阅读说明：本技术 一种中空介孔二氧化硅负载鱼藤酮的纳米颗粒及其制备方法 (Hollow mesoporous silica supported rotenone nano-particles and preparation method thereof ) 是由 孟志远 范添乐 陈小军 王智超 徐王瑾 刘莉 杨春梅 孙成 缪心忆 沈殿晶 林宝 于 2021-06-19 设计创作，主要内容包括：本发明涉及一种中空介孔二氧化硅负载鱼藤酮的纳米颗粒及其制备方法,所述纳米颗粒包括有效成份、纳米载体,有效成份为鱼藤酮；其中,所述鱼藤酮占所述纳米颗粒总重量的重量百分比为10.0%,余量为纳米载体。通过本发明,采用自模板合成法,在合成实心介孔二氧化硅纳米粒子(HMSNs)的基础上,以水为刻蚀剂制备中空介孔二氧化硅纳米粒子(HMSNs)。研究表明所制备的HMSNs的粒径约250 nm,比表面积达999.4 m～(2)/g；通过溶剂挥发法将生物源农药鱼藤酮(Rot)负载到HMSNs的孔道中,制备得到的载鱼藤酮纳米颗粒(Rot@HMSNs)粒径均一,载药率达46.7%,且具有良好的释放特性,对菜粉蝶幼虫具有较好的防治效果。(The invention relates to a hollow mesoporous silica supported rotenone nanoparticle and a preparation method thereof, wherein the nanoparticle comprises an effective component and a nano carrier, and the effective component is rotenone; wherein, the rotenone accounts for 10.0 percent of the total weight of the nano particles, and the balance is nano carrier. According to the invention, the Hollow Mesoporous Silica Nanoparticles (HMSNs) are prepared by adopting a self-template synthesis method and taking water as an etching agent on the basis of synthesizing the solid mesoporous silica nanoparticles (HMSNs). The study showed that the prepared HMSNs have a particle size of about 250nm, as shown in the tableThe area reaches 999.4m 2 (ii)/g; the biological source pesticide rotenone (Rot) is loaded into the pore channel of the HMSNs through a solvent volatilization method, the prepared rotenone-loaded nanoparticles (Rot @ HMSNs) are uniform in particle size, the drug loading rate reaches 46.7%, and the rotenone-loaded nanoparticles have good release characteristics and good control effect on pieris rapae larvae.)

1. A hollow mesoporous silica loaded rotenone nanoparticle is characterized by comprising an effective component and a nano carrier, wherein the effective component is rotenone; wherein, the rotenone accounts for 10.0 percent of the total weight of the nano particles, and the balance is nano carrier.

2. A preparation method of hollow mesoporous silica supported rotenone nanoparticles is characterized by comprising the following steps:

(1) preparing hollow mesoporous silica nano particles HMSNs;

1-1) synthesizing solid mesoporous silica MSNs by adopting a self-template method, then synthesizing HMSNs with considerable specific surface area and large inner cavity volume by using water as an etching agent and controlling etching time and temperature;

1-2), adding 0.16g of hexadecyl trimethyl ammonium chloride, 26mL of absolute ethyl alcohol and 55mL of deionized water into a round-bottom flask, mixing and stirring to fully dissolve the hexadecyl trimethyl ammonium chloride, adding 1mL of ammonia water after 5min, then dropwise adding 1mL of tetraethyl orthosilicate into the mixed solution at the speed of 1mL/min to ensure that the mixed solution reacts completely, keeping the room temperature, centrifugally collecting precipitates after the mixed solution is mixed and reacts for 3h, and washing the precipitates for 3 times by using the ethanol and the deionized water respectively to obtain the solid mesoporous silica nanoparticles;

1-3), adding the synthesized solid mesoporous silica nanoparticles into 100mL of deionized water, continuously stirring for 24h at the temperature of 60 ℃, then centrifugally collecting precipitates, and washing with the deionized water for 3 times to obtain hollow mesoporous silica nanoparticles HMSNs;

(2) preparing rotenone HMSNs nanoparticles Rot @ HMSNs;

