Hierarchical self-assembly of a small monomer with two orthogonal binding sites: from discrete hexagonal containers to a stimuli-responsive supramolecular gel
Hierarchical self-assembly of a small monomer with two orthogonal binding sites: from discrete hexagonal containers to a stimuli-responsive supramolecular gel
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DOI：
10.1080/10610278.2017.1392020
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发表时间：
2018-01-01
影响因子：
3.3
通讯作者：
Schmuck, Carsten
中科院分区：
文献类型：
--
作者：
Grossert, Kerstin;Sicking, Wilhelm;Schmuck, Carsten
描述了一种小型自互补单体1，具有基于离子配对和金属配体配位的两种正交结合相互作用，可在极性溶液（DMSO）中的单体，环状低聚物以及线性和3d网状聚合物之间可逆切换。采用原子力显微镜、透射电子显微镜、氦离子显微镜和扩散有序谱对其聚集进行了研究。首先，在较低浓度下，六角形环状容器形成，而在较高浓度下，分层自组装导致金属凝胶。这种凝胶可以通过不同的刺激，如pH值、温度变化或添加金属和金属螯合剂，分别在溶胶/凝胶状态之间切换。超分子凝胶相当稳定，并表现出有趣的剪切变薄行为。
A small self-complementary monomer 1 is described, with two orthogonal binding interactions based on ion pairing and metal-ligand coordination, which is reversibly switchable between monomer, cyclic oligomers as well as linear- and 3D-netlike polymers in polar solution (DMSO). The aggregation was studied by atomic force microscopy, transmission electron microscopy, helium ion microscopy (HIM) and diffusion ordered spectroscopy (DOSY NMR). First, at lower concentrations, hexagonal cyclic containers are formed, whereas at higher concentrations hierarchical self-assembly leads to a metallogel. This gel can be switched between the sol/gel-state using different stimuli like pH, temperature changes or the addition of metal and metal-chelators, respectively. The supramolecular gel is rather stable and shows interesting shear thinning behavior.[GRAPHICS].