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Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(II)-OOH species and a copper mediated NO reductive coupling reaction.

ABSTRACT: New peroxynitrite-copper chemistry ensues via addition of nitric oxide (?NO(g)) to a Cu(II)-hydroperoxo species. In characterizing the system, the ligand-Cu(i) complex was shown to effect a seldom observed ?NO(g) reductive coupling reaction. Biological implications are discussed.

SUBMITTER: Kim S

PROVIDER: S-EPMC3931255 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature

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Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(II)-OOH species and a copper mediated NO reductive coupling reaction.

Kim Sunghee S Siegler Maxime A MA Karlin Kenneth D KD

Chemical communications (Cambridge, England) 20131209 22

New peroxynitrite-copper chemistry ensues via addition of nitric oxide (˙NO(g)) to a Cu(II)-hydroperoxo species. In characterizing the system, the ligand-Cu(i) complex was shown to effect a seldom observed ˙NO(g) reductive coupling reaction. Biological implications are discussed. ...[more]

PMID: 24322625

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Project description:The Cu2+ complexes formed by a series of cyclen derivatives bearing sulfur pendant arms, 1,4,7,10-tetrakis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO4S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO3S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-10-acetamido-1,4,7,10-tetraazacyclododecane (DO3SAm), and 1,7-bis[2-(methylsulfanyl)ethyl]-4,10-diacetic acid-1,4,7,10-tetraazacyclododecane (DO2A2S), were studied in aqueous solution at 25 °C from thermodynamic and structural points of view to evaluate their potential as chelators for copper radioisotopes. UV-vis spectrophotometric out-of-cell titrations under strongly acidic conditions, direct in-cell UV-vis titrations, potentiometric measurements at pH >4, and spectrophotometric Ag+-Cu2+ competition experiments were performed to evaluate the stoichiometry and stability constants of the Cu2+ complexes. A highly stable 1:1 metal-to-ligand complex (CuL) was found in solution at all pH values for all chelators, and for DO2A2S, protonated species were also detected under acidic conditions. The structures of the Cu2+ complexes in aqueous solution were investigated by UV-vis and electron paramagnetic resonance (EPR), and the results were supported by relativistic density functional theory (DFT) calculations. Isomers were detected that differed from their coordination modes. Crystals of [Cu(DO4S)(NO3)]·NO3 and [Cu(DO2A2S)] suitable for X-ray diffraction were obtained. Cyclic voltammetry (CV) experiments highlighted the remarkable stability of the copper complexes with reference to dissociation upon reduction from Cu2+ to Cu+ on the CV time scale. The Cu+ complexes were generated in situ by electrolysis and examined by NMR spectroscopy. DFT calculations gave further structural insights. These results demonstrate that the investigated sulfur-containing chelators are promising candidates for application in copper-based radiopharmaceuticals. In this connection, the high stability of both Cu2+ and Cu+ complexes can represent a key parameter for avoiding in vivo demetalation after bioinduced reduction to Cu+, often observed for other well-known chelators that can stabilize only Cu2+.

Dataset Information

Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(II)-OOH species and a copper mediated NO reductive coupling reaction.

Publications

Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(II)-OOH species and a copper mediated NO reductive coupling reaction.

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