摘要

我国作为人口大国，粮食安全的重要性不言而喻，而农药作为重要的农业生产资料，可防治各种植物病害，保证粮食产量。然而，部分农药存在抗干扰能力差、药效期短、施用条件苛刻等问题。为解决上述问题，本文将醚菌酯、噻呋酰胺作为模型农药，利用多巴胺碱性条件下氧化自聚合形成聚多巴胺，间苯二酚和甲醛酚醛缩合形成树脂的机理，对醚菌酯、噻呋酰胺进行原位包覆和负载，设计并且制备两种缓释胶囊以及两种载药介孔纳米粒子。随后，对复合材料的结构特性和载药释放性能进行研究，证明载有醚菌酯、噻呋酰胺的纳米材料具有长效缓释能力、较好的粘附性以及抗飞溅特性。本文旨在使用环保型生物可降解材料负载农药，解决农药有效期短、易在叶片表面滑落、飞溅等问题，为农药施用能够做到低量高效提供一种新的思路，也为农药行业的创新发展提供一个新的方向。具体研究结果如下：

（1）醚菌酯、噻呋酰胺聚多巴胺纳米胶囊及悬浮液的制备及其性能研究。首先，使用机械力乳化载药油相和溶有表面活性剂水相形成稳定的乳液，碱性条件下，多巴胺氧化自聚合原位包覆载药液滴，制备两种约180 nm的聚多巴胺纳米胶囊。随后，筛选复配农药助剂制备了相对应纳米胶囊悬浮液。醚菌酯和噻呋酰胺纳米胶囊负载率分别为50%、34%，纳米胶囊相比原药的释放时间延长1倍，累计释放率基本持平，两种农药纳米悬浮液的悬浮率分别为92%和83%，具有适宜的pH值以及良好的稳定性、贮藏性。

（2）噻呋酰胺酚醛纳米介孔球制备及其性能研究。首先，在碱性条件下，使用间苯二酚与甲醛进行酚醛缩合制备间苯二酚-甲醛介孔纳米球，聚合过程中原位负载噻呋酰胺。载药纳米介孔球负载率为33.78%，粒径约400 nm，释放农药96 h后仍能检测其有效成分。随后，利用不同释放模型对数据进行模拟，确定不同条件下的释放机理。接触角实验以及液滴碰撞试验表明，材料具有较强的粘附性和沉积效率，可有效抑制液滴反弹。

（3）醚菌酯聚多巴胺介孔纳米瓶的制备及其性能研究。首先，在碱性条件下，通过溶剂介导聚合诱导自组装制备聚多巴胺介孔纳米瓶，并原位负载醚菌酯。随后，测得载药介孔纳米瓶负载率约为49.25%，粒径约为710 nm，农药缓释可持续300 h。不同温度、pH影响下也具有稳定的释放能力。而且，对释放数据进行拟合，确定其不同因素影响下的释放机理。接触角和液滴碰撞试验证明其具有优异的基质亲和性和抗飞溅性，从多方面提高农药的利用率。

关键词：聚多巴胺；间苯二酚；醚菌酯；噻呋酰胺；缓释

Abstract

As a populous country, the importance of food security is self-evident, and pesticides, as an important means of agricultural production, can prevent and control various plant diseases and ensure food production. However, some pesticides have problems such as poor resistance to interference, short efficacy period and harsh application conditions. To solve the above problems, in this thesis, kresoxim-methyl and thifluzamide were used as model pesticides, and the mechanism of polydopamine formation by oxidative self-polymerization of dopamine under alkaline conditions, and the formation of resin by phenolic condensation of resorcinol and formaldehyde was utilized for the in situ coating and loading of kresoxim-methyl and thifluzamide, so that two kinds of slow-release capsules and two kinds of drug-carrying mesoporous nanoparticles were designed and prepared. Subsequently, the structural properties and drug-loaded release performance of the composites were investigated, and it was proved that the nanomaterials containing kresoxim-methyl and thifluzamide had a long-lasting and slow-release ability, better adhesion, and anti-splash properties. The aim of this paper is to use environmentally friendly biodegradable materials loaded with pesticides to solve the problems of pesticides with short effective period, easy to slip and splash on the surface of leaves, providing a new way of thinking for pesticide application to be able to achieve low volume and high efficiency, and providing a new direction for the innovative development of the pesticide industry. Specific research results are as follows:

(1) Preparation and properties of polydopamine nanocapsules of kresoxim-methyl and thifluzamide, as well as their suspensions. First, two types of polydopamine nanocapsules of about 180 nm were prepared using mechanical force emulsification of the drug-carrying oil phase and surfactant-solubilized aqueous phase to form stable emulsions, and in situ encapsulation of the drug-carrying droplets by autoxidative polymerization of dopamine. Subsequently, the corresponding nanocapsule suspensions were screened and compounded. The loading capacity of nanocapsules of kresoxim-methyl and thifluzamide was 50% and 34%, respectively, and the release time of nanocapsules was extended by 1 time compared with that of the original drug, and the cumulative release rate was basically the same, and the suspension rate of two kinds of pesticide nano-suspension was 92% and 83%, respectively, and it had a suitable pH value as well as a good stability and storability.

(2) Preparation of resorcinol-formaldehyde mesoporous nanospheres of thifluzamide and study of their properties. First, resorcinol-formaldehyde mesoporous nanospheres were prepared by phenolic condensation of resorcinol and formaldehyde under alkaline conditions, and thifluzamide was loaded in situ during the polymerization process. The loading rate of the loaded mesoporous nanospheres was 33.78% with a particle size of about 400 nm, and the active ingredients could still be detected after 96 h of pesticide release. Subsequently, the data were simulated using different release models to determine the release mechanism under different conditions. The contact angle experiments and droplet collision tests showed that the material has strong adhesion and deposition efficiency, which can effectively inhibit the droplet rebound.

(3) Preparation of polydopamine mesoporous nanobottles with kresoxim-methyl and study of their properties. First, polydopamine mesoporous nanobottles were prepared by solvent-mediated polymerization-induced self-assembly under alkaline conditions and loaded with kresoxim-methyl in situ. Subsequently, the loading rate of drug-loaded mesoporous nanobottles was measured to be about 49.25%, the particle size was about 710 nm, and the pesticide slow-release could be sustained for 300 h. Stable release ability was also observed under the influence of different temperatures and pH. Moreover, the release data were fitted to determine its release mechanism under the influence of different factors. The contact angle and droplet collision tests proved that it has excellent matrix affinity and splash resistance, which improves the utilization of pesticides in many ways.

Key words: Polydopamine; Resorcinol; Kresoxim-methyl; Thifluzamide; Slow release

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