阅读说明：本技术 一种介孔二氧化硅负载ppte的纳米农药制剂 (Mesoporous silica supported PPTE nano pesticide preparation ) 是由 陈小军 沈殿晶 范添乐 任永霞 胡珊 任亚军 赵明 陆春良 董飒 张铭瑞 王智超 于 2019-10-23 设计创作，主要内容包括：本发明涉及一种介孔二氧化硅负载PPTE的纳米农药制剂,属于农药制剂学研究领域,所述农药制剂由PPTE、介孔二氧化硅制备而成,其中PPTE占所述纳米制剂总质量的质量百分比分别为0.1～15%。所制备的纳米制剂具有高度的环境相容性,有助于提高其靶向性和智能性,避免活性成分的过快降解、延长持效期、降低施药量、提高防治效果。(The invention relates to a mesoporous silica supported PPTE nano pesticide preparation, belonging to the field of pesticide preparation science research, wherein the pesticide preparation is prepared from PPTE and mesoporous silica, wherein the mass percentages of PPTE and mesoporous silica are respectively 0.1-15%. The prepared nano preparation has high environmental compatibility, is beneficial to improving the targeting property and intelligence of the nano preparation, avoids the too fast degradation of active ingredients, prolongs the lasting period, reduces the application dosage and improves the prevention and treatment effect.)

1. The nano pesticide preparation of the mesoporous silica-loaded PPTE is characterized by being prepared from an effective component PPTE and a mesoporous silica capsule wall material, wherein the mass percentage of PPTE in the total mass of the nano pesticide preparation is 0.1-15%, and the balance is the mesoporous silica capsule wall material.

2. The mesoporous silica supported PPTE nano pesticide preparation as claimed in claim 1, wherein in the mesoporous silica capsule wall material, when mesoporous silica is prepared:

preparing mesoporous silicon dioxide by using hexadecyl trimethyl ammonium chloride as a template agent and tetraethoxysilane as a silicon source: weighing 0.4g of hexadecyl trimethyl ammonium chloride, adding the hexadecyl trimethyl ammonium chloride into a 150mL round-bottom flask, respectively adding 16mL of ethanol, 40mL of deionized water and 0.1mL of ethylenediamine, and stirring at 70 ℃ until the hexadecyl trimethyl ammonium chloride is completely dissolved; adding 96mg of resorcinol, and stirring for 30min at 500 rpm; respectively adding 0.575mL of tetraethyl orthosilicate and 0.065mL of formaldehyde, and stirring for 24 hours; and (3) centrifugally washing the reaction liquid by using deionized water and ethanol for 3 times, drying at 60 ℃, finally calcining in a muffle furnace at 600 ℃ for 5 hours, taking out a sample, and preserving at normal temperature to prepare the mesoporous silicon dioxide.

3. The mesoporous silica supported PPTE nano pesticide preparation as claimed in claim 2, which is prepared by the following steps:

weighing 100mg of PPTE in a round bottom flask, adding acetonitrile, performing ultrasonic treatment until the PPTE is completely dissolved in an acetonitrile solvent to enable the concentration of the PPTE to be 5mg/mL, heating in a water bath at 60 ℃ to enable the PPTE to be dissolved, adding 100mg of mesoporous silica, performing ultrasonic treatment to enable the PPTE to be completely dispersed in the acetonitrile, stirring for 4 hours under a sealed condition, continuing stirring under an open condition to enable the acetonitrile to slowly volatilize until the mesoporous silica is in a wet state, washing residues with 5mL of hot ethanol, and finally performing vacuum freeze drying to obtain the PPTE-loaded mesoporous silica nano pesticide preparation (PPTE @ MSN).

4. The mesoporous silica supported PPTE nano pesticide formulation as claimed in claim 2, wherein the characteristics of the mesoporous silica supported PPTE nano pesticide formulation are as follows: the morphology of the prepared nano preparation is observed by using a transmission electron microscope, the average particle size of the nano particles is about 200nm, and the nano preparation has the controlled release characteristic.

Technical Field

The invention relates to a mesoporous silica supported PPTE nano pesticide preparation, belonging to the field of pesticide formulation research.

