenite is 5: 1.
Preferably, the rotation speed of the low-speed centrifugation is 1500 rpm; the centrifugation time was 5 min.
Preferably, the rotating speed of the high-speed centrifugation is 13000 rpm; centrifuging for 20 min; the centrifugation temperature was 4 ℃.
Preferably, after the aqueous solution A and the aqueous solution B are mixed, ultrasonic treatment can be carried out for 5min at the temperature of 20-37 ℃.
Preferably, the mixed solution can be subjected to ultrasonic treatment for 10min, and then is kept still for more than 4 h.
Preferably, the BTH-SeNPs precipitate needs to be prepared into a mother solution for storage, and the concentration range of the mother solution is 50-100 mg/L. When the precipitate of BTH-SeNPs is stored dry and then reconstituted at the time of use, the solubility thereof tends to be lowered. The concentration of BTH-SeNPs mother liquor can be obtained by freeze drying, weighing and calculating.
The invention also protects the application of the benzothiadiazole-selenium nano complex in preparing a resistance inducer.
The invention also protects the application of the benzothiadiazole-selenium nano complex in preparing the drugs for preventing anthracnose.
Preferably, the anthracnose prevention drug is a cruciferous vegetable anthracnose prevention drug.
More preferably, the cruciferous vegetables are cabbage heart, chinese cabbage, etc.
Preferably, the application mode of the anthracnose preventive drug is foliage spraying or root irrigation.
Compared with the prior art, the invention has the following beneficial effects:
(1) the benzothiadiazole-selenium nano complex (BTH-SeNPs) is nano particles, the particle size is 30-100nm, the stability and the dispersibility are better, and the use is more convenient; the absorption and transformation of the leaf surfaces are facilitated, and the utilization efficiency of the leaf surfaces to the medicament is improved;
(2) compared with the independent use of BTH, the BTH-SeNPs have better effect of preventing anthracnose, less dosage and lower cost;
(3) the BTH-SeNPs are beneficial to reducing the use of chemical pesticides, improving the quality and safety of the vegetable heart, improving the yield and economic value of the vegetable heart and having better application effects in disease prevention and control of other similar vegetables while improving the disease resistance of the vegetables, effectively preventing anthracnose and reducing the incidence rate of anthracnose diseases of the vegetable heart.
Drawings
FIG. 1 shows the aqueous solution properties of BTH-SeNPs prepared in example 1 and their Tyndall effect.
FIG. 2 is a Scanning Electron Microscope (SEM) picture of BTH-SeNPs prepared in example 1, wherein A is BTH-SeNPs; b is Na2SeO3(ii) a C is BTH.
FIG. 3 shows the effect of different treatments on anthracnose incidence.
FIG. 4 shows the effect of different drugs on the incidence of anthracnose of cabbage heart.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
Example 1
A benzothiadiazole-selenium nanocomplex (BTH-SeNPs) is prepared from the following raw materials: 1,2, 3-benzothiadiazole-7-thioformic acid S-methyl ester (BTH), sodium selenite, ascorbic acid and water.
The preparation method comprises the following specific steps:
(1) preparing an aqueous solution A of 1,2, 3-benzothiadiazole-7-thioformic acid S-methyl ester (BTH), wherein the concentration of BTH is 150 mg/L;
(2) preparing sodium selenite water solution B, wherein the concentration of sodium selenite is 150 mg/L;
(3) uniformly mixing the aqueous solution A and the aqueous solution B according to the volume ratio of 1: 1; in order to mix the two solutions more uniformly, the solutions can be mixed and then subjected to ultrasonic treatment for 5min at the temperature of 20-37 ℃;
(4) adding ascorbic acid (the amount of the ascorbic acid is 5 times of that of the sodium selenite substance) into the solution obtained in the step (3), uniformly stirring, carrying out ultrasonic treatment for 10min, standing at room temperature for reaction, gradually changing the color of the reaction solution from colorless to red, reacting slowly, and standing for more than 4 hours;
(5) centrifuging the mixed solution obtained in the step (4) at 1500rpm for 5min at a low speed, and collecting supernatant;
(6) and centrifuging the obtained supernatant at 13000rpm at 4 ℃ for 20min, and collecting fluid-like precipitate to obtain the benzothiadiazole-selenium nano complex (BTH-SenPs).
The BTH-SeNPs sediment needs to be prepared into mother liquor for storage. When the precipitate of BTH-SeNPs is stored dry and then reconstituted at the time of use, the solubility thereof tends to be lowered.
In order to accurately measure the concentration of the BTH-SeNPs, a certain volume of BTH-SeNPs mother liquor is freeze-dried by adopting a freeze-drying method, the weight of the BTH-SeNPs mother liquor is accurately weighed by using an analytical balance, the concentration of the mother liquor can be calculated, and the BTH-SeNPs mother liquor is diluted according to the required concentration before use.
And adding a certain amount of purified water into the prepared BTH-SeNPs precipitate to obtain clear and transparent red liquid, namely BTH-SeNPs mother liquor, wherein the concentration of the BTH-SeNPs mother liquor can be measured by a freeze drying method.
