Tailored Tolane‐Perfluorotolane Assembly as Supramolecular Base Pair Replacement in DNA. (1st December 2022)

• Record Type: Journal Article
• Authors: Neitz, Hermann; Bessi, Irene; Kachler, Valentin; Michel, Manuela; Höbartner, Claudia
• Is Part Of: Angewandte Chemie. Volume 135:Number 1(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-01
• Subjects: Arene-Fluoroarene -- Artificial Base Pair -- DNA -- Supramolecular Interaction -- XNA; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202214456
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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. Abstract : Polar π‐interactions and preferential stacking were observed by attaching tolane and perfluorotolanes as nucleobase surrogates to acyclic backbone replacements in an otherwise unmodified DNA duplex. The butyl nucleic acid (BuNA) was identified as privileged scaffold for exploiting the supramolecular arene‐fluoroarene recognition in DNA.