
G-quadruplex self-assembly regulated by coulombic interactions
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ABSTRACT 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. Access through your institution Buy or subscribe This is a preview of
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SALT Article 10 February 2021 SEQUENCE-ENCODED INTERMOLECULAR BASE PAIRING MODULATES FLUIDITY IN DNA AND RNA CONDENSATES Article Open access 07 May 2025 REFERENCES * Whitesides, G. M. &
Grzybowski, B. Self-assembly at all scales. _Science_ 295, 2418–2421 (2002). Article CAS PubMed Google Scholar * Schmittel, M. & Kalsani, V. Functional, discrete, nanoscale
supramolecular assemblies. _Top. Curr. Chem._ 245, 1–53 (2005). Article CAS Google Scholar * Prins, L. J., De Jong, F., Timmerman, P. & Reinhoudt, D. N. An enantiomerically pure
hydrogen-bonded assembly. _Nature_ 408, 181–184 (2000). Article CAS PubMed Google Scholar * Sato, S. et al. Fluorous nanodroplets structurally confined in an organopalladium sphere.
_Science_ 313, 1273–1276 (2006). Article CAS PubMed Google Scholar * Sugimoto, T., Suzuki, T., Shinkai, S. & Sada, K. A double-stranded helix by complexation of two polymer chains
with a helical supramolecular assembly. _J. Am. Chem. Soc._ 129, 270–271 (2007). Article CAS PubMed Google Scholar * Janssen, P. G. A., Vandenbergh, J., van Dongen, J. L., Meijer, E.W.
& Schenning, A. P. H. J. ssDNA templated self-assembly of chromophores. _J. Am. Chem. Soc._ 129, 6078–6079 (2007). Article CAS PubMed Google Scholar * Ikeda, A., Numata, M. &
Shinkai, S. A novel attempt to control the aggregation number of dendrons with a saccharide. _Chem. Lett._ 9, 929–930 (1999). Article Google Scholar * Michelsen, U. & Hunter, C. A.
Self-assembled porphyrin polymers. _Angew. Chem. Int. Ed._ 39, 764–767 (2000). Article CAS Google Scholar * Brunsveld, L., Folmer, B. J. B., Meijer, E. W. & Sijbesma, R.
Supramolecular polymers. _Chem. Rev._ 101, 4071–4098 (2001). Article CAS PubMed Google Scholar * Sundquist, W. I. & Klug, A. Telomeric DNA dimerizes by formation of guanine tetrads
between hairpin loops. _Nature_ 342, 825–829 (1989). Article CAS PubMed Google Scholar * Huppert, J. L. Four-stranded nucleic acids: structure, function and targeting of G-quadruplexes.
_Chem. Soc. Rev._ 37, 1375–1384 (2008). Article CAS PubMed Google Scholar * Davis, J. T. G-quartets 40 years later: From 5′-GMP to molecular biology and supramolecular chemistry. _Angew.
Chem. Int. Ed._ 43, 668–698 (2004). Article CAS Google Scholar * Davis, J. T. & Spada, G. P. Supramolecular architectures generated by self-assembly of guanosine derivatives. _Chem.
Soc. Rev._ 36, 296–313 (2007). Article CAS PubMed Google Scholar * Gu, J., Leczczynski, J. & Banal, M. A new insight into the structure and stability of Hoogsteen hydrogen-bonded
G-tetrad: An _ab initio_ SCF study. _Chem. Phys. Lett._ 311, 209–214 (1999). Article CAS Google Scholar * García-Arriaga, M., Hobley, G. & Rivera, J. M. Isostructural self-assembly of
2′-deoxyguanosine derivatives in aqueous and organic media. _J. Am. Chem. Soc._ 130, 10492–10493 (2008) Article PubMed PubMed Central Google Scholar * Guschlbauer, W., Chantot, J. F.
& Thiele, D. Four-stranded nucleic acid structures 25 years later: From guanosine gels to telomer DNA. _J. Biomol. Struct. Dyn._ 8, 491–511 (1990). Article CAS PubMed Google Scholar
* Gottarelli, G. et al. The self-assembly of lipophilic guanosine derivatives in solution and on solid surfaces. _Chem. Eur. J._ 6, 3242–3248 (2000). Article CAS PubMed Google Scholar *
Marlow, A. L. et al. Cation-templated self-assembly of a lipophilic deoxyguanosine: Solution structure of a K+-dG8 octamer. _J. Org. Chem._ 64, 5116–5123 (1999). Article CAS PubMed Google
Scholar * Forman, S. L., Fettinger, J. C., Pieraccini, S., Gottarelli, G. & Davis, J. T. Toward artificial ion channels: A lipophilic G-quadruplex. _J. Am. Chem. Soc._ 122, 4060–4067
(2000). Article CAS Google Scholar * Shi, X., Fettinger, J. C. & Davis, J. T. Homochiral G-quadruplexes with Ba2+ but not with K+: The cation programs enantiomeric self-recognition.
