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Nat Commun. 2019 Apr 8;10(1):1612. doi: 10.1038/s41467-019-09486-2.

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

Author information

1
Laboratory of Molecular Simulation (LSMO), Institut des Sciences et Ingénierie Chimiques (ISIC), École Polytechnique Fédérale de Lausanne (EPFL Valais Wallis), Rue de l'Industrie 17, CH-1951, Sion, Switzerland.
2
Department of Chemistry, University College London, 20 Gordon St, London, WC1H 0AJ, UK.
3
Laboratory of Magnetic Resonance (LRM), Institut des Sciences et Ingénierie Chimiques (ISIC), École Polytechnique Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland.
4
School of Chemistry, University of Southampton, Highfield Campus, Southampton, SO17 1BJ, UK.
5
Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.
6
Laboratory of Molecular Simulation (LSMO), Institut des Sciences et Ingénierie Chimiques (ISIC), École Polytechnique Fédérale de Lausanne (EPFL Valais Wallis), Rue de l'Industrie 17, CH-1951, Sion, Switzerland. kyriakos.stylianou@epfl.ch.

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.

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