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Neutralization of Reactive Oxygen Species at Dinuclear Cu(II)-Cores: Tuning the Antioxidant Manifold in Water by Ligand Design

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journal contribution
posted on 19.06.2020, 13:03 by Andrea Squarcina, Alice Santoro, Neal Hickey, Rita De Zorzi, Mauro Carraro, Silvano Geremia, Marco Bortolus, Marilena Di Valentin, Marcella Bonchio
Dinuclear Cu2(II,II)-cores stabilized by the N3O donorset of HL1 = (2-{[[di­(2-pyridyl)­methyl]­(methyl)­amino]­methyl}­phenol), HL2 = 2-({[di­(2-pyridyl)­methyl]­amino}­methyl)­phenol), and HL3 = 2-({[di­(2-pyridyl)­methyl]­amino}­methyl)-4-nitrophenol display a unique superoxide dismutase (SOD) combined with catalase (CAT)-like activity in water, at neutral pH. The Cu2L12 < Cu2L22 < Cu2L32 structure–reactivity trend puts a spotlight on the electron-deficient core of Cu2L32 that exhibits the highest SOD (log kcat(O2•–) = 7.55) and CAT-like (kH2O2 = 0.66 M–1 s–1) performance. Time-lapse ESI-MS and EPR experiments indicate that a dimeric core is essential for oxygenic turnover upon H2O2 decomposition.

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