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Single-molecule analysis of chirality in a multicomponent reaction network

Nature Chemistry volume 6, pages 603–607 (2014)Cite this article

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Abstract

Single-molecule approaches to chemical reaction analysis can provide information that is not accessible by studying ensemble systems. Changes in the molecular structures of compounds tethered to the inner wall of a protein pore are known to affect the current carried through the pore by aqueous ions under a fixed applied potential. Here, we use this approach to study the substitution reactions of arsenic(III) compounds with thiols, stretching the limits of the protein pore technology to track the interconversion of seven reaction components in a network that comprises interconnected Walden cycles. Single-molecule pathway analysis of ‘allowed’ and ‘forbidden’ reactions reveals that sulfur–sulfur substitution occurs with stereochemical inversion at the arsenic centre. Hence, we demonstrate that the nanoreactor approach can be a valuable technique for the analysis of dynamic reaction systems of relevance to biology.

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Figure 1: The αHL nanoreactor.
Figure 2: Assignment of current levels.
Figure 3: Analysis of the reaction network.
Figure 4: Transition counts and computed reaction rates.
Figure 5: The complete reaction network.

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Acknowledgements

This work was supported by the Medical Research Council and a European Research Council advanced grant. H.B. was the holder of a Royal Society–Wolfson Research Merit Award. M.B.S. was the holder of a Ruth L. Kirschstein NIH Postdoctoral Fellowship (F32L078236).

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Author notes

  1. Mackay B. Steffensen & Dvir Rotem

    Present address: Present addresses: Southern Utah University, Physical Science Department, 351 West Center, Cedar City, Utah 84720, USA (M.B.S.), Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel (D.R.),

  2. Mackay B. Steffensen and Dvir Rotem: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK

    Mackay B. Steffensen, Dvir Rotem & Hagan Bayley

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  1. Mackay B. Steffensen
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Contributions

M.B.S. and D.R. contributed equally to this work. M.B.S. and H.B. designed the research. M.B.S. performed the experimental work. M.B.S., D.R. and H.B. analysed data and wrote the manuscript.

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Correspondence to Hagan Bayley.

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The authors declare no competing financial interests.

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Steffensen, M., Rotem, D. & Bayley, H. Single-molecule analysis of chirality in a multicomponent reaction network. Nature Chem 6, 603–607 (2014). https://doi.org/10.1038/nchem.1949

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