Background

Cruciferous vegetables including white cabbage, mustard, radish, aquatic vegetable, rape and the like are popular with consumers because of high nutritive value and the components of cancer prevention and cancer resistance and the like. The pests harmful to the cruciferous vegetables are various in types and common in occurrence, and are main restriction factors for healthy production of the cruciferous vegetables). The pest identification capability of farmers is poor and the pesticide application blindness is large in production, and along with long-term continuous cropping and continuous increase of pesticide dosage of the farmers, the pesticide resistance of pests is continuously improved, and the prevention difficulty is continuously increased. In recent years, with the continuous increase of planting area and the improvement of multiple cropping index, the variety and the number of pests are obviously increased, the occurrence period is long, the pests are serious, and the situation that the yield is not always high is caused by the increase of the drug resistance of the pests caused by long-term abuse of chemical pesticides, so that the development and the safety of the vegetable industry are seriously influenced. For example, Plutella xylostella (Plutella xylostella) is a devastating pest of cruciferous vegetables worldwide. The incidence area of diamondback moths in China is increased year by year, and the annual incidence area is 14.67 kilohm from 1990²213.33 ten thousand hm rising to 2014²Is at least oneShowing the characteristics of large generating area, serious harm and the like.

The application of pesticide is an important measure for preventing and controlling pests. For years, the use amount of pesticides generally rises due to the fact that the crop seeding area is enlarged year by year and the difficulty of pest control is increased continuously. According to statistics, the annual average using amount of the crop pest control pesticide is 31.1 ten thousand tons (hundred-fold) in 2012-2014, and is increased by 9.2% compared with that in 2009-2011; in 2018, the usage amount of the pesticide is slightly reduced, and the consumption is about 30 ten thousand tons. The realization of the reduction and the control of the harm of pesticides is an important problem to be solved urgently in the field of plant protection at present. In 2015, "document 1 at the center" and the national agricultural working conference propose "to greatly promote the reduction and efficiency improvement of chemical fertilizers and the reduction and harm control of pesticides, and actively explore and produce a modern agricultural development way which is efficient, safe in products, resource-saving and environment-friendly". In the face of the severe situation of disease, pest and weed prevention and control, the structure of a pesticide product must be adjusted as soon as possible, green pesticides are promoted to replace traditional chemical pesticides, and the use proportion of environment-friendly pesticides such as biological pesticides is increased.

The light activated pesticide is a pesticide with a brand new design idea, the light activated pesticide utilizes sunlight and oxygen to exert insecticidal activity, the active ingredients are only media for transmitting light energy, the process of exerting the insecticidal action is also the process of photodegradation of the active ingredients, the active ingredients cannot be permanently remained in the environment after exerting the insecticidal action, the pesticide is called as ecological pesticide, and the pesticide has the advantages which cannot be compared with the traditional pesticide. At present, the number of alpha-terthiophene derivatives based on reasonable molecular design is small, the modification of the structure of the alpha-terthiophene derivatives is only limited to the replacement of some simple small molecules, and lead compounds with good photoactivation insecticidal performance and application prospect are lacked, so that the problems of the existing photoactivation insecticides are not fundamentally solved. In the research, alpha-terthiophene is taken as a lead compound to be subjected to derivation transformation to obtain various derivatives of ethynylthiophene, the activity effect of ethynylthiophene substituent is preliminarily studied by analyzing the relationship between the structure and the activity, and the activity of the compound is considered to increase along with the increase of the power supply of the substituent and decrease along with the increase of the hydrophobicity and the space volume of the substituent. PPTE (2-phenyl-1- (5- (2-phenylethynyl) thiophene-2-yl) ethanone) and the like are screened from compounds synthesized in series and have excellent insecticidal activity.

Meanwhile, many scientists in the world are taking the search of high-efficiency, low-toxicity, low-residue and environmentally-friendly biologically reasonable pesticides as the development direction of pesticide research and development. In China, with the development of economy and society, agriculture is undergoing a deep historical revolution from quantity type to quality type and from yield type to benefit type, and in order to adapt to the sustainable development strategy of agriculture in China, the currently developed new pesticide must have the characteristics of high safety, low residue, no pollution, high biological activity, low use cost and high selectivity. For high-efficiency and low-toxicity pesticides, the advantages of the low-toxicity pesticides cannot be embodied without developing a novel environment-friendly formulation. If the PPTE preparation does not reduce the dosage of organic solvent and research and develop water-based preparations and other safe formulations, the advantage of the PPTE on the ecological environment safety cannot be effectively highlighted. China also advocates the development of novel environment-friendly formulations vigorously, the yield of some novel environment-friendly formulations in chemical pesticides is gradually increased, and the development of novel environment-friendly PPTE formulations is a necessary trend in times. The PPTE microcapsule suspending agent is a water-based preparation and does not contain organic solvent. Compared with the traditional preparation, the stability and guidance of the preparation are improved, and the control effect of the preparation is greatly improved, so that the preparation has higher competitiveness.

