CN-122004204-A - ROS response type pesticide based on cinnamaldehyde and preparation method thereof

CN122004204ACN 122004204 ACN122004204 ACN 122004204ACN-122004204-A

Abstract

The invention discloses a reactive ROS pesticide based on cinnamaldehyde, which is prepared by reacting cinnamaldehyde and a sulfhydryl reagent to obtain an intermediate compound, wherein the intermediate compound reacts with hydrazine hydrate to obtain an amphiphilic small molecular compound, and the amphiphilic small molecular compound self-assembles to form a nano micelle-entrapped hydrophobic pesticide. The invention provides a green and intelligent ROS response pesticide based on natural cinnamaldehyde, which is characterized in that natural cinnamaldehyde is used as a raw material to construct a delivery carrier with both activity and response functions, and the ROS response pesticide has good environmental compatibility.

Inventors

XIE YUYING
QIU YUPENG
Shen Zhuochao
GE YANGCHUN
LI ZHONGYU

Assignees

温州大学

Dates

Publication Date: 20260512
Application Date: 20260122

Claims (10)

1. An ROS-responsive pesticide based on cinnamaldehyde, characterized in that: Reacting cinnamaldehyde with a sulfhydryl reagent to obtain an intermediate compound; The intermediate compound reacts with hydrazine hydrate to obtain an amphiphilic small molecular compound; The nano micelle formed by self-assembly of the amphiphilic small molecular compound encapsulates the hydrophobic pesticide.
2. The cinnamaldehyde-based ROS-responsive pesticide of claim 1, wherein: The sulfhydryl reagent is one or more of ethyl 3-mercaptopropionate and methyl 3-mercaptopropionate.
3. The cinnamaldehyde-based ROS-responsive pesticide of claim 1, wherein: the molar ratio of aldehyde groups in the cinnamaldehyde to functional groups of sulfhydryl groups in the sulfhydryl reagent is 1:1-1.2.
4. The cinnamaldehyde-based ROS-responsive pesticide of claim 1, wherein: The molar ratio of the intermediate compound to the hydrazine hydrate is 1:4-6.
5. A cinnamaldehyde-based ROS-responsive pesticide according to claim 1 or 2 or 3 or 4, wherein: reacting cinnamaldehyde, a sulfhydryl reagent and Lewis acid in a solvent to obtain an intermediate compound; The intermediate compound reacts with hydrazine hydrate to obtain an amphiphilic small molecular compound; The nano micelle formed by self-assembly of the amphiphilic small molecular compound encapsulates the hydrophobic pesticide.
6. The cinnamaldehyde-based ROS-responsive pesticide of claim 5, wherein: the solvent is one or more of ethyl acetate, chloroform, absolute ethyl alcohol and N, N-dimethylformamide.
7. The cinnamaldehyde-based ROS-responsive pesticide of claim 5, wherein: the Lewis acid is one or more of p-toluenesulfonic acid and trifluoroacetic acid.
8. A method for preparing a ROS-responsive pesticide based on cinnamaldehyde as defined in any one of claims 1 to 7, wherein: Comprising Dissolving cinnamaldehyde and a sulfhydryl reagent in a first solvent, stirring and mixing in a reaction container to obtain a first mixed system, then adding Lewis acid, and magnetically stirring at 20-30 ℃ for reaction; Step two, the reaction is carried out for 6 to 8 hours, the solvent is removed by decompression rotary evaporation, the crude product is obtained, and then the column chromatography is adopted to purify the crude product, and finally the intermediate compound is obtained; dissolving an intermediate compound in a second solvent, adding hydrazine hydrate to obtain a second mixed system, reacting for 8-10 hours at 50-70 ℃, concentrating the system after the reaction is finished, separating out white solid, washing the solid by using the second solvent to obtain a pure amphiphilic small molecular compound, and fully drying a final product in a vacuum drying oven for later use; And fourthly, dissolving 10-20mg of amphiphilic small molecular compound and 3-6mg of hydrophobic pesticide in a third solvent to obtain a third mixed system, slowly dripping the third mixed system into 30-60 mL high-speed stirred deionized water, and dialyzing to remove the third solvent and free drug to obtain drug-loaded micelle, namely the ROS responsive pesticide.
9. The method for preparing a ROS-responsive pesticide based on cinnamaldehyde according to claim 8, wherein: in the first step, the mass fraction of cinnamaldehyde in the first mixed system is 10% -30%, and the addition amount of Lewis acid is 0.03% -0.08% of the mass of the first solvent; in the third step, the mass fraction of the intermediate compound in the second solvent is 5% -20%.
10. The method for preparing a ROS-responsive pesticide based on cinnamaldehyde according to claim 8, wherein: The first solvent is ethyl acetate; The second solvent is ethanol; the third solvent is N, N-dimethylformamide.

