Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Homochiral porous nanosheets for enantiomer sieving

Nature Materials volume 17, pages 599–604 (2018)Cite this article

Subjects

Abstract

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Self-assembly of dimeric chiral pores into a gated homochiral porous nanosheet.
Fig. 2: Structural characterization of homochiral porous nanosheets.
Fig. 3: Two-dimensional growth of chiral pores and gating behaviour.
Fig. 4: Enantiomer sieving and pumping action.

Similar content being viewed by others

References

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

Download references

Acknowledgements

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

Author information

Authors and Affiliations

  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

Authors
  1. Bo Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yongju Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yanqiu Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Huaxin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jehan Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xin Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Myongsoo Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

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.

Corresponding authors

Correspondence to Yongju Kim or Myongsoo Lee.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Supplementary information

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sun, B., Kim, Y., Wang, Y. et al. Homochiral porous nanosheets for enantiomer sieving. Nature Mater 17, 599–604 (2018). https://doi.org/10.1038/s41563-018-0107-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-018-0107-4

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing