Journalartikel

Autorenliste: Kole, GK; Košćak, M; Amar, A; Majhen, D; Božinović, K; Brkljaca, Z; Ferger, M; Michail, E; Lorenzen, S; Friedrich, A; Krummenacher, I; Moos, M; Braunschweig, H; Boucekkine, A; Lambert, C; Halet, JF; Piantanida, I; Müller-Buschbaum, K; Marder, TB

Jahr der Veröffentlichung: 2022

Zeitschrift: Chemistry - A European Journal

Bandnummer: 28

Heftnummer: 40

ISSN: 0947-6539

eISSN: 1521-3765

Open Access Status: Green

DOI Link: https://doi.org/10.1002/chem.202200753

Verlag: Wiley

Abstract: 
A series of bis-(4'-pyridylethynyl)arenes (arene=benzene, tetrafluorobenzene, and anthracene) were synthesized and their bis-N-methylpyridinium compounds were investigated as a class of pi-extended methyl viologens. Their structures were determined by single crystal X-ray diffraction, and their photophysical and electrochemical properties (cyclic voltammetry), as well as their interactions with DNA/RNA were investigated. The dications showed bathochromic shifts in emission compared to the neutral compounds. The neutral compounds showed very small Stokes shifts, which are a little larger for the dications. All of the compounds showed very short fluorescence lifetimes (<4 ns). The neutral compound with an anthracene core has a quantum yield of almost unity. With stronger acceptors, the analogous bis-N-methylpyridinium compound showed a larger two-photon absorption cross-section than its neutral precursor. All of the dicationic compounds interact with DNA/RNA; while the compounds with benzene and tetrafluorobenzene cores bind in the grooves, the one with an anthracene core intercalates as a consequence of its large, condensed aromatic linker moiety, and it aggregates within the polynucleotide when in excess over DNA/RNA. Moreover, all cationic compounds showed highly specific CD spectra upon binding to ds-DNA/RNA, attributed to the rare case of forcing the planar, achiral molecule into a chiral rotamer, and negligible toxicity toward human cell lines at <= 10 mu M concentrations. The anthracene-analogue exhibited intracellular accumulation within lysosomes, preventing its interaction with cellular DNA/RNA. However, cytotoxicity was evident at 1 mu M concentration upon exposure to light, due to singlet oxygen generation within cells. These multi-faceted features, in combination with its two-photon absorption properties, suggest it to be a promising lead compound for development of novel light-activated theranostic agents.

Harvard-Zitierstil: Kole, G., Košćak, M., Amar, A., Majhen, D., Božinović, K., Brkljaca, Z., et al. (2022) Methyl Viologens of Bis-(4’-Pyridylethynyl)Arenes – Structures, Photophysical and Electrochemical Studies, and their Potential Application in Biology, Chemistry - A European Journal, 28(40), Article e202200753. https://doi.org/10.1002/chem.202200753

APA-Zitierstil: Kole, G., Košćak, M., Amar, A., Majhen, D., Božinović, K., Brkljaca, Z., Ferger, M., Michail, E., Lorenzen, S., Friedrich, A., Krummenacher, I., Moos, M., Braunschweig, H., Boucekkine, A., Lambert, C., Halet, J., Piantanida, I., Müller-Buschbaum, K., & Marder, T. (2022). Methyl Viologens of Bis-(4’-Pyridylethynyl)Arenes – Structures, Photophysical and Electrochemical Studies, and their Potential Application in Biology. Chemistry - A European Journal. 28(40), Article e202200753. https://doi.org/10.1002/chem.202200753