Description

ROS response type pesticide based on cinnamaldehyde and preparation method thereof Technical Field The technical field of agricultural pesticides, in particular to an intelligent response type pesticide delivery system, and especially relates to a nano micelle system based on natural cinnamaldehyde derivatives and capable of responding to Reactive Oxygen Species (ROS) stimulation and releasing pesticides, a preparation method thereof and application thereof in targeted pest control. Background The pesticide is indispensable in modern agricultural production, but the traditional preparation has the problems of easy photolysis, hydrolysis, serious migration and loss of active ingredients in the environment, and the like, so that the field utilization rate is low and the ecological risk is high. The development of efficient, low-toxicity, environmentally friendly green pesticides and intelligent delivery technologies is an important direction. The stimulus response type delivery system can realize the controlled release and targeted delivery of pesticides according to environmental signals (such as pH, enzyme, ROS and the like), so that the utilization efficiency is improved, and the residues are reduced. Reactive Oxygen Species (ROS) are a class of signaling molecules that organisms produce under stress metabolism. After feeding, the pests have the intestinal cell metabolism aggravated, and can generate high-level ROS, which provides ideal trigger signals for designing a targeted delivery system. Cinnamaldehyde is a natural plant source active substance and has various biological activities such as insect killing, bacteria resisting and the like, but has strong volatility and poor stability, so that the direct application of the cinnamaldehyde is limited. Meanwhile, the aldehyde group is a modifiable active site. At present, the natural active substances are taken as a functional framework and an active ingredient at the same time, and the research on constructing an intelligent pesticide delivery system aiming at the environment response of the intestinal ROS of pests is not seen. Disclosure of Invention Aiming at the defects existing in the prior art, the pesticide delivery system which is based on natural cinnamaldehyde, has ROS response and has the functions of efficient disinsection and intelligent controlled release is provided. In order to achieve the above purpose, the present invention provides the following technical solutions: an ROS responsive pesticide based on cinnamaldehyde, Reacting cinnamaldehyde with a sulfhydryl reagent to obtain an intermediate compound; The intermediate compound reacts with hydrazine hydrate to obtain an amphiphilic small molecular compound; The nano micelle formed by self-assembly of the amphiphilic small molecular compound encapsulates the hydrophobic pesticide. As a further improvement of the present invention, The sulfhydryl reagent is one or more of ethyl 3-mercaptopropionate and methyl 3-mercaptopropionate. As a further improvement of the present invention, The molar ratio of aldehyde groups in the cinnamaldehyde to functional groups of sulfhydryl groups in the sulfhydryl reagent is 1:1-1.2. As a further improvement of the present invention, The molar ratio of the intermediate compound to the hydrazine hydrate is 1:4-6. As a further improvement of the present invention, The cinnamaldehyde, a sulfhydryl reagent and Lewis acid react in a solvent to obtain an intermediate compound; The intermediate compound reacts with hydrazine hydrate to obtain an amphiphilic small molecular compound; The nano micelle formed by self-assembly of the amphiphilic small molecular compound encapsulates the hydrophobic pesticide. As a further improvement of the present invention, The solvent is one or more of ethyl acetate, chloroform, absolute ethyl alcohol and N, N-dimethylformamide. As a further improvement of the present invention, The Lewis acid is one or more of p-toluenesulfonic acid and trifluoroacetic acid. As another object of the present invention, there is provided a method for preparing a ROS-responsive pesticide based on cinnamaldehyde, comprising Dissolving cinnamaldehyde and a sulfhydryl reagent in a first solvent, stirring and mixing in a reaction container to obtain a first mixed system, then adding Lewis acid, and magnetically stirring at 20-30 ℃ for reaction; Step two, the reaction is carried out for 6 to 8 hours, the solvent is removed by decompression rotary evaporation, the crude product is obtained, and then the column chromatography is adopted to purify the crude product, and finally the intermediate compound is obtained; dissolving an intermediate compound in a second solvent, adding hydrazine hydrate to obtain a second mixed system, reacting for 8-10 hours at 50-70 ℃, concentrating the system after the reaction is finished, separating out white solid, washing the solid by using the second solvent to obtain a pure amphiphilic small molecular compound, and fully dr