2-1), respectively weighing 200mg of rotenone, adding the rotenone into 25mL of ethanol solution to prepare a rotenone solution, and then adding 100mg of hollow mesoporous silica nano particles HMSNs into the rotenone solution to obtain a mixed solution;

2-2) stirring the mixed solution for 6 hours in a water bath condition at 60 ℃ to ensure that the hollow mesoporous silica nano particles HMSNs fully adsorb the rotenone; and then, stirring the mixture with an opening, slowly volatilizing ethanol to ensure that the hollow mesoporous silica nano particles HMSNs are in a wet state, washing the residual rotenone on the surfaces of the hollow mesoporous silica nano particles HMSNs by using 5mL of hot ethanol solution, washing the washed hollow mesoporous silica nano particles HMSNs by using deionized water for 3 times to remove the residual ethanol, and finally putting the washed hollow mesoporous silica nano particles HMSNs into a freeze dryer for vacuum freeze drying to obtain rotenone-loaded nano particles Rot @ HMSNs, thus obtaining the rotenone-loaded nano particles of the hollow mesoporous silica.

Technical Field

The invention relates to a hollow mesoporous silica supported rotenone nanoparticle and a preparation method thereof, belonging to the technical field of plant protection.

Background

The hollow microsphere is a nano material with a special structure, and compared with materials with similar sizes, the hollow microsphere has the characteristics of low relative density, less raw material consumption and the like. However, when the surface of the hollow microsphere has no pore channel, the intracavity drug is difficult to release, so the pore channel connectivity of the microsphere is very important. The Hollow Mesoporous Silica Nanoparticles (HMSNs) have the dual characteristics of mesoporous and Hollow cavity structures, have considerable specific surface area and good biocompatibility and stability, and are good carriers for loading pesticides. In recent years, researchers have also demonstrated that HMSNs-loaded pesticides can improve pesticide utilization efficiency. Gao takes HMSNs as a carrier to prepare the pH-sensitive abamectin nano pesticide, and the result shows that the HSMNs can greatly improve the lasting period of the abamectin. HMSNs with the particle size of 80-100 nm are prepared by Tan through a hard template method, the HMSNs loaded with uniconazole have good controlled-release characteristics, and the inhibition effect on the growth of rice is improved. In the formation process of HMSNs, the synthesized template plays a crucial role, and the method mainly comprises a hard template method, a soft template method and a self-template method according to the synthesis mechanism of the template. The self-template method has the advantages that the self-template method can be used as a template, and etching agent is adopted for etching, so that HMSNs are converted, the method is convenient and efficient, and other chemical agents are not added.

Rotenone (Rotenone) is a biological source pesticide and has good insecticidal activity on vegetable pests such as thrips, aphids, cabbage caterpillars and the like. However, it is unstable in the environment, and is susceptible to photolysis and hydrolysis, resulting in a shortened duration. In addition, only a small amount of the pesticide enters the plant body after being applied, so that the utilization rate and the control effect of the pesticide are greatly reduced. According to statistics, 20 registered preparation products, 2 original medicine products and no related rotenone nano-dosage form registration are obtained by 2021 for 2 months in China. The prodenia litura is a lepidoptera noctuidae omnivorous pest, has wide host plants, more than 300 host plants and mainly harms field crops such as cruciferous vegetables, tobacco, peanuts, soybeans, sweet potatoes and the like. Researchers find that the 7.5 percent rotenone emulsifiable solution has higher control effect on 3-year larvae of spodoptera litura through experiments, but the persistent period of the rotenone emulsifiable solution in the environment is shorter. In order to prolong the lasting period of rotenone and improve the effective utilization rate of the rotenone, the method adopts a self-template method, takes water as an etchant on the basis of synthesizing solid mesoporous silica, prepares HMSNs with the particle size of 250nm, good dispersion degree, large inner cavity volume and obvious mesoporous structure by adjusting etching time and temperature, and then adopts a solvent volatilization method to prepare the rotenone-loaded HMSNs nanoparticles (Rot @ HMSNs), aiming at improving the stability and the effective utilization rate of the rotenone. In the invention, the nano carrier HMSNs is used as the carrier to develop the novel dosage form of the rotenone in a functionalized way, so that the control effect of the rotenone on the pests of cruciferous vegetables can be improved, the development of the rotenone industry can be effectively promoted, and the invention has important practical significance for improving the quality of agricultural products.

