Nuclear localization of dirhodium(ii) complexes in breast cancer cells by X-ray fluorescence microscopy

Abstract

X-ray fluorescence microscopy confirms the necessity of vacant axial sites in dirhodium(ii) carboxylates for their cellular uptake and cytotoxicity.

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

“…Dinuclear complexes with a paddlewheel structure show a rich chemistry and different electronic configurations as a consequence of the distribution of the energy levels and the number of electrons in the dimetallic unit [1,2]. Dirhodium complexes and, in particular, the tetracarboxylato derivatives, are among the most important and versatile paddlewheel compounds [1,2], and their reactivity has been explored in several fields such as catalysis [3][4][5][6][7][8][9] or bioinorganic chemistry [10][11][12][13]. The ground state electron configuration for most of these complexes is σ 2 π 4 δ 2 δ* 2 π* 4 for a diamagnetic Rh 2 4+ unit, which, therefore, displays a single metal-metal bond order [1,2].…”

Unambiguous Intracellular Localization and Quantification of a Potent Iridium Anticancer Compound by Correlative 3D Cryo X‐Ray Imaging

“…Half-sandwich complex ACC25 of formula [Ir(h 5 :k 1 -C 5 Me 4 CH 2 py)(phpy)]PF 6 (Figure 1), where C 5 Me 4 CH 2 py is 2-[(2,3,4,5-tetramethylcyclopentadienyl)methyl]pyridine,a nd phpy = 2-phenylpyridine,w as synthesized by chloride abstraction from [Ir(h 5 :k 1 -C 5 Me 4 CH 2 py)Cl 2 ] [18] with silver nitrate,a nd subsequent addition of 2-phenylpyridine in dichloromethane.C ation [Ir(h 5 :k 1 -C 5 Me 4 CH 2 py)(phpy)] + was isolated as the hexafluorophosphate salt in good yield (60 %). Compound ACC25 was characterized by 1 Ha nd 13 CNMR spectroscopy (Supporting Information, Figure S1), elemental analysis and mass spectrometry.…”

Deciphering the Metal Speciation in Low‐Molecular‐Weight Complexes by IMS‐MS: Application to the Detection of Manganese Superoxide Dismutase Mimics in Cell Lysates

“…The reliable detection and quantification of exogenous metal complexes, such as metallodrugs or metal‐based probes in intricate biological media, is essential for a good understanding of their bioactivity and can be particularly challenging. Various imaging techniques [1] based on fluorescence, [2–4] vibrational spectroscopies, including Fourier transform infrared spectroscopy (μ‐FTIR), [5–12] μ‐Raman, [13, 14] laser ablation inductively coupled plasma mass spectrometry LA‐ICP‐MS, [15, 16] or X‐ray fluorescence (XRF) [5, 17–29] can be used for the intracellular detection and mapping of metal complexes. Furthermore, mass spectrometry‐based techniques, [30] such as ICP‐MS, [30–33] electrospray ionization tandem mass spectrometry (ESI‐MS/MS), [34] liquid chromatography‐mass spectrometry (LC‐MS), [35, 36] as well as electron paramagnetic resonance (EPR) [25, 37] or atomic absorption spectrometry (AAS), [35, 38–44] have been used for their detection and quantification in cells or organisms.…”