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

doi:10.1016/j.isci.2024.109689

Supramolecular DNA-based catalysis in organic solvents

iScience. 2024 Apr 9;27(5):109689. doi: 10.1016/j.isci.2024.109689. eCollection 2024 May 17.

Authors

Gurudas Chakraborty^{1

2}, Konstantin Balinin^{1

2

3}, Rafael Del Villar-Guerra⁴, Meike Emondts^{2

5}, Giuseppe Portale¹, Mark Loznik^{1

2}, Wiebe Jacob Niels Klement¹, Lifei Zheng², Tanja Weil³, Jonathan B Chaires⁴, Andreas Herrmann^{1

2

5}

Affiliations

¹ Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, the Netherlands.
² DWI-Leibniz Institute for Interactive Materials, Forckenbeckstraße 50, 52056 Aachen, Germany.
³ Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
⁴ James Graham Brown Cancer Center, University of Louisville, 505 S. Hancock St., Louisville, KY 40202, USA.
⁵ Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074 Aachen, Germany.

Abstract

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.

Keywords: Biomolecular engineering; Catalysis; Chemistry.