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

Martha Zoumpoulaki (1, 2, 3, 4, 5) , Gabrielle Schanne (1, 2, 3, 4, 5) , Nicolas Delsuc (1, 2, 3, 4, 5) , Hugues Preud'Homme (6) , Elodie Quévrain (1, 5, 2, 3, 4) , Nicolas Eskenazi (7) , Géraldine Gazzah (5, 8, 9) , Régis Guillot, (10) , Philippe Seksik (3) , Joelle Vinh (11, 7, 12) , Ryszard Lobinski (6) , Clotilde Policar (1, 2, 3, 4, 5)

1 LBM UMR 7203 - Laboratoire des biomolécules
2 ENS-PSL - École normale supérieure - Paris
3 SU - Sorbonne Université
4 INC-CNRS - Institut de Chimie - CNRS Chimie
5 Département de Chimie - ENS Paris
6 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
7 SMBP - Spectrométrie de Masse Biologique et Protéomique (USR3149 / FRE2032)
8 LBM-E1 - Peptides, glycoconjugués et métaux en biologie
9 UPMC - Université Pierre et Marie Curie - Paris 6
10 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay
11 ESPCI Paris - Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris
12 PdC - Laboratoire Plasticité du Cerveau Brain Plasticity (UMR 8249)

The detection and quantification of exogenous metal complexes are crucial to understanding their activity in intricate biological media. MnII complexes are difficult to detect and quantify because of low association constants, and high lability. The superoxide dismutase (SOD) mimic (or mimetic) labelled Mn1 is based on a 1,2-di-aminoethane functionalized with imidazole and phenolate and has good intrinsic anti-superoxide, antioxidant and anti-inflammatory activities in lipopolysaccharide (LPS)-activated intestinal epithelial HT29-MD2 cells, similar to that of its propylated analogue labelled Mn1P. Ion mobility spectrometry-mass spectrometry (IMS-MS) is a powerful technique for separating low molecular weight (LMW) metal complexes and can even separate complexes with the same ligand but bound to different divalent metal cations with similar ionic radii. We demonstrated the intracellular presence of the Mn1 and Mn1P complexes, at least partly intact, in lysates of cells incubated with the complexes and estimated the intracellular Mn1P concentration using a Co-13C6 analogue.

Mots clés: Bioinorganic Chemistry; Intracellular Detection; Ion Mobility Spectroscopy; Manganese(II) Superoxide Dismutase Mimics or Mimetics; Mass Spectrometry

Domaines: Chimie

Martha Zoumpoulaki, Gabrielle Schanne, Nicolas Delsuc, Hugues Preud'Homme, Elodie Quévrain, et al.. Deciphering the Metal Speciation in Low‐Molecular‐Weight Complexes by IMS‐MS: Application to the Detection of Manganese Superoxide Dismutase Mimics in Cell Lysates. Angewandte Chemie International Edition, 2022, ⟨10.1002/anie.202203066⟩. ⟨hal-03699781⟩