4.8 Article

Diarylethene-Powered Light-Induced Folding of Supramolecular Polymers

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 15, 页码 5845-5854

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c00592

关键词

-

资金

  1. JSPS KAKENHI [19H02760]
  2. Kumagai Foundation for Science and Technology
  3. Iketani Science and Technology Foundation
  4. Photon Factory Program Advisory Committee [2016G550]
  5. Grants-in-Aid for Scientific Research [19H02760] Funding Source: KAKEN

向作者/读者索取更多资源

The research investigates the helical folding mechanism of a novel type of SPs, realizing a reversible folding/unfolding process driven by photoisomerization. The helical folding is driven by internal structure ordering of the SP fiber that repairs defects and occurs only for the resulting helicoidal structure.
Helical folding of randomly coiled linear polymers is an essential organization process not only for biological polypeptides but also for synthetic functional polymers. Realization of this dynamic process in supramolecular polymers (SPs) is, however, a formidable challenge because of their inherent lability of main chains upon changing an external environment that can drive the folding process (e.g., solvent, concentration, and temperature). We herein report a photoinduced reversible folding/unfolding of rosette-based SPs driven by photoisomerization of a diarylethene (DAE). Temperature-controlled supramolecular polymerization of a barbiturate-functionalized DAE (open isomer) in nonpolar solvent results in the formation of intrinsically curved, but randomly coiled, SPs due to the presence of defects. Irradiation of the randomly coiled SPs with UV light causes efficient ring-closure reaction of the DAE moieties, which induces helical folding of the randomly coiled structures into helicoidal ones, as evidenced by atomic force microscopy and small-angle X-ray scattering. The helical folding is driven by internal structure ordering of the SP fiber that repairs the defects and interloop interaction occurring only for the resulting helicoidal structure. In contrast, direct supramolecular polymerization of the ring-closed DAE monomers by temperature control affords linearly extended ribbon-like SPs lacking intrinsic curvature that are thermodynamically less stable compared to the helicoidal SPs. The finding represents an important concept applicable to other SP systems; that is, postpolymerization (photo)reaction of preorganized kinetic structures can lead to more thermodynamically stable structures that are inaccessible directly through temperature-controlled protocols.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.8
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据