氨基-酰胺类智能超分子水凝胶农药载体制备

doi:10.11949/0438-1157.20200199

摘要/Abstract

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

中图分类号:

TB 381

郝丽, 黄丹丹, 关梅, 周红军, 周新华. 氨基-酰胺类智能超分子水凝胶农药载体制备[J]. 化工学报, 2020, 71(8): 3819-3829.

Li HAO, Dandan HUANG, Mei GUAN, Hongjun ZHOU, Xinhua ZHOU. Preparation of supramolecular-assemble hydrogels as pesticide carriers based on amphiphilic amino-amide compounds[J]. CIESC Journal, 2020, 71(8): 3819-3829.

图/表 10

图1 合成路线：硬脂酸与DMPDA缩合反应生成氨基-酰胺(a)；氨基-酰胺与柠檬酸组装形成温度响应超分子(b)；氨基-酰胺与马来酸组成形成pH响应超分子(c)

Fig.1 Synthesis routes: stearic acid and DMPDA condensation to form amino-amide(a); amino-amide and citric acid assemble to form temperature-responsive supramolecule(b); amino-amide and maleic acid to form pH-responsive supramolecule(c)

图2 氨基-酰胺/柠檬酸温度响应超分子水凝胶溶胶-凝胶转变(a)；氨基-酰胺/马来酸pH响应超分子水凝胶溶胶-凝胶转变(b)

Fig.2 Amino-amide/citric acid temperature-responsive supramolecular hydrogel sol-gel transition (a); amino-amide/maleic acid pH-responsive supramolecular hydrogel sol-gel transition(b)

图3 氨基-酰胺/柠檬酸(a)和氨基-酰胺/马来酸(b)超分子水凝胶黏度随温度变化曲线

Fig.3 Viscosity of amino-amide/citric acid(a) and amino-amide/maleic acid(b) supramolecular hydrogels vs. temperature

图4 氨基-酰胺及其与柠檬酸和马来酸的超分子冻干凝胶的DSC谱图

Fig.4 DSC curves of amino-amide and two supramolecular lyophilized gels with citric acid and maleic acid

图5 氨基-酰胺及其与柠檬酸和马来酸的超分子冻干凝胶的红外光谱图a—amino-amide; b—amino-amide/citric acid; c—amino-amide/maleic acid

Fig.5 FTIR spectra of amino-amide and its supramolecular lyophilized gels with citric acid and maleic acid

图6 氨基-酰胺/柠檬酸超分子（a）及氨基-酰胺/马来酸超分子(b)的1H NMR谱图

Fig.6 1H NMR spectra of amino-amide/citric acid supramolecular (a) and amino-amide/maleic acid supramolecular (b)

图7 氨基-酰胺与柠檬酸(a)和马来酸(b)的超分子冻干凝胶的SEM图像；氨基-酰胺/柠檬酸和氨基-酰胺/马来酸溶胶胶束的粒径分布(c)；氨基-酰胺/柠檬酸和氨基-酰胺/马来酸装载农药阿维菌素后胶束的粒径分布(d)

Fig.7 SEM images of amino-amide/citric acid supramolecular lyophilized gel (a), amino-amide/maleic acid supramolecular lyophilized gel (b); particle size distribution of amino-amide/citric acid and amino-amide/maleic acid sol micelles (c); micelle size distribution of amino-amide/citric acid and amino-amide/maleic acid loaded with avermectin (d)

图8 氨基-酰胺与柠檬酸(a)和马来酸(b)超分子装载阿维菌素后的冻干凝胶的SEM图像

Fig.8 SEM images of amino-amide/citric acid supramolecular lyophilized gel (a) and amino-amide/maleic acid supramolecular lyophilized gel (b) after avermectin loading

表1 氨基-酰胺/柠檬酸和氨基-酰胺/马来酸超分子对农药阿维菌素的包封率及稳定性

Table 1 Encapsulation efficiency and stability of avermectin by amino-amide/citric acid and amino-amide/maleic acid supramolecules

Sample	Encapsulation efficiency (EE)/%	EE after placing three days/%
AVM@amino-amide/citric acid	89.12±4.72	88.27±5.11
AVM@amino-amide/maleic acid	82.39±2.52	64.80±4.23

图9 阿维菌素@氨基-酰胺/柠檬酸载药超分子(a)和阿维菌素@氨基-酰胺/马来酸载药超分子(b)在不同温度、pH环境下的缓释曲线

Fig.9 Sustained-release curves of avermectin loaded amino-amide/citric acid supramoleculars (a) and avermectin loaded amino-amide/maleic acid supramolecular (b) under different temperatures and pH environments

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