Disclosure of Invention

The invention aims to provide a hollow mesoporous silica supported rotenone nanoparticle and a preparation method thereof aiming at the defects of the prior art.

The purpose of the invention is realized as follows: a hollow mesoporous silica loaded rotenone nanoparticle is characterized by comprising an effective component and a nano carrier, wherein the effective component is rotenone; wherein, the rotenone accounts for 10.0 percent of the total weight of the nano particles, and the balance is nano carrier.

A preparation method of hollow mesoporous silica supported rotenone nanoparticles is characterized by comprising the following steps:

(1) preparing hollow mesoporous silica nano particles HMSNs;

1-1) synthesizing solid mesoporous silica MSNs by adopting a self-template method, then synthesizing HMSNs with considerable specific surface area and large inner cavity volume by using water as an etching agent and controlling etching time and temperature;

1-2), adding 0.16g of hexadecyl trimethyl ammonium chloride, 26mL of absolute ethyl alcohol and 55mL of deionized water into a round-bottom flask, mixing and stirring to fully dissolve the hexadecyl trimethyl ammonium chloride, adding 1mL of ammonia water after 5min, then dropwise adding 1mL of tetraethyl orthosilicate into the mixed solution at the speed of 1mL/min to ensure that the mixed solution reacts completely, keeping the room temperature, centrifugally collecting precipitates after the mixed solution is mixed and reacts for 3h, and washing the precipitates for 3 times by using the ethanol and the deionized water respectively to obtain solid mesoporous silica nano particle MSNs;

1-3), adding the synthesized solid mesoporous silica nanoparticles into 100mL of deionized water, continuously stirring for 24h at the temperature of 60 ℃, then centrifugally collecting precipitates, and washing with the deionized water for 3 times to obtain hollow mesoporous silica nanoparticles HMSNs;

(2) preparing rotenone HMSNs nanoparticles Rot @ HMSNs;

2-1), respectively weighing 200mg of rotenone, adding the rotenone into 25mL of ethanol solution to prepare a rotenone solution, and then adding 100mg of hollow mesoporous silica nano particles HMSNs into the rotenone solution to obtain a mixed solution;

2-2) stirring the mixed solution for 6 hours in a water bath condition at 60 ℃ to ensure that the hollow mesoporous silica nano particles HMSNs fully adsorb the rotenone; and then, stirring the mixture with an opening, slowly volatilizing ethanol to ensure that the hollow mesoporous silica nano particles HMSNs are in a wet state, washing rotenone remained on the surfaces of the hollow mesoporous silica nano particles HMSNs by using 5mL of hot ethanol solution, washing with deionized water for 3 times to remove the remained ethanol, and finally putting the washed hollow mesoporous silica nano particles HMSNs into a freeze dryer for vacuum freeze drying to obtain rotenone-carried nano particles Rot @ HMSNs, thus obtaining the hollow mesoporous silica rotenone-carried nano particles.

The method is advanced and scientific, and provides the hollow mesoporous silica-loaded rotenone nano-particles and the preparation method thereof, wherein the nano-particles comprise active ingredients of rotenone and a nano-carrier, wherein the rotenone accounts for 10.0 percent of the total weight of the nano-particles, and the balance is the nano-carrier.

The synthesis method of the Hollow Mesoporous Silica Nanoparticles (HMSNs) comprises the following steps: a self-template method is adopted, solid mesoporous silicon dioxide (HMSNs) is firstly synthesized, then water is used as an etching agent, and by controlling the etching time and temperature, the HMSNs with considerable specific surface area and large inner cavity volume are synthesized. Adding 0.16g of hexadecyl trimethyl ammonium chloride, 26mL of anhydrous ethanol and 55mL of deionized water into a round bottom flask, mixing and stirring to fully dissolve the hexadecyl trimethyl ammonium chloride, adding 1mL of ammonia water after 5min, then dropwise adding 1mL of tetraethyl orthosilicate into the mixed solution at the speed of 1mL/min to completely react, keeping the temperature at room temperature, after the mixed solution is mixed and reacted for 3h, centrifugally collecting precipitates, washing the precipitates for 3 times by using ethanol and deionized water respectively to obtain solid silica nanoparticles, adding the synthesized solid mesoporous silica nanoparticles into 100mL of deionized water, continuously stirring for 24h at the temperature of 60 ℃, centrifugally collecting the precipitates, and washing for 3 times by using the deionized water to obtain the HMSNs.

