Issue 15, 2022

Anticancer half-sandwich Ir(iii) complex and its interaction with various biomolecules and their mixtures – a case study with ascorbic acid

Abstract

The extent of interactions with various biomolecules is a crucial feature of newly developed metallodrugs, worthy of thorough investigation, as its understanding helps uncover the fate of these xenobiotics in the physiological environment. In this work, promisingly cytotoxic half-sandwich complexes [Ru(η6-pcym)Cl(L1)]PF6 (1), [Ir(η5-Cp*)Cl(L1)]PF6 (2) and [Ir(η5-Cp*)Cl(L2)]PF6 (3), with 2-{n-[(E)-phenyldiazenyl]pyridin-2-yl}-1H-benzimidazole as a bidentate N-donor azo ligand (n = 5 for L1 and 6 for L2; pcym = p-cymene, Cp* = pentamethylcyclopentadienyl), were subjected to an extensive and detailed study of interactions with a plethora of extra- and intracellular biologically relevant molecules. For the first time in the field of anticancer half-sandwich complexes, mixtures of 3 with ascorbic acid (ASA) and its combinations with reduced glutathione (GSH) and/or reduced nicotinamide adenine dinucleotide (NADH) were studied. Complex 3 undergoes azo bond reduction when mixed with NADH or ASA, which oxidizes to NAD+ or dehydroascorbate (DHA), respectively. Intriguingly, the presence of the natural antioxidant ASA has a relevant prooxidative impact on GSH, which is connected with ASA recovery from DHA. Although the azo bond of L2 involved in 3 seems to be the reaction centre for the dehydrogenation reactions of the biomolecules, L2 by itself is a negligible oxidant and thus complexation in 3 represents a necessary prerequisite for the redox reactions.

Graphical abstract: Anticancer half-sandwich Ir(iii) complex and its interaction with various biomolecules and their mixtures – a case study with ascorbic acid

Supplementary files

Article information

Article type
Research Article
Submitted
10 Mar 2022
Accepted
31 May 2022
First published
01 Jun 2022

Inorg. Chem. Front., 2022,9, 3758-3770

Anticancer half-sandwich Ir(III) complex and its interaction with various biomolecules and their mixtures – a case study with ascorbic acid

L. Masaryk, J. Orvoš, K. Słoczyńska, R. Herchel, J. Moncol, D. Milde, P. Halaš, R. Křikavová, P. Koczurkiewicz-Adamczyk, E. Pękala, R. Fischer, I. Šalitroš, I. Nemec and P. Štarha, Inorg. Chem. Front., 2022, 9, 3758 DOI: 10.1039/D2QI00535B

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