Electron spin-relaxation via vibronic level of nickel (I) and nickel (III) cyanide complexes in NaCl single crystals.

Electron spin-lattice relaxation rates for the low spin [Ni(CN)(4)](1-) and [Ni(CN)(4)](3-) complexes in NaCl host lattice were measured by the inversion recovery technique in the temperature range 7-50K. The data for both paramagnetic species fit very well to a relaxation process involving localized anharmonic vibration modes, also responsible for the g-tensor temperature dependence.

Electron spin relaxation via vibronic level of rhodium(II) hexacyanide complex in KCl crystal.

Electron spin-lattice relaxation rates for the low-spin [Rh(CN)(6)](4-) complex in KCl were measured by the inversion recovery and saturation recovery techniques, in the range of 5 to 30 K. Angular variation experiments indicate that electron spin-lattice relaxation times present axial symmetry. The data fit very well to a relaxation process involving localized anharmonic vibration modes, also responsible for the g tensor temperature dependence.

Characterization of the bactericidal effects of sodium nitroprusside and other pentacyanonitrosyl complexes on the food spoilage bacterium Clostridium sporogenes.

The potent bactericidal activity of sodium nitroprusside (SNP; Na2[Fe(CN)5(NO)]) towards Clostridium sporogenes has been investigated. SNP inhibited cell growth in the concentration range of 10 to 40 microM. Concentrations above 80 microM caused irreversible loss of cell viability and cell lysis. Inhibition of cell growth was similar in complex and in defined media. SNP was found to be unreactive towards individual components of the defined medium, with the exception of cysteine. The chemical characteristics responsible for the potency of SNP were investigated by synthesizing analogs of SNP in which the Fe was replaced by different metals. The inhibitory potency of the pentacyanonitrosyl complexes decreased in the order Fe > Cr > V, which correlates with N-O stretching frequency (vNO). In contrast, the Ru complex which had a vNO comparable to that of Fe was a poor inhibitor. Electron paramagnetic resonance spectroscopy showed that SNP was rapidly reduced to the paramagnetic Fe(I) compound [Fe(CN)4(NO)](2-) on contact with cells. Analysis of fractions from SNP-treated cells showed 90% oxidation of thiols in the cell walls compared with those in control cells. The toxicity of SNP involves S-nitrosation and reduction, the lack of toxicity of the Ru analog being consistent with the fact that it has poor reactivity towards thiols. When C. sporogenes cells were exposed to sublethal concentrations of SNP and viewed under the electron microscope, they showed blisters on the surface. These results point to the cell wall surface as a primary point of attack of the nitrosyl complex.

EPR dating CO2- sites in tooth enamel apatites by ENDOR and triple resonance.

In this work we combine electron paramagnetic resonance (EPR), high-resolution electron nucleus double resonance (ENDOR) and general triple resonance (GTR) spectroscopies, to study the local environment of the CO2- groups created by ionizing radiation in fossil tooth enamel. We demonstrate that the CO2- groups occupy slightly modified phosphate sites in the hydroxyapatite lattice. In quaternary shark enamel we found these groups to be interacting with water molecules in the apatite channels. The absence of water molecules as first neighbors in mammalian samples indicate, however, that these molecules are not significantly responsible for the stabilization of CO2- dating centers in enamel.