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Controlled Stacking and Unstacking of Peripheral Chlorophyll Units Drives the Spring-Like Contraction and Expansion of a Semi-Artificial Helical Polymer

  作者 NUMATA MUNENORI; KINOSHITA DAIKI; HIROSE NAOYA; KOZAWA TOMOHIRO; TAMIAKI HITOSHI; KIKKAWA YOSHIHIRO; KANESATO MASATOSHI  
  选自 期刊  Chemistry-A European Journal;  卷期  2013年19-5;  页码  1592-1598  
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[摘要]Developing new strategies for controlling polymer conformations through precise molecular recognition can potentially generate a machine-like motion that is dependent on molecular informationan important process for the preparation of new intelligent nanomaterials (e.g., polymer-based nanomachines) in the field bordering between polymer chemistry and conventional supramolecular sciences. Herein, we propose a strategy to endow a helical polymer chain with dynamic spring-like (contraction/expansion) motion through the one-dimensional self-assembly (aggregation/disaggregation) of peripheral amphiphilic molecules. In this developing system, we employed a semi-artificial helical polysaccharide presenting peripheral amphiphilic chlorophyll units as a power device that undergoes contractive motion in aqueous media, driven by strong pp interactions of its chlorophyll units or by cooperative molecular recognition of bipyridyl-type ligands through pairs of chlorophyll units, thereby converting molecular information into the regulated motion of a spring. In addition, this system also undergoes expansive motion through coordination of pyridine. We anticipate that this strategy will be applicable (when combined with the established wrapping chemistry of the helical polysaccharide) to the development of, for example, drug carriers (e.g., nano-syringes), actuators (stimuli-responsive films), and directional transporters (nano-railways), thereby extending the frontiers of supramolecular science.

 
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