Tailored Tolane-Perfluorotolane Assembly as Supramolecular Base Pair Replacement in DNA.

Hermann Neitz, Irene Bessi, Valentin Kachler, Manuela Michel, Claudia Höbartner

Angewandte Chemie (International ed. in English) 2023 Jan 02

filter terms:

Arene-fluoroarene interactions offer outstanding possibilities for engineering of supramolecular systems, including nucleic acids. Here, we implement the tolane-perfluorotolane interaction as base pair replacement in DNA. Tolane (THH) and perfluorotolane (TFF) moieties were connected to acyclic backbone units, comprising glycol nucleic acid (GNA) or butyl nucleic acid (BuNA) building blocks, that were incorporated via phosphoramidite chemistry at opposite positions in a DNA duplex. Thermodynamic analyses by UV thermal melting revealed a compelling stabilization by THH/TFF heteropairs only when connected to the BuNA backbone, but not with the shorter GNA linker. Detailed NMR studies confirmed the preference of the BuNA backbone for enhanced polar π-stacking. This work defines how orthogonal supramolecular interactions can be tailored by small constitutional changes in the DNA backbone, and it inspires future studies of arene-fluoroarene-programmed assembly of DNA. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Citation

Hermann Neitz, Irene Bessi, Valentin Kachler, Manuela Michel, Claudia Höbartner. Tailored Tolane-Perfluorotolane Assembly as Supramolecular Base Pair Replacement in DNA. Angewandte Chemie (International ed. in English). 2023 Jan 02;62(1):e202214456