Tautomers of a Fluorescent G Surrogate and Their Distinct Photophysics Provide Additional Information Channels

Thienoguanosine (thG) is an isomorphic nucleoside analogue acting as a faithful fluorescent substitute of G, with respectable quantum yield in oligonucleotides. Photophysical analysis of thG reveals the existence of two ground‐state tautomers with significantly shifted absorption and emission wavele...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie 2016-07, Vol.128 (28), p.8106-8110
Main Authors: Sholokh, Marianna, Improta, Roberto, Mori, Mattia, Sharma, Rajhans, Kenfack, Cyril, Shin, Dongwon, Voltz, Karine, Stote, Roland H., Zaporozhets, Olga A., Botta, Maurizio, Tor, Yitzhak, Mély, Yves
Format: Article
Language:English
Subjects:
Ab-initio-Rechnungen
Absorption
Binding
Binding sites
Buffers
Channels
Chemistry
Deoxyribonucleic acid
DNA
Emission
Emission analysis
Fluorescence
Fluoreszenz
Genes
Information dissemination
Mathematical analysis
Molekülmodellierung
Nucleinsäuren
Nucleoside analogs
Nucleosides
Oligonucleotides
Residues
Sensitivity
Sensitivity analysis
Single-nucleotide polymorphism
Tautomerie
Tautomers
Wavelengths
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Thienoguanosine (thG) is an isomorphic nucleoside analogue acting as a faithful fluorescent substitute of G, with respectable quantum yield in oligonucleotides. Photophysical analysis of thG reveals the existence of two ground‐state tautomers with significantly shifted absorption and emission wavelengths, and high quantum yield in buffer. Using (TD)‐DFT calculations, the tautomers were identified as the H1 and H3 keto‐amino tautomers. When incorporated into the loop of (−)PBS, the (−)DNA copy of the HIV‐1 primer binding site, both tautomers are observed and show differential sensitivity to protein binding. The red‐shifted H1 tautomer is strongly favored in matched (−)/(+)PBS duplexes, while the relative emission of the H3 tautomer can be used to detect single nucleotide polymorphisms. These tautomers and their distinct environmental sensitivity provide unprecedented information channels for analyzing G residues in oligonucleotides and their complexes. Das isomorphe Guanosin‐Analogon thG liegt in Form zweier Tautomere vor. Beide treten in Einzelstrang‐Oligonukleotiden auf und sind empfindlich gegenüber Proteinbindung, aber nur das thG‐H1‐Tautomer ist für Doppelstränge günstig. Die Tautomere und ihre photophysikalischen Eigenschaften sind von größtem Nutzen für die Analyse von G‐Resten in Oligonukleotiden und ihren Komplexen. (d)Rib=2′‐Desoxy‐d‐ribose.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201601688