Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Studies on the subcellular localization of the porphycene CPO

This study was designed to provide more detailed information on the subcellular sites of binding of the porphycene, termed 9-capronyloxytetrakis (methoxyethyl) porphycene (CPO), with a fluorescence resonance energy transfer (FRET) technique. The proximity of CPO to two fluorescent probes was determined: nonyl acