Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer
Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer
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DOI：
10.1038/nchem.1938
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发表时间：
2014-07-01
期刊：
影响因子：
21.8
通讯作者：
Moore, Jeffrey S.
中科院分区：
文献类型：
--
作者：
Diesendruck, Charles E.;Peterson, Gregory I.;Moore, Jeffrey S.
生物系统依赖于可回收的物质资源，如氨基酸、碳水化合物和核酸。当生物材料因老化或应力而受损时，组织通过重构的解聚合-再聚合序列进行修复。将这一概念集成到合成材料系统中可能会导致设备寿命延长。在这里，我们展示了一种亚稳聚合物，端盖聚（邻苯二醛），经过机械引发的解聚，将材料还原为单体。诱捕实验和定向分子动力学模拟与异裂机制一致。得到的单体通过化学引发剂进行再聚合，有效地完成了解聚-再聚合循环。通过模拟生物材料的重塑，该模型系统表明了老化或机械损伤触发解聚的智能材料的可能性，并且在必要的时候和地方正交条件下再生聚合物。
Biological systems rely on recyclable materials resources such as amino acids, carbohydrates and nucleic acids. When biomaterials are damaged as a result of aging or stress, tissues undergo repair by a depolymerization-repolymerization sequence of remodelling. Integration of this concept into synthetic materials systems may lead to devices with extended lifetimes. Here, we show that a metastable polymer, end-capped poly(o-phthalaldehyde), undergoes mechanically initiated depolymerization to revert the material to monomers. Trapping experiments and steered molecular dynamics simulations are consistent with a heterolytic scission mechanism. The obtained monomer was repolymerized by a chemical initiator, effectively completing a depolymerization-repolymerization cycle. By emulating remodelling of biomaterials, this model system suggests the possibility of smart materials where aging or mechanical damage triggers depolymerization, and orthogonal conditions regenerate the polymer when and where necessary.