The synthesis method of the rotenone-carrying HMSNs nanoparticles (Rot @ HMSNs) comprises the following steps: 200mg of rotenone was weighed out separately and added to 25mL of ethanol solution to prepare a rotenone solution, and then 100mg of HMSNs was added thereto. And stirring the mixed solution for 6 hours in a water bath condition at the temperature of 60 ℃ to ensure that the HMSNs fully adsorb the rotenone. And then stirring the mixture with an opening, slowly volatilizing ethanol to enable the HMSNs to be in a wet state, washing residual rotenone on the surface of the HMSNs by using 5mL of hot ethanol solution, washing away the residual ethanol by using deionized water (the step is repeated for 3 times), and finally putting the washed HMSNs into a freeze dryer for vacuum freeze drying to obtain the rotenone-carrying nano-particles Rot @ HMSNs.

The characterization methods and results of HMSNs and Rot @ HMSNs are respectively as follows:

(1) and (3) analyzing appearance and appearance: firstly, plating gold on the HMSNs, and then observing the appearance of the HMSNs under a scanning electron microscope. In order to further observe the microstructure of the nano carrier, a transmission electron microscope is adopted for analysis, a certain amount of HMSNs and Rot @ HMSNs are dispersed in an ethanol solution, the ethanol solution is subjected to ultrasonic treatment to be uniformly dispersed, a small amount of solution is dropwise added onto a copper net with a carbon film, drying is carried out under an infrared lamp, and then the nano carrier is placed under the transmission electron microscope to observe the morphological characteristics. The research result of a scanning electron microscope shows that the prepared HMSNs are spherical, uniform in particle size, rough in surface structure and compact in mesoporous structure (figures 1 and 2). Further, the results of the research on the transmission electron microscope show that the HMSNs have uniform particle size, clear mesoporous structure and considerable lumen space (FIG. 3). After rotenone loading, the lumenal space of the HMSNs became smaller and the shaded area was darker, indicating successful rotenone loading (fig. 4).

(2) X-ray diffraction analysis (XRD): the prepared rotenone, HMSN and Rot @ HMSN were analyzed by X-ray diffractometry. XRD analysis conditions of the samples were as follows: the radiation source is a CuK alpha target, and the scanning range is 1.5-8 degrees and 10-80 degrees. From the small-angle XRD of HMSNs, it can be seen that HMSNs have a typical MCM-41 type mesoporous structure with hexagonal phase symmetry diffraction peaks (100), (110) and (200), indicating that the mesoporous structure of HMSNs has uniformity and order, which is also beneficial for loading and releasing rotenone pesticide molecules (fig. 5A). From the wide angle XRD pattern of HMSNs, a large and broad diffraction peak appears between 20 ° and 30 °, which is typical of amorphous silica diffraction peaks, thus also indicating successful synthesis of HMSNs (fig. 5B).

(3) And (3) particle size analysis: dynamic Light Scattering (DLS) is adopted for analysis, firstly, 2mg of HMSNs and Rot @ HMSNs are respectively weighed, and a certain amount of deionized water is respectively added to prepare a solution with the concentration of 100 mg/L. 4mL of the two solutions were added to the cuvette and subjected to DLS assay. The DLS analysis results indicated that HMSNs and Rot @ HMSNs had good dispersibility in water, and the drug-loaded HMSNs had a similar particle size to the HMSNs (fig. 6A). As can be seen from FIG. 6A, the HMSNs have a relatively concentrated particle size, mainly distributed around 250 nm. Similarly, the particle size distribution of Rot @ HMSNs is more concentrated and also mainly at 250 nm. Furthermore, Rot @ HMSNs have a weak peak around 5000nm, which may be due to agglomeration of part of the HMSNs after loading rotenone. The polymer dispersion coefficients (PdI) of the nanocarriers and the nanoparticles were 0.259 and 0.367, respectively (table 1). The research result shows that the medicine carrying method adopted by the patent can keep similar particle size while achieving considerable medicine carrying rate.

