Premium
Synthesis and J‐Dimer Formation of Tetrapyrazinoporphyrazines with Different Functional Groups for Potential Biomolecular Probe Applications
Author(s) -
Demuth Jiri,
Miletin Miroslav,
Machan Matej,
Kantor Michal,
Zimcik Petr,
Novakova Veronika
Publication year - 2020
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.202000026
Subject(s) - chemistry , dimer , hexa , intramolecular force , pyridine , azide , functional group , monomer , titration , quenching (fluorescence) , surface modification , crystallography , stereochemistry , fluorescence , medicinal chemistry , organic chemistry , polymer , physics , quantum mechanics
Though tetrapyrazinoporphyrazines (TPyzPzs) are generally presented as universal dark quenchers for oligonucleotide probes, the availability of TPyzPzs bearing different functional groups suitable for attachment to 3′, and 5′ ends or intrastrand positions remains rather limited. Therefore, a synthetic route to hexa(bis(2‐methoxyethyl)amino) or hexa(diethylamino) TPyzPzs functionalized by an azide, hydroxy, or carboxy group or their combinations was developed. Studies of self‐assembly into J‐dimers in nonpolar solvents and their stability upon titration with pyridine (association constants, K P values, ranging 0.32–12.7×10 2 M −1 ) revealed that smaller peripheral substituents and functionalization of TPyzPzs improves the stability of J‐dimers. Φ Δ and Φ F were low for the monomers ( Φ F <0.0001, Φ Δ <0.008, DMF) due to quenching by intramolecular charge transfer; however, they increased in nonpolar solvents and after self‐assembly into J‐dimer (up to Φ F =0.027, Φ Δ =0.28).