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Homochiral porous nanosheets for enantiomer sieving

Nature Materials (2018) | Download Citation


Protein pores are highly specific in binding to chiral substrates and in catalysing stereospecific reactions, because their active pockets are asymmetric and stereoselective1,2. Chiral binding materials from molecular-level pores with high specificity have not been achieved because of problems with pore deformation and blocking3. A promising solution is the self-assembly of single sheets where all pores are exposed to the environment, for example as metal–organic frameworks4, polymers5,6 or non-covalent aromatic networks7,8,9,10, but, typically, the pores are distant from the internal cavities with chirality. Here, we report the synthesis of homochiral porous nanosheets achieved by the 2D self-assembly of non-chiral macrocycles, with open/closed pore switching. Pore chirality is spontaneously induced by a twisted stack of dimeric macrocycles. The porous 2D structures can serve as enantiomer sieving membranes that exclusively capture a single enantiomer in a racemic mixture solution, with uptake capacity greater than 96%. Moreover, the entrapped guests inside the pores can be pumped out by pore closing triggered by external stimuli. This strategy could provide new opportunities for controlled molecule release, as well as for artificial cells.

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  1. 1.

    Gilson, M. K. & Zhou, H.-X. Calculation of protein–ligand binding affinities. Annu. Rev. Biophys. Biomol. Struct. 36, 21–42 (2007).

  2. 2.

    Stank, A., Kokh, D. B., Fuller, J. C. & Wade, R. C. Protein binding pocket dynamics. Acc. Chem. Res. 49, 809–815 (2016).

  3. 3.

    Cui, Y. et al. Metal–organic frameworks as platforms for functional materials. Acc. Chem. Res. 49, 483–493 (2016).

  4. 4.

    Peng, Y. et al. Metal–organic framework nanosheets as building blocks for molecular sieving membranes. Science 346, 1356–1359 (2014).

  5. 5.

    Kissel, P. et al. A two-dimensional polymer prepared by organic synthesis. Nat. Chem. 4, 287–291 (2012).

  6. 6.

    Kissel, P., Murray, D. J., Wulftange, W. J., Catalano, V. J. & King, B. T. A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization. Nat. Chem. 6, 774–778 (2014).

  7. 7.

    Colson, J. W. et al. Oriented 2D covalent organic framework thin films on single-layer graphene. Science 332, 228–231 (2011).

  8. 8.

    Dong, R. et al. Large-area, free-standing, two-dimensional supramolecular polymer single-layer sheets for highly efficient electrocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 54, 12058–12063 (2015).

  9. 9.

    Zhang, K. D. et al. Toward a single-layer two-dimensional honeycomb supramolecular organic framework in water. J. Am. Chem. Soc. 135, 17913–17918 (2013).

  10. 10.

    Yue, L. et al. Flexible single-layer ionic organic–inorganic frameworks towards precise nano-size separation. Nat. Commun. 7, 10742 (2016).

  11. 11.

    Iyoda, M. & Shimizu, H. Multifunctional π-expanded oligothiophene macrocycles. Chem. Soc. Rev. 44, 6411–6424 (2015).

  12. 12.

    Huang, Z. et al. Pulsating tubules from noncovalent macrocycles. Science 337, 1521–1526 (2012).

  13. 13.

    Percec, V. et al. Self-assembly of amphiphilic dendritic dipeptides into helical pores. Nature 430, 764–768 (2004).

  14. 14.

    Colson, J. W. & Dichtel, W. R. Rationally synthesized two-dimensional polymers. Nat. Chem. 5, 453–465 (2013).

  15. 15.

    Kim, Y. et al. Switchable nanoporous sheets by the aqueous self-assembly of aromatic macrobicycles. Angew. Chem. Int. Ed. 52, 6426–6429 (2013).

  16. 16.

    Shimizu, H. et al. Synthesis, structures, and photophysical properties of π-expanded oligothiophene 8-mers and their Saturn-like C60 complexes. J. Am. Chem. Soc. 137, 3877–3885 (2015).

  17. 17.

    Lee, S., Chen, C.-H. & Flood, A. H. A pentagonal cyanostar macrocycle with cyanostilbene CH donors binds anions and forms dialkylphosphate [3]rotaxanes. Nat. Chem. 5, 704–710 (2013).

  18. 18.

    Würthner, F., Kaiser, T. E. & Saha‐Möller, C. R. J-aggregates: from serendipitous discovery to supramolecular engineering of functional dye materials. Angew. Chem. Int. Ed. 50, 3376–3410 (2011).

  19. 19.

    Wang, Y., Xu, J., Wang, Y. & Chen, H. Emerging chirality in nanoscience. Chem. Soc. Rev. 42, 2930–2962 (2013).

  20. 20.

    Huang, K. & Szleifer, I. Design of multifunctional nanogate in response to multiple external stimuli using amphiphilic diblock copolymer. J. Am. Chem. Soc. 139, 6422–6430 (2017).

  21. 21.

    Nelson, J. C., Saven, J. G., Moore, J. S. & Wolynes, P. G. Solvophobically driven folding of nonbiological oligomers. Science 277, 1793–1796 (1997).

  22. 22.

    Chen, L. et al. Separation of rare gases and chiral molecules by selective binding in porous organic cages. Nat. Mater. 13, 954–960 (2014).

  23. 23.

    Zhang, G.-W. et al. Triptycene-based chiral macrocyclic hosts for highly enantioselective recognition of chiral guests containing a trimethylamino group. Angew. Chem. Int. Ed. 55, 5304–5308 (2016).

  24. 24.

    Hauser, A. W. et al. Functionalized graphene as a gatekeeper for chiral molecules: an alternative concept for chiral separation. Angew. Chem. Int. Ed. 53, 9957–9960 (2014).

  25. 25.

    Seo, J. S. et al. A homochiral metal–organic porous material for enantioselective separation and catalysis. Nature 404, 982–986 (2000).

  26. 26.

    Xie, R., Chu, L.-Y. & Deng, J.-G. Membranes and membrane processes for chiral resolution. Chem. Soc. Rev. 37, 1243–1263 (2008).

  27. 27.

    Kim, Y. et al. Open–closed switching of synthetic tubular pores. Nat. Commun. 6, 8650 (2015).

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This work was supported by the National Natural Science Foundation of China (grants 21634005, 51473062 and 21574055) and Jilin University Funding (JLUSTIRT).

Author information


  1. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, China

    • Bo Sun
    • , Yongju Kim
    • , Yanqiu Wang
    • , Huaxin Wang
    • , Xin Liu
    •  & Myongsoo Lee
  2. Pohang Accelerator Laboratory, Postech, Pohang, Gyeongbuk, Korea

    • Jehan Kim


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B.S. synthesized molecules, measured spectroscopic data, carried out the uptake experiments. Y.K. performed chiral separation and molecular simulations, and supervised the research. Y.W. performed TEM experiments. H.W. carried out NMR experiments. J.K. performed X-ray experiments. X.L. measured electron diffraction. M.L. developed the concept, supervised the research and wrote the manuscript with input from all authors.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Yongju Kim or Myongsoo Lee.

Electronic supplementary material

  1. Supplementary information

    Supplementary Schemes 1–2, Supplementary Figures 1–34, Supplementary References 1–3

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