化工学报 ›› 2020, Vol. 71 ›› Issue (8): 3819-3829.DOI: 10.11949/0438-1157.20200199

• 材料化学工程与纳米技术 • 上一篇    下一篇

氨基-酰胺类智能超分子水凝胶农药载体制备

郝丽1,2(),黄丹丹1,关梅1,周红军1,2,周新华1,2()   

  1. 1.仲恺农业工程学院化学化工学院,广东 广州 510225
    2.广东省普通高校农业绿色精细化学品重点实验室,广东 广州 510225
  • 收稿日期:2020-02-28 修回日期:2020-06-01 出版日期:2020-08-05 发布日期:2020-08-05
  • 通讯作者: 周新华
  • 作者简介:郝丽(1988—),女,博士,讲师,haoli20@tju.edu.cn
  • 基金资助:
    广东省自然科学基金项目(2017A030311003);广州市科技计划项目(20190301011);广东省教育厅创新团队项目(2018KCXTD15);广东省教育厅青年创新人才项目(KA2001959)

Preparation of supramolecular-assemble hydrogels as pesticide carriers based on amphiphilic amino-amide compounds

Li HAO1,2(),Dandan HUANG1,Mei GUAN1,Hongjun ZHOU1,2,Xinhua ZHOU1,2()   

  1. 1.School of Chemistry and Chemical Engineering,Zhongkai University of Agriculture and Engineering, Guangzhou 510225, Guangdong, China
    2.Key Laboratory of Agriculture Green Fine Chemicals of Guangdong Higher Education Institution, Guangzhou 510225, Guangdong, China
  • Received:2020-02-28 Revised:2020-06-01 Online:2020-08-05 Published:2020-08-05
  • Contact: Xinhua ZHOU

摘要:

为了提高疏水性农药的水分散性,利用氨基-酰胺类两亲分子和多元羧酸通过氢键作用自组装形成一种智能超两亲分子水凝胶,在较低浓度[5.8%(质量)]下即可形成稳定的缠绕交联三维网状结构。通过DSC、FTIR、1H NMR、SEM、DLS、黏度测试等表征手段对比了氨基-酰胺与两种多元羧酸形成的超分子的性能和结构,发现两种超分子凝胶具有不同的刺激响应相行为及表观形貌,如氨基-酰胺/柠檬酸超分子具有热响应溶胶-凝胶可逆转换相行为,凝胶态可在70~80℃获得,临界凝胶化温度为76℃,冻干凝胶呈球状缠绕结构;氨基-酰胺/马来酸超分子具有pH诱导溶胶-凝胶可逆转换行为,pH在7~8之间可形成水凝胶态,冻干凝胶呈柱状囊泡结构。氨基-酰胺/柠檬酸超分子对农药的包封率略高于氨基-酰胺/马来酸,三元羧酸与氨基-酰胺形成的超分子与二元羧酸相比,从结构和电荷的角度,更有利于实现农药的智能缓释效果。

关键词: 凝胶, 胶体, 界面, 超分子组装, 农药缓控释

Abstract:

To improve the water dispersibility of hydrophobic pesticides, herein, an intelligent and controllable amphiphilic supramolecular hydrogel system is developed. This system consists of a kind of amphiphilic molecules named amino-amide and polycarboxylic acids including maleic acid and citric acid as examples, which was formed at a lower concentration [5.8%(mass)] via self-assembled by hydrogen bonding. Such supramolecular hydrogels exhibited a stable three-dimensional cross-linked network structure. The performance and structure of two kinds supramolecular hydrogels were compared by means of differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), 1H nuclear magnetic resonance (1H NMR), scanning electron microscope (SEM), dynamic light scattering (DLS) and viscosity test, which two supramolecular gels exhibited different stimulus responsive phase behaviors and different morphologies. Specifically, amino amide/citric acid supramolecular had thermal responsive phase behavior in a reversible conversion of sol-gel, and supramolecular gel state could be obtained at 70—80℃ with a critical gelation temperature of 76℃, and its freeze-dried state gel possessed a cross-linked spherical structure. Comparatively, amino amido/maleic acid supramolecular possessed pH induced reversible conversion of sol-gel cycle, and could form hydrogel state between pH of 7—8, and its corresponding freeze-dried gel exhibited pillar-like vesicle structure. The encapsulation rate of amino-amide/citric acid supramolecules to pesticides is slightly higher than that of amino-amide/maleic acid. Compared with dicarboxylic acids, supramolecules formed by tricarboxylic acids and amino-amides, from the perspective of structure and charge, it is more conducive to achieve the intelligent slow-release effect of pesticides.

Key words: gels, colloid, interface, supramolecular assembly, controlled release of pesticides

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