G-quadruplex self-assembly regulated by Coulombic interactions

Self-assembly offers the possibility to organize molecules in a given architecture through a subtle interplay between different noncovalent interactions. Although the kind of molecular

association can often be predicted from information present in the individual molecules, the synthesis of supramolecular assemblies having a perfectly defined size and shape remains

challenging. Here, we introduce the use of Coulombic interactions to control the supramolecular synthesis of finite, well-defined nanostructures. In particular, we demonstrate that the

energy associated with the separation of ion pairs can regulate very precisely guanosine self-assembly into discrete G-quadruplexes. Assemblies comprising 8, 12, 16 or 24 guanosine molecules

can be selectively and quantitatively obtained simply by tuning the stabilization of the dissociated anions in the solvent environment. Thus, factors such as solvent polarity, the nature of

the anion and the cation–anion distance are shown to have a decisive role in the growth of G-quadruplexes.

The authors are grateful for financial support from the Council for the Chemical Sciences of the Netherlands Organization for Scientific Research (CW-NWO). D.G.-R. would like to acknowledge

a Marie Curie Intraeuropean Fellowship. We would also like to thank A. de la Escosura for his help with the transmission electron microscopy, P.G.A. Janssen and T. de Greef for discussions,

and G.P. Spada and G. Gottarelli for discussions and support at the beginning of this project.

Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600 MB, The Netherlands

David González-Rodríguez, Joost L. J. van Dongen, Albertus P. H. J. Schenning & E. W. Meijer

Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Faculty of Science, Utrecht University, Padualaan 8, Utrecht, 3584 CH, The Netherlands

Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600 MB, The Netherlands

D.G.-R. designed and performed the synthesis and experiments and wrote the paper. J.L.J.v.D. contributed to the MS experiments. M.L. and A.L.S. contributed to the X-ray structural analysis.

A.P.H.J.S. and E.W.M. supervised the work.

Crystallographic data for the 16-mer complex formed from compound 3 and KI (CIF 102 kb)

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