Organometallic Ni(III) intermediates have been proposed in several Nickel-catalyzed cross-coupling reactions, yet no isolated bis(hydrocarbyl)Ni(III) complexes have been reported to date. Herein we report the synthesis and detailed characterization of stable organometallic Ni(III) complexes that contain two trifluoromethyl ligands and are supported by tetradentate N-donor ligands (R)N4 (R = Me ...

We use spatially resolved photoelectron spectroscopy performed in operando to identify the reaction intermediates of the hydrogen electro-oxidation reaction on yttria-stabilized zirconia (YSZ) electrolytes with Pt electrodes. We find that hydroxyl on the zirconia electrolyte is a reaction intermediate in the hydrogen oxidation reaction and that it participates in the rate-determining step. In c...

Skeletal muscle mitochondrial dysfunction, evidenced by incomplete beta oxidation and accumulation of fatty acid intermediates in the form of long and medium chain acylcarnitines, may contribute to ectopic lipid deposition and insulin resistance during high fat diet (HFD)-induced obesity. The present review discusses the roles of anterograde and retrograde communication in nucleo-mitochondrial ...

Water oxidation is a key half reaction in the energy conversion scheme. The reaction mechanism for the oxidation of H2O to O2 catalyzed by single-Ru-substituted polyoxometalates, [Ru(III)(H2O)XW11O39](n-) (X = Si(IV), Ge(IV)), was investigated by means of density functional calculations. The electronic structure of the pre-activation intermediates indicates that the aqua ligand is prone to acco...

The regioselective attack on microsomal phospholipid (PL) polar heads (PH) and fatty acyl chains (FC) demonstrated in vitro has been exploited for the selective quantitation in vivo of the biochemical damages produced by the oxidation and reduction products of CHCl3 metabolism. Five hours after CHCl3 injection (60 mg/kg body weight, ip) to control Sprague-Dawley rats, most of the label covalent...

Introduction Direct transfer of metabolites between consecutive enzymes, or channelling, is a controversial topic, especially if the enzymes do not form a stable complex, i.e. ‘dynamic’ channelling [ 1-41. The level of passion aroused by discussions of metabolite channelling reflects a belief, not always explicitly stated, that if it occurs then it must have major metabolic consequences [ 51. V...