Article | Published:

Switchable enantioseparation based on macromolecular memory of a helical polyacetylene in the solid state

Nature Chemistry volume 6, pages 429434 (2014) | Download Citation

Abstract

In the chromatographic separation of enantiomers the order of elution is determined by the strength of diasteromeric interactions between the components of the mixture and a chiral stationary phase. For analytical purposes, it is ideal to have the minor component elute first, whereas in the preparative mode a faster elution of the major component is desirable. Here we describe a stationary phase constructed from a polyacetylene that bears 2,2′-bisphenol-derived side chains in which chirality can be switched in the solid state prior to use. Both the macromolecular helicity of the polymer backbone and the axial chirality of the side chains can be switched in the solid state by interaction with a chiral alcohol, but importantly are maintained after removal of the chiral alcohol because of a memory effect. The chiral stationary phase thus prepared was used to separate the enantiomers of trans-stilbene oxide with the enantiomer elution order determined by the preseparation treatment.

  • Compound C30H42O5

    4-(Dodecyloxy)-4'-ethynyl-2,2'-bis(methoxymethoxy)-1,1'-biphenyl

  • Compound C8H10O

    (R)-1-Phenylethanol

  • Compound C8H10O

    (S)-1-Phenylethanol

  • Compound C20H30O

    1-(Dodecyloxy)-4-ethynylbenzene

  • Compound C32H46O5

    4-(Dodecyloxy)-2,2'-bis(ethoxymethoxy)-4'-ethynyl-1,1'-biphenyl

  • Compound C28H38O3

    4-(Dodecyloxy)-4'-ethynyl-2,2'-dimethoxy-1,1'-biphenyl

  • Compound C32H46O3

    4-(Dodecyloxy)-4'-ethynyl-2,2'-dipropoxy-1,1'-biphenyl

  • Compound C14H12O

    Trans-2,3-diphenyloxirane

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Acknowledgements

This work was supported in part by a grant from the Adaptable and Seamless Technology Transfer Program through Target-driven R&D from the Japan Science and Technology Agency, Grant-in-Aid for Scientific Research (S) from the Japan Society for the Promotion of Science and by the Nanotechnology Platform Program (Molecule and Material Synthesis) of the Ministry of Education, Culture, Sports, Science and Technology, Japan. We acknowledge H. Iida for his help in the measurements of the VCD spectra.

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Affiliations

  1. Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan

    • Kouhei Shimomura
    • , Tomoyuki Ikai
    • , Shigeyoshi Kanoh
    •  & Katsuhiro Maeda
  2. Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan

    • Eiji Yashima

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Contributions

K.M. conceived the project and designed the experiments. K.M. and E.Y. directed the research. K.S. principally performed the experiments. K.S. and T.I. performed experiments on enantioseparations. K.M. and E.Y. co-wrote the manuscript. All authors discussed the results and edited the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Eiji Yashima or Katsuhiro Maeda.

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DOI

https://doi.org/10.1038/nchem.1916

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