_J. Am. Chem. Soc._ 123, 6738–6739 (2001). Article CAS PubMed Google Scholar * Shi, X. et al. Lipophilic G-quadruplexes are self-assembled ion pair receptors, and the bound anion
modulates the kinetic stability of these complexes. _J. Am. Chem. Soc._ 125, 10830–10841 (2003). Article CAS PubMed Google Scholar * Ma, L., Iezzi, M., Kaucher, M. S., Lam, Y.-F. &
Davis, J. T. Cation exchange in lipophilic G-quadruplexes: Not all ion binding sites are equal. _J. Am. Chem. Soc._ 128, 15269–15277 (2006). Article CAS PubMed Google Scholar * Kaucher,
M. S., Lam, Y.-F., Pieraccini, S., Gottarelli, G. & Davis, J. T. Using diffusion NMR to characterize guanosine self-association: insights into structure and mechanism. _Chem. Eur. J._
11, 164–173 (2005). Article Google Scholar * Prins, L. J., De Jong, F., Timmerman, P. & Reinhoudt, D. N. Noncovalent synthesis using hydrogen bonding. _Angew. Chem. Int. Ed._ 40, 2382
(2001). Article CAS Google Scholar * Krossing, I. & Raabe, I. Noncoordination anions—Fact or fiction? A survey of likely candidates. _Angew. Chem. Int. Ed._ 43, 2066–2090 (2004).
Article CAS Google Scholar * Kotch, F. W. et al. Water-mediated association provides an ion pair receptor. _J. Am. Chem. Soc._ 125, 15140–15150 (2003). Article CAS PubMed Google
Scholar * Wüthrich, K. _NMR of Proteins and Nucleic Acids_ 208 (Wiley, 1986). * Sessler, J. L., Sathiosatham, M., Doerr, K., Lynch, V. & Abboud, K. A. A G-quartet formed in the absence
of a templating metal cation: A new 8-(_N_,_N_-dimethylaniline)guanosine derivative. _Angew. Chem. Int. Ed._ 39, 1300–1303 (2000). Article CAS Google Scholar * Giorgi, T. et al.
Supramolecular helices via self-assembly of 8-oxoguanosines. _J. Am. Chem. Soc._ 125, 14741–14749 (2002). Article Google Scholar * Mezzina, E. et al. The self-assembly of a lipophilic
guanosine nucleoside into polymeric columnar aggregates: the nucleoside structure contains sufficient information to drive the process towards a strikingly regular polymer. _Chem. Eur. J._
7, 388–395 (2001). Article CAS PubMed Google Scholar * Mariani, P., Mazabard, C., Garbesi, A. & Spada, G. P. A study of the structure of the lyomesophases formed by the dinucleoside
phosphate d(GpG). An approach by x-ray diffraction and optical microscopy. _J. Am. Chem. Soc._ 111, 6369–6373 (1989). Article CAS Google Scholar Download references ACKNOWLEDGEMENTS 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. AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * 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 Martin Lutz &
Anthony L. Spek * Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600 MB, The Netherlands E. W. Meijer Authors * David González-Rodríguez
View author publications You can also search for this author inPubMed Google Scholar * Joost L. J. van Dongen View author publications You can also search for this author inPubMed Google
Scholar * Martin Lutz View author publications You can also search for this author inPubMed Google Scholar * Anthony L. Spek View author publications You can also search for this author
inPubMed Google Scholar * Albertus P. H. J. Schenning View author publications You can also search for this author inPubMed Google Scholar * E. W. Meijer View author publications You can
also search for this author inPubMed Google Scholar CONTRIBUTIONS 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. CORRESPONDING AUTHOR Correspondence to E. W. Meijer. SUPPLEMENTARY
INFORMATION SUPPLEMENTARY INFORMATION Supplementary information (PDF 5953 kb) SUPPLEMENTARY INFORMATION Crystallographic data for the 16-mer complex formed from compound 3 and KI (CIF 102
kb) RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE González-Rodríguez, D., van Dongen, J., Lutz, M. _et al._ G-quadruplex self-assembly regulated by
Coulombic interactions. _Nature Chem_ 1, 151–155 (2009). https://doi.org/10.1038/nchem.177 Download citation * Received: 18 December 2008 * Accepted: 10 March 2009 * Published: 19 April 2009
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