TABLE 1 DLS analysis results of HMSNs and Rot @ HMSNs

Sample (I)	Average particle diameter (nm)	Aggregate Dispersion index PdI
			HMSNs	254.4	0.259
[email protected]	267.9	0.367

(4) Physical adsorption analysis: and (3) carrying out physical adsorption analysis by using a specific surface area tester, evaluating the characteristics of the mesoporous structure by using a Brunauer-Emmett-Teller (BET) gas adsorption method and a Barrett-Joyner-Halenda (BJH) analysis model according to the obtained desorption and adsorption isotherm data, and calculating the specific surface area, the pore volume and the average pore diameter of the MSNs. The detection environment is as follows: degassing temperature 120 deg.C, degassing time 120min, ambient temperature 30 deg.C, saturated vapor pressure 101.5KPa and constant temperature bath temperature 77.3K. Research shows that the HMSNs isotherm is a typical IV-type isothermal curve, and when the partial pressure is 0.3-1.0, a long and wide H4-type hysteresis loop (figure 6B) appears, which shows that the HMSNs isotherm has mesopores with a parallel plate structure. The isotherm of Rot @ HMSNs changes due to the filling of rotenone molecules, with much less adsorbed than HMSNs. The research shows that the specific surface area of HMSNs is 999.4m²Per g, pore volume of 0.62cm³The pore diameter is 3.3nm (table 2), and indexes such as specific surface area of Rot @ HMSNs are all sharply reduced due to the load of rotenone, so that the fact that the rotenone successfully occupies the mesoporous structure of the HMSNs is proved.

TABLE 2 results of physical adsorption characteristics of HMSNs and Rot @ HMSNs

Sample (I)	Specific surface area (m)2/g)	Pore volume (cm3/g)	Pore size (nm)
				HMSNs	999.4	0.62	3.3
[email protected]	21.8	0.16	3.1

(5) Fourier infrared spectroscopy (FTIR): the dried Rot @ HMSNs and potassium bromide were mixed well and ground thoroughly, and the samples were prepared in a ratio of 1:10 by tabletting method and analyzed by Fourier Infrared Spectroscopy. The infrared spectrum measurement result shows that characteristic peaks of rotenone and HMSNs appear at corresponding positions of Rot @ HMSNs and are 457cm^-1、813cm^-1A symmetric stretching peak of Si-O bond appears; at 1085cm^-1Has an antisymmetric Si-O-Si stretching vibration peak at 3658cm^-1The weak peak is a structural water-OH antisymmetric stretching vibration peak; in addition, at 1454cm^-1、1514cm^-1、1610cm^-1、1674cm^-1The characteristic absorption peak (fig. 6C) similar to rotenone appears, which is the vibration peak of the benzene ring. Therefore, the successful loading of the rotenone into the HMSNs pore channels can be proved, and the changes such as oxidative photolysis and the like do not occur.

(6) The method for determining the drug loading rate of Rot @ HMSNs comprises the following steps: 5mg Rot @ HMSNs was added to 25mL acetonitrile and dispersed ultrasonically for 2h to release the loaded rotenone completely from the HMSNs and the experiment was repeated 3 times. And (3) carrying out high performance liquid chromatography analysis on the completely released solution for the content of the rotenone, wherein the detection conditions of the high performance liquid chromatography analysis are as follows: c₁₈Chromatography column (250 mm. times.4.6 mm); the detection wavelength is 297 nm; the column temperature is 25 ℃; the sample volume is 10 mu L; the flow rate is 1 mL/min; the mobile phase is V (acetonitrile) and V (water) is 70: 30. The rotenone content of the ethanol solution containing Rot @ HMSNs after 2h of ultrasonic detection is detected by high performance liquid chromatography, and the result shows that the drug loading rate of the HMSNs is 46.7%.

