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Selection of supramolecular chirality by application of rotational and magnetic forces

Nature Chemistry volume 4, pages 201–207 (2012)Cite this article

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Abstract

Many essential biological molecules exist only in one of two possible mirror-image structures, either because they possess a chiral unit or through their structure (helices, for example, are intrinsically chiral), but so far the origin of this homochirality has not been unraveled. Here we demonstrate that the handedness of helical supramolecular aggregates formed by achiral molecules can be directed by applying rotational, gravitational and orienting forces during the self-assembly process. In this system, supramolecular chirality is determined by the relative directions of rotation and magnetically tuned effective gravity, but the magnetic orientation of the aggregates is also essential. Applying these external forces only during the nucleation step of the aggregation is sufficient to achieve chiral selection. This result shows that an almost instantaneous chiral perturbation can be transferred and amplified in growing supramolecular self-assemblies, and provides evidence that a falsely chiral influence is able to induce absolute enantioselection.

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Figure 1: Characterization of the supramolecular aggregates.
Figure 2: Experimental procedure.
Figure 3: Selection of supramolecular chirality.
Figure 4: Correlation between the observed chirality and the applied physical forces.
Figure 5: Proposed model for the chiral selection and amplification.

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Acknowledgements

We thank P.W. Albers for technical assistance with the magnet set-up. This work was supported by EuroMagNET II under EU Contract No. 228043, PRIN 2008- 2008A9C4HZ and 20088NTBKR (Ministero dell'Istruzione, dell'Università e della Ricerca) and by the Stichting voor Fundamenteel Onderzoek der Materie financially supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek.

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Authors and Affiliations

  1. CNR-IPCF Istituto per i Processi Chimico-Fisici, Messina, Italy

    N. Micali

  2. High Field Magnet Laboratory, Institute for Molecules and Materials, Radboud University Nijmegen, The Netherlands

    H. Engelkamp, P. G. van Rhee, P. C. M. Christianen & J. C. Maan

  3. Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, and C.I.R.C.M.S.B., Italy

    L. Monsù Scolaro

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Contributions

N.M. and L.M.S. initiated the project. N.M., H.E., P.C.M.C. and L.M.S. designed and realized the experimental set-up for chiral selection. N.M., H.E. and L.M.S. performed the chiral selection experiments. P.G.R. and P.C.M.C. developed the LD set-up and P.G.R. performed these experiments. N.M., H.E., P.G.R., P.C.M.C. and L.M.S. analysed the results. H.E., P.C.M.C. N.M. and L.M.S. co-wrote the paper. All the authors discussed the results and commented on the manuscript.

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Correspondence to L. Monsù Scolaro.

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Micali, N., Engelkamp, H., van Rhee, P. et al. Selection of supramolecular chirality by application of rotational and magnetic forces. Nature Chem 4, 201–207 (2012). https://doi.org/10.1038/nchem.1264

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