Disclosure of Invention

Aiming at the problems, the invention provides a mesoporous silica-loaded PPTE nano pesticide preparation which is used for preventing and controlling vegetable pests such as diamondback moth and the like with high efficiency, long lasting period, small environmental pollution and simple and convenient pesticide application.

The invention aims to realize the mesoporous silica-supported PPTE nano pesticide preparation, which is characterized by being prepared from an effective component PPTE and a mesoporous silica capsule wall material, wherein the mass percentage of PPTE in the total mass of the pesticide preparation is 0.1-15%, and the balance is the mesoporous silica capsule wall material.

In the mesoporous silica capsule wall material, when the mesoporous silica is prepared:

preparing mesoporous silicon dioxide by using hexadecyl trimethyl ammonium chloride as a template agent and tetraethoxysilane as a silicon source; weighing 0.4g of hexadecyl trimethyl ammonium chloride, adding the hexadecyl trimethyl ammonium chloride into a 150mL round-bottom flask, respectively adding 16mL of ethanol, 40mL of deionized water and 0.1mL of ethylenediamine, and stirring at 70 ℃ until the hexadecyl trimethyl ammonium chloride is completely dissolved; adding 96mg of resorcinol, and stirring for 30min at 500 rpm; respectively adding 0.575mL of tetraethyl orthosilicate and 0.065mL of formaldehyde, and stirring for 24 hours; and (3) centrifugally washing the reaction liquid by using deionized water and ethanol for 3 times, drying at 60 ℃, finally calcining in a muffle furnace at 600 ℃ for 5 hours, taking out a sample, and preserving at normal temperature to prepare the mesoporous silicon dioxide.

When the mesoporous silica supported PPTE nano pesticide preparation is prepared, the preparation method comprises the following steps:

weighing 100mg of PPTE in a round bottom flask, adding acetonitrile, performing ultrasonic treatment until the PPTE is completely dissolved in an acetonitrile solvent to enable the concentration of the PPTE to be 5mg/mL, heating in a water bath at 60 ℃ to enable the PPTE to be dissolved, adding 100mg of mesoporous silica, performing ultrasonic treatment to enable the PPTE to be completely dispersed in the acetonitrile, stirring for 4 hours under a sealed condition, continuing stirring under an open condition to enable the acetonitrile to slowly volatilize until the mesoporous silica is in a wet state, washing residues with 5mL of hot ethanol, and finally performing vacuum freeze drying to obtain the PPTE-loaded mesoporous silica nano pesticide preparation (PPTE @ MSN).

The mesoporous silica is characterized in that: the shape of the mesoporous silica is observed by using a transmission electron microscope, the existence of the mesoporous structure can be clearly seen through the transmission electron microscope, the surface is in a dendritic structure, the dispersibility is good, and the average particle size is about 200 nm.

The nano pesticide preparation is prepared by taking PPTE as an active ingredient and loading the PPTE by mesoporous silica, wherein the chemical name of the PPTE is (2-phenyl-1- (5- (2-phenylethynyl) thiophene-2-yl) ethanone), and the chemical structural formula of the PPTE is shown in figure 1.

A mesoporous silica supported PPTE nano pesticide preparation for efficiently preventing and controlling vegetable pests such as diamondback moth and the like is prepared from an effective component PPTE and a mesoporous silica capsule wall material, wherein the mass percent of PPTE in the total mass of the nano preparation is 0.1-15%.

Preparation of Mesoporous Silica (MSN): the mesoporous silicon dioxide is prepared by taking hexadecyl trimethyl ammonium chloride as a template agent and tetraethoxysilane as a silicon source. Weighing 0.4g of hexadecyl trimethyl ammonium chloride, adding the hexadecyl trimethyl ammonium chloride into a 150mL round-bottom flask, respectively adding 16mL of ethanol and 40mL of deionized water, and 0.1mL of ethylenediamine, and stirring at 70 ℃ until the hexadecyl trimethyl ammonium chloride and the deionized water are completely dissolved; adding 96mg of resorcinol, and stirring for 30min at 500 rpm; respectively adding 0.575mL of tetraethyl orthosilicate and 0.065mL of formaldehyde, and stirring for 24 hours; and (2) centrifugally washing the reaction liquid for 3 times by using deionized water and ethanol respectively, then drying at 60 ℃, finally calcining in a muffle furnace at 600 ℃ for 5h, taking out a sample, preserving at normal temperature, and preparing the prepared Mesoporous Silica (MSN).

Characterization of Mesoporous Silica (MSN): the shape of the mesoporous silica is observed by using a transmission electron microscope, the existence of the mesoporous structure can be clearly seen by using the transmission electron microscope, the surface is in a dendritic structure, the dispersibility is good, the average particle size is about 200nm, and the microcapsule diagram of the prepared mesoporous silica is shown in figure 2.

To confirm the potential ability of Mesoporous Silica (MSN) to control pesticide release, surface area analysis and pore size and volume analysis were used to confirm the specific surface area, mesoporous volume, and pore size distribution of mesoporous silica. The isotherm of the mesoporous silica can be seen as a typical IV-type isothermal curve, P/P₀The curve rapidly rises between 0.2 and 0.4, which indicates that nitrogen molecules are adsorbed by a monolayer at this stage, gas is adsorbed by a monolayer at the point A, and after all pores are filled with gas molecules, adsorption is saturated at the point B, so that the gas is liquefied, and the adsorption amount rapidly rises. Researches find that the mesoporous silicon dioxide has a good mesoporous structure, and the pore size distribution is mainly concentrated at 2.46 nm. The specific surface area of the mesoporous silica is calculated to be 820.32m according to the desorption branch data of the adsorption isotherm²Pore volume 0.76mL/g, average pore diameter 3.70nm, and most probable pore diameter 2.46 nm.

Preparation of mesoporous silica nano preparation (PPTE @ MSN) loaded with PPTE: weighing 100mg of PPTE in a round-bottom flask, adding an appropriate amount of acetonitrile, performing ultrasonic treatment until the PPTE is completely dissolved in a solvent to enable the concentration of the PPTE to be 5mg/mL, heating in a water bath at 60 ℃ to enable the medicine to be dissolved, adding 100mg of mesoporous silica, performing ultrasonic treatment to enable the PPTE to be completely dispersed in the acetonitrile, stirring for 4 hours under a sealed condition, continuing stirring under an open condition to enable the acetonitrile to slowly volatilize until the mesoporous silica is in a wet state, washing residual medicine with 5mL of hot ethanol, and finally performing vacuum freeze drying to obtain the PPTE-loaded mesoporous silica nano preparation (PPTE @ MSN).

Determination of drug loading rate of PPTE-loaded mesoporous silica (PPTE @ MSN): 10mg of PPTE @ MSN is dispersed in 25mL of ethanol, ultrasonic treatment is carried out for 2h, and the test is repeated for 3 times, so that PPTE is completely released from the mesoporous silica carrier. The drug loading rate of PPTE @ MSN to PPTE is 34.8% by adopting high performance liquid chromatography for detection.

In vitro release characteristics of the supported PPTE mesoporous silica (PPTE @ MSN): to determine the release properties of PPTE in plants in the prepared PPTE @ MSN, an aqueous solution containing 30% acetonitrile was used as the release medium. In the release test, 20mg of PPTE @ MSN was loaded into a semipermeable membrane and placed into a centrifuge tube containing 30mL of release medium, and the centrifuge tube was placed in a shaker at a set temperature of 25 ℃ and an oscillation rate of 200 rpm. At time intervals, 1mL of release medium was removed for hplc analysis and the same volume of 30% acetonitrile-water solution was added to keep the total volume of release medium constant.

The cumulative release formula is:

wherein E_pIs the cumulative amount (%) released, V_eTo remove the volume of release medium (1mL), C_i(mg/mL) concentration of PPTE pesticide in the release medium at sampling time i, C_n(mg/mL) concentration of PPTE pesticide in the release medium at sampling time n, V₀Volume of release medium (30mL), and M_p(mg) is loaded into mesoporous silicaThe total amount of the pesticide PPTE.

Research results show that the PPTE @ MSN prepared by the soft template method has the characteristics of a sustained release agent, can be slowly released in 30% acetonitrile-water solution, the duration can reach more than 14d, and the graph shows that the accumulated release amount of the drug is linearly increased and does not tend to be stable, which indicates that the original drug exists in the pore channel of the mesoporous silica in a crystal form, and the pore channel has a certain constraint effect on the drug.

Drawings

FIG. 1 is a diagram of the chemical structure of PPTE in the present invention.

FIG. 2 is a schematic view of mesoporous silica according to the present invention.

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 (all compositions of the following examples are in mass percent).