The BTH-SeNPs preparation prepared by the method has stable liquid chemical property, is red and transparent, does not precipitate after standing for more than 1 month, and generates obvious Tyndall effect (figure 1) when irradiated by a laser pen, wherein the Tyndall effect is a common physical method for distinguishing colloid and solution, and the particle size of the BTH-SeNPs is very small and can reach less than 100 nm.
The results of the detection by a scanning electron microscope are shown in FIG. 2, wherein A is BTH-SeNPs particles, B is sodium selenite particles and C is BTH particles; comparing the scanning pictures of the electron microscope of BTH and sodium selenite, the particles of BTH-SeNPs are spherical, the size range of the nanoparticles is about 30-100nm, and the independent BTH and inorganic selenium are both in an irregular state, so that the BTH-SeNPs are further verified to be spherical nanoparticles, the dispersibility of the spherical nanoparticles is excellent, the particle size is small, the spherical nanoparticles can be easily absorbed by plants, the absorption and transformation efficiency of the crops can be improved, and the dosage of the medicament can be reduced.
Example 2
A benzothiadiazole-selenium nanocomplex (BTH-SeNPs), the preparation process of which is the same as that in example 1, except that in step (3), after the aqueous solution a and the aqueous solution B are mixed, the final concentration of BTH is 5mg/L and the final concentration of sodium selenite is 5 mg/L; the centrifugal rotating speed in the step (5) is 500 rpm; the centrifugal rotation speed in the step (6) was 15000 rpm.
Example 3
A benzothiadiazole-selenium nanocomplex (BTH-SeNPs), the preparation process is the same as that in example 1, except that the preparation concentration of the solution A in the step (1) is 200 mg/L; the solution B prepared in the step (2) has the concentration of 2000 mg/L; in the step (3), after the aqueous solution A and the aqueous solution B are mixed in equal volume, the final concentration of BTH is 100mg/L and the final concentration of sodium selenite is 1000 mg/L; the centrifugal rotating speed in the step (5) is 2000 rpm; the centrifugal rotation speed in the step (6) is 10000 rpm.
After the BTH-SeNPs prepared in examples 2 and 3 were prepared into solutions, the liquid chemistry and color thereof, and the results of SEM examination were the same as those of the BTH-SeNPs prepared in example 1.
Example 4
The BTH-SeNPs prepared in the example 1 are taken as test objects, mother liquor is taken, purified water is added to prepare a BTH-SeNPs liquid preparation with the concentration of 10mg/L for standby.
And (3) sowing and cultivating the flowering cabbage according to a conventional method, performing leaf spraying treatment by using a BTH-SeNPs preparation with the concentration of 10mg/L, a BTH aqueous solution and a sodium selenite aqueous solution when the flowering cabbage seedling grows to a 3-4 leaf stage, and spraying purified water to a blank control group. 3 days after spraying, the anthracnose of cabbage is inoculated by adopting a needle-stick inoculation method, and each leaf treated differentlySurface puncture sites were accurately inoculated with 10 μ L concentrations of 1 x 105CFU/mL anthrax spore suspension. The flowering plants were covered with a PE bag after inoculation to maintain a high humidity state for 48 hours, and the incidence of inoculated leaves was counted and the diameter of lesions was measured by observing for 3 days from the 4 th day after inoculation.
The incidence of anthracnose of cabbage is shown in FIG. 3, and the lesion diameter on day 6 after inoculation with the pathogenic bacteria is shown in Table 1.
TABLE 1 lesion diameter of leaf spray treated flowering cabbage with different agents on day 6 of anthrax inoculation
Name of process Diameter of lesion (mm)
Blank control (pure water) 5.21
BTH control (10mg/L) 4.83
BTH-SeNPs(10mg/L) 4.02
The results show that: the incidence of anthracnose of the cabbage heart is continuously improved 4-6 days after the artificial inoculation of the anthrax, but the incidence of the anthracnose of the cabbage heart treated by the 10mg/L BTH-SeNPs preparation leaf spraying is improved at a lower speed and is obviously lower than that of a blank control group and a BTH control group. On the 6 th day after artificial inoculation, the incidence rate of flowering cabbage treated by spraying the 10mg/L BTH-SeNPs preparation is 60.3 percent, while the incidence rate of flowering cabbage in the 10mg/L BTH control group is 78.2 percent and the incidence rate in the blank control group is 91.8 percent; therefore, the induced resistance effect of the 10mg/L BTH-SeNPs prepared in the embodiment is obviously higher than that of the BTH control group and the blank control group, and the BTH-SeNPs treatment group and the two control groups have obvious difference; in addition, as can be seen from table 1, the lesion diameter of the BTH-SeNPs formulation spray-treated group was significantly lower than that of the BTH control group and the blank control group; the BTH-SeNPs preparation can obviously improve the resistance of the flowering cabbage to anthracnose during cultivation by using a leaf spraying treatment method.
Example 3
The BTH-SeNPs prepared in example 1 are taken as test objects, mother liquor is taken, purified water is added to prepare a BTH-SeNPs liquid preparation with the concentration of 5mg/L for standby.
