Supramolecular DNA-based catalysis in organic solvents
Gurudas Chakraborty,
Konstantin Balinin,
Rafael del Villar-Guerra,
Meike Emondts,
Giuseppe Portale,
Mark Loznik,
Wiebe Jacob Niels Klement,
Lifei Zheng,
Tanja Weil,
Jonathan B. Chaires,
Andreas Herrmann
Affiliations
Gurudas Chakraborty
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, the Netherlands; DWI-Leibniz Institute for Interactive Materials, Forckenbeckstraße 50, 52056 Aachen, Germany
Konstantin Balinin
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, the Netherlands; DWI-Leibniz Institute for Interactive Materials, Forckenbeckstraße 50, 52056 Aachen, Germany; Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
Rafael del Villar-Guerra
James Graham Brown Cancer Center, University of Louisville, 505 S. Hancock St., Louisville, KY 40202, USA
Meike Emondts
DWI-Leibniz Institute for Interactive Materials, Forckenbeckstraße 50, 52056 Aachen, Germany; Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074 Aachen, Germany
Giuseppe Portale
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, the Netherlands
Mark Loznik
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, the Netherlands; DWI-Leibniz Institute for Interactive Materials, Forckenbeckstraße 50, 52056 Aachen, Germany
Wiebe Jacob Niels Klement
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, the Netherlands
Lifei Zheng
DWI-Leibniz Institute for Interactive Materials, Forckenbeckstraße 50, 52056 Aachen, Germany
Tanja Weil
Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
Jonathan B. Chaires
James Graham Brown Cancer Center, University of Louisville, 505 S. Hancock St., Louisville, KY 40202, USA
Andreas Herrmann
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, the Netherlands; DWI-Leibniz Institute for Interactive Materials, Forckenbeckstraße 50, 52056 Aachen, Germany; Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074 Aachen, Germany; Corresponding author
Summary: The distinct folding accompanied by its polymorphic character renders DNA G-quadruplexes promising biomolecular building blocks to construct novel DNA-based and supramolecular assemblies. However, the highly polar nature of DNA limits the use of G-quadruplexes to water as a solvent. In addition, the archetypical G-quadruplex fold needs to be stabilized by metal-cations, which is usually a potassium ion. Here, we show that a noncovalent PEGylation process enabled by electrostatic interactions allows the first metal-free G-quadruplexes in organic solvents. Strikingly, incorporation of an iron-containing porphyrin renders the self-assembled metal-free G-quadruplex catalytically active in organic solvents. Hence, these “supraG4zymes” enable DNA-based catalysis in organic media. The results will allow the broad utilization of DNA G-quadruplexes in nonaqueous environments.