(7) The method for determining the sustained release performance of Rot @ HMSNs comprises the following steps: the release profile of rotenone-loaded HMSNs in cucumber dilutions (prepared from 50g of cucumber plant extract in 100mL of deionized water containing 30% acetonitrile) containing 0.1% tween 80 was evaluated by dialysis. The weighed 20mg of Rot @ HMSNs was added to a dialysis bag with a molecular weight cut-off of 3500Da, and placed in a centrifuge tube containing 100mL of release medium, the tube was placed in a constant temperature shaker at 25 ℃ and an oscillation rate of 200 r/min. At regular intervals 1mL of release medium was removed and subjected to hplc analysis while 1mL of cucumber diluted solution containing 0.1% tween 80 was added, keeping the total volume constant. The release amount is calculated according to the following formula:

in the formula: e_pIs cumulative release,%; v_eTo remove the volume of release medium (1 mL); c_iIs the mass concentration of rotenone in the release medium at sampling time i, mg/mL; c_nIs the mass concentration of rotenone in the release medium at the sampling time n, mg/mL; v₀Volume of release medium (30 mL); m is_pMg is the total mass of rotenone loaded into HMSNs. The research result shows that: when the release time is 0-10 h, the release amount of the rotenone is slightly larger than Rot @ HMSNs, and at the moment, the release of the rotenone is limited due to the restriction of the HMSNs pore channels and the aggregation of a large amount of the rotenone in the HMSNs. When the release time is longer than 10h, the rotenone on the surface of the HMSNs and in the pore channels is completely released, the release of the rotenone in the inner cavity is not limited any more, the release amount is initially larger than that of the rotenone raw material, the rotenone release amount of Rot @ HMSNs reaches 74% after 168h, the release amount of the rotenone raw material is 67%, and the trend of slow increase exists (fig. 6D).

The first purpose of the invention is realized by the following technical scheme that the hollow mesoporous silica-loaded biopesticide nano-particles for controlling brassicaceous vegetable pests comprise the active ingredient of rotenone, wherein the rotenone accounts for 10.0 percent of the total weight of the nano-particles, and the balance is a nano-carrier. The second purpose of the invention is realized by the following technical scheme, the preparation and the application of the hollow mesoporous silica supported rotenone nano-particles are as follows: mixing the raw materials in the weight ratio, and preparing the mixture into nano particles by adopting a nano preparation processing technology. Compared with the prior art, the invention has the following beneficial effects:

(1) the active ingredient rotenone is a known pesticide in the field, can be easily purchased from the market, has certain control effect on brassicaceous vegetable pests such as pieris rapae larvae and the like, can effectively control the pests in time and in a large area, is not easy to generate drug resistance, and has low selection pressure on the environment for the selected drug.

(2) The invention adopts the active ingredient rotenone to prepare the nano particles, and the prepared nano particles have the slow release and controlled release characteristics, thoroughly kill pests such as pieris rapae larvae and the like, and are suitable for the chemical control of brassicaceous vegetable pests.

In summary, the invention relates to a hollow mesoporous silica supported rotenone nanoparticle and a preparation method thereof, wherein the effective component is rotenone, the rotenone accounts for 10.0 percent of the total weight of the nanoparticle, and the balance is a nano carrier. The research shows that the prepared HMSNs have the particle size of about 250nm and the specific surface area of 999.4m²(ii)/g; the biological source pesticide rotenone is loaded into the pore channels of the HMSNs through a solvent volatilization method, and the prepared rotenone-loaded nanoparticles (Rot @ HMSNs) are uniform in particle size, have the drug loading rate of 46.7 percent, have good release characteristics, have good control effect on pieris rapae larvae, and are suitable for controlling brassicaceous vegetable pests.