And (3) sowing and cultivating the flowering cabbage conventionally, after the 1 st main leaf of the flowering cabbage grows out, irrigating the root with 5mg/L BTH-SeNPs preparation, BTH aqueous solution and sodium selenite aqueous solution for 1 time, irrigating the root with purified water of the same volume in a blank control group, and continuously cultivating the flowering cabbage by using a conventional method before and after root irrigation treatment. When the cabbage heart grows to 3-4 leaves, inoculating anthracnose bacteria by needle-prick inoculation, and accurately inoculating 10 μ L of Bacillus anthracis with concentration of 1 x 10 at the pricked part on the surface of each leaf treated differently5CFU/mL anthrax spore suspension. The flowering plants were covered with a PE bag after inoculation to maintain a high humidity state for 48 hours, and the incidence of inoculated leaves was observed and the diameter of lesions was measured for 3 consecutive days after the 4 th day of inoculation.
The incidence of anthracnose of cabbage is shown in FIG. 4, and the lesion diameter on day 6 after inoculation with the pathogenic bacteria is shown in Table 2.
TABLE 2 influence of different Agents on the diameter of anthracnose lesion in cabbage heart
Name of process Diameter of lesion (mm)
Blank control (pure water) 5.43
BTH control (5mg/L) 4.95
BTH-SeNPs(5mg/L) 4.12
The results show that: the incidence rate of anthracnose of the cabbage heart is continuously improved 4-6 days after the artificial inoculation of the anthrax, but the incidence rate of the cabbage heart treated by root irrigation of 5mg/L BTH-SeNPs preparation is slower and is obviously lower than that of a blank control group and a BTH control group. On the 6 th day, the incidence rate of the cabbage heart treated by root irrigation of 5mg/L BTH-SeNPs preparation is 65.5 percent, while the incidence rate of the cabbage heart treated by root irrigation of 5mg/L BTH aqueous solution is 82.1 percent and the incidence rate of the blank control group is 90.3 percent, and the treated group and the control group have significant difference; in addition, as can be seen from table 2, the lesion diameter of the BTH-SeNPs formulation irrigated root treated group was significantly lower than that of the blank control group and the BTH control group. The BTH-SeNPs preparation can obviously improve the resistance to anthracnose during the cultivation of the Chinese flowering cabbage by using the root irrigation treatment method.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and that those skilled in the art can make other variations or modifications on the basis of the above description and idea, and that all embodiments are neither necessary nor exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The diazosulfide-selenium nano complex is characterized by being prepared by the following steps: respectively preparing an aqueous solution A of 1,2, 3-benzothiadiazole-7-thioformic acid S-methyl ester and an aqueous solution B of sodium selenite; mixing the two solutions uniformly to ensure that the final concentration of the 1,2, 3-benzothiadiazole-7-thioformic acid S-methyl ester in the mixed solution is 1-100 mg/L and the final concentration of sodium selenite is 1-1000 mg/L; adding ascorbic acid, mixing uniformly, standing and reacting for more than 2 hours; and then centrifuging the reaction solution at a low speed of 500-2000 rpm for 2-10 min, taking the supernatant, centrifuging the supernatant at a high speed of 10000-15000 rpm for 10-30 min at 4-20 ℃, and collecting the precipitate, namely the diazosulfide-selenium nano complex.
2. The benzothiadiazole-selenium nanocomplex according to claim 1, wherein the final concentration of S-methyl 1,2, 3-benzothiadiazole-7-thiocarbamate in the mixed solution is 40-80 mg/L, and the final concentration of sodium selenite is 50-200 mg/L.
3. The benzothiadiazole-selenium nanocomplex according to claim 2, wherein the final concentration of S-methyl 1,2, 3-benzothiadiazole-7-thiocarbamate in the mixed solution is 75mg/L and the final concentration of sodium selenite is 75 mg/L.
4. The benzothiadiazole-selenium nanocomplex according to claim 1, wherein the ascorbic acid is L-ascorbic acid; the molar mass ratio of the ascorbic acid to the sodium selenite is 3-10: 1.
5. The benzothiadiazole-selenium nanocomplex according to claim 4, wherein the molar mass ratio of ascorbic acid to sodium selenite is 5: 1.
6. The benzothiadiazole-selenium nanocomplex of claim 1, wherein the rotation speed of the low speed centrifugation is 1500 rpm; the centrifugation time was 5 min.
7. The benzothiadiazole-selenium nanocomplex according to claim 1, wherein the rotation speed of the high speed centrifugation is 13000 rpm; centrifuging for 20 min; the centrifugation temperature was 4 ℃.
8. Use of the benzothiadiazole-selenium nanocomplexes of any one of claims 1 to 7 for the preparation of a drug resistance inducer.
9. Use of the benzothiadiazole-selenium nanocomplex of any one of claims 1 to 7 in the preparation of a medicament for the prevention of anthracnose.
10. The use according to claim 9, wherein the anthracnose-preventing agent is a cruciferous vegetable anthracnose-preventing agent.
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