RESUMO
Source-based calibration methods used for photon attenuation and coincidence summing corrections are time consuming and require multiple certified standards that match sample geometry with varying densities. Three programs which are capable of simulating a variety of sample geometries, matrix compositions, and sample densities have been examined as alternatives. LabSOCS, ANGLE 3 and GESPECOR are effective at generating efficiency curves for food matrices with a range with different densities. The curves generated have been successfully used to determine activity in food samples.
Assuntos
Contaminação Radioativa de Alimentos/análise , Radiometria/métodos , Espectrometria gama/métodos , Calibragem , Radioisótopos de Césio/análise , Radioisótopos de Cobalto/análise , Raios gama , Humanos , Fótons , Radiometria/estatística & dados numéricos , Software , Espectrometria gama/estatística & dados numéricosRESUMO
Mononuclear copper complexes, [(tmpa)Cu(II)(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)Cu(II)(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3) in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)Cu(II)(O2)Cu(II)(tmpa)](2+), the two-electron reduced product of O2 with Sc(3+) is observed to be scandium peroxide ([Sc(III)(O2(2-))](+)). In the presence of 3 equiv of hexamethylphosphoric triamide (HMPA), [Sc(III)(O2(2-))](+) was oxidized by [Fe(bpy)3](3+) (bpy = 2,2-bipyridine) to the known superoxide species [(HMPA)3Sc(III)(O2(â¢-))](2+) as detected by EPR spectroscopy. A kinetic study revealed that the rate-determining step of the catalytic cycle for the two-electron reduction of O2 with 1 is electron transfer from Fc* to 1 to give a cuprous complex which is highly reactive toward O2, whereas the rate-determining step with 2 is changed to the reaction of the cuprous complex with O2 following electron transfer from ferrocene derivatives to 2. The explanation for the change in catalytic O2-reaction stoichiometry from four-electron with Brønsted acids to two-electron reduction in the presence of Sc(3+) and also for the change in the rate-determining step is clarified based on a kinetics interrogation of the overall catalytic cycle as well as each step of the catalytic cycle with study of the observed effects of Sc(3+) on copper-oxygen intermediates.
Assuntos
Cobre/química , Ácidos de Lewis/química , Mesilatos/química , Escândio/química , 2,2'-Dipiridil/química , Catálise , Complexos de Coordenação/química , Cristalografia por Raios X , Espectroscopia de Ressonância de Spin Eletrônica , Elétrons , Compostos Ferrosos/química , Metalocenos , Oxirredução , Oxigênio/química , Piridinas/químicaRESUMO
New five- and six-coordinate complexes containing the [Mn(III)(Br4cat)2](-) core (Br4cat(2-) = tetrabromo-1,2-catecholate) have been prepared. Homoleptic [Mn(III)(Br4cat)3](3-) reacts rapidly with O2 to produce tetrabromo-1,2-benzoquinone (Br4bq). The [Mn(III)(Br4cat)2](-) fragment is a robust catalytic platform for the aerobic conversion of catechols to quinones. The oxidase activity apparently derives from the coupling of metal- and ligand-centered redox events.