Kinetically Controlling the Length of Self-Assembled Polymer Nanofibers Formed by Intermolecular Hydrogen Bonds
Kinetically Controlling the Length of Self-Assembled Polymer Nanofibers Formed by Intermolecular Hydrogen Bonds
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DOI：
10.1021/acsmacrolett.1c00296
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发表时间：
2021-06-23
影响因子：
7.015
通讯作者：
Brendel, Johannes C.
中科院分区：
文献类型：
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作者：
Gruschwitz, Franka, V;Klein, Tobias;Brendel, Johannes C.
强的方向性氢键代表了一种合适的超分子力来驱动聚合物两亲物的一维（1D）水溶液自组装，从而产生圆柱形聚合物刷。然而，我们对这些组装过程中的动力学的理解仍然有限。我们在这里证明，我们最近报道的苯三脲和三肽共轭物的形态是强烈的路径依赖性。从有机溶剂中的溶液到水性环境的受控转移使得能够以速率依赖的方式形成从小的圆柱形或球形物体（2 μ m）的动力学捕获但稳定的纳米结构。一个详细的分析的基本组装机制揭示了合作的性质，尽管立体的要求的聚合物。成核是由疏水相互作用引起的，通过临界水含量，随后是由于强氢键的伸长过程。这些发现为控制一维聚合物纳米结构的长度开辟了一条有趣的新途径。
Strong directional hydrogen bonds represent a suitable supramolecular force to drive the one-dimensional (1D) aqueous self-assembly of polymeric amphiphiles resulting in cylindrical polymer brushes. However, our understanding of the kinetics in these assembly processes is still limited. We here demonstrate that the obtained morphologies for our recently reported benzene tris-urea and tris-peptide conjugates are strongly pathway-dependent. A controlled transfer from solutions in organic solvents to aqueous environments enabled a rate-dependent formation of kinetically trapped but stable nanostructures ranging from small cylindrical or spherical objects (2 mu m). A detailed analysis of the underlying assembly mechanism revealed a cooperative nature despite the steric demands of the polymers. Nucleation is induced by hydrophobic interactions crossing a critical water content, followed by an elongation process due to the strong hydrogen bonds. These findings open an interesting new pathway to control the length of 1D polymer nanostructures.