Nucleobase pairing and photodimerization in a biologically derived metal-organic framework nanoreactor

Samantha L. Anderson, Peter G. Boyd, Andrzej Gładysiak, Tu N. Nguyen, Robert G. Palgrave, Dominik Kubicki, Lyndon Emsley, Darren Bradshaw, Matthew J. Rosseinsky, Berend Smit and Kyriakos C. Stylianou ()
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Samantha L. Anderson: École Polytechnique Fédérale de Lausanne (EPFL Valais Wallis)
Peter G. Boyd: École Polytechnique Fédérale de Lausanne (EPFL Valais Wallis)
Andrzej Gładysiak: École Polytechnique Fédérale de Lausanne (EPFL Valais Wallis)
Tu N. Nguyen: École Polytechnique Fédérale de Lausanne (EPFL Valais Wallis)
Robert G. Palgrave: University College London
Dominik Kubicki: École Polytechnique Fédérale de Lausanne (EPFL)
Lyndon Emsley: École Polytechnique Fédérale de Lausanne (EPFL)
Darren Bradshaw: University of Southampton
Matthew J. Rosseinsky: University of Liverpool
Berend Smit: École Polytechnique Fédérale de Lausanne (EPFL Valais Wallis)
Kyriakos C. Stylianou: École Polytechnique Fédérale de Lausanne (EPFL Valais Wallis)

Nature Communications, 2019, vol. 10, issue 1, 1-8

Abstract: Abstract Biologically derived metal-organic frameworks (bio-MOFs) are of great importance as they can be used as models for bio-mimicking and in catalysis, allowing us to gain insights into how large biological molecules function. Through rational design, here we report the synthesis of a novel bio-MOF featuring unobstructed Watson-Crick faces of adenine (Ade) pointing towards the MOF cavities. We show, through a combined experimental and computational approach, that thymine (Thy) molecules diffuse through the pores of the MOF and become base-paired with Ade. The Ade-Thy pair binding at 40–45% loading reveals that Thy molecules are packed within the channels in a way that fulfill both the Woodward-Hoffmann and Schmidt rules, and upon UV irradiation, Thy molecules dimerize into Thy Thy. This study highlights the utility of accessible functional groups within the pores of MOFs, and their ability to ‘lock’ molecules in specific positions that can be subsequently dimerized upon light irradiation, extending the use of MOFs as nanoreactors for the synthesis of molecules that are otherwise challenging to isolate.

Date: 2019
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DOI: 10.1038/s41467-019-09486-2

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