In summary, the invention relates to a hollow mesoporous silica supported rotenone nanoparticle and a preparation method thereof, which adopts a self-template synthesis method to prepare Hollow Mesoporous Silica Nanoparticles (HMSNs) by taking water as an etching agent on the basis of synthesizing solid Mesoporous Silica Nanoparticles (MSNs). The research shows that the prepared HMSNs have the particle size of about 250nm and the specific surface area of 999.4m²(ii)/g; the biological source pesticide rotenone (Rot) is loaded into the pore channel of the HMSNs through a solvent volatilization method, the prepared rotenone-loaded nanoparticles (Rot @ HMSNs) are uniform in particle size, the drug loading rate reaches 46.7%, and the rotenone-loaded nanoparticles have good release characteristics and good control effect on pieris rapae larvae. The utilization rate of rotenone can be improved through the nano carrier HMSNs, and the research has the effects of reducing the usage amount of pesticides and reducing environmental pollutionHas important significance.

Drawings

FIG. 1 is a scanning electron micrograph of HMSNs.

FIG. 2 is a scanning electron micrograph of HMSNs.

FIG. 3 is a transmission electron micrograph of HMSNs.

FIG. 4 is a transmission electron micrograph of Rot @ HMSNs.

FIG. 5 is an XRD pattern of HMSNs;

wherein A is a small-angle XRD pattern of HMSNs, and B is a wide-angle XRD pattern of HMSNs.

FIG. 6 is a graph of a characterization analysis of HMSNs and Rot @ HMSNs;

wherein A is a dynamic light scattering particle size distribution diagram of HMSNs and Rot @ HMSNs; b is a nitrogen adsorption desorption isotherm and a pore size distribution diagram of HMSNs and Rot @ HMSNs; c is a Fourier infrared spectrogram of Rotenone, Rot @ HMSNs and HMSNs; d is the release profile of Rot @ HMSNs.

Detailed Description

The following examples are further illustrative of the technical solution of the present invention, but the content of the present invention is not limited thereto.

Example 1: the composition and preparation method of 10.0% rotenone nano-particles comprises the following steps: 23.8mg of rotenone was weighed out and added to 25mL of ethanol solution to prepare a rotenone solution, and then 100mg of HMSNs was added thereto. And stirring the mixed solution for 6 hours in a water bath condition at the temperature of 60 ℃ to ensure that the HMSNs fully adsorb the rotenone. And then stirring the mixture with an opening, slowly volatilizing ethanol to enable the HMSNs to be in a wet state, washing the residual rotenone on the surface of the HMSNs by using 5mL of hot ethanol solution, washing away the residual ethanol by using deionized water, repeating the step for 3 times, and finally putting the washed HMSNs into a freeze dryer for vacuum freeze drying to obtain the rotenone-carrying nano-particles Rot @ HMSNs.

Example 2: evaluating the field pesticide effect: in the test, the larvae of the Pieris rapae in the plot are heavier in the small green vegetable base of the small town of the Jiangzhou city of Yangzhou city of Jiangsu province. Preparing each medicinal preparation into medicinal liquid with required concentration, repeating for 3 times each treatment, and having cell area of 20m²The materials are randomly arranged and evenly sprayed by a knapsack sprayer, and the application amount per mu is 50 kg. Every cell is according to east, west, south and northAnd two plants at each fixed point in the process, wherein the total number of the plants is 10. The population base number of the worms is checked before the application, and the number of the live worms is checked 7 days after the application. And calculating the prevention and treatment effect by using an Abbot formula. Adding trisiloxane organosilicon cationic surfactant into 10.0% rotenone nano particles to prepare Pickering emulsion, diluting by 1000 times, and spraying. Simultaneously, clear water and 10.0% rotenone suspending agent are respectively arranged to be used as a control treatment group (diluted by 1000 times) for spraying application, and each treatment is repeated for 3 times. The test results are shown in Table 3. As can be seen from table 3: in a field pesticide effect test, the 10.0% rotenone nano-particles have good control effect on pieris rapae larvae, and the prepared nano-particles can meet the requirement of controlling brassicaceous vegetable pests.

TABLE 3 field test of efficacy of each preparation on pieris rapae larvae

Treatment of	Rate of oral cavity decline
		10.0% rotenone nanoemulsion formulation	95.62％
10.0% rotenone suspension	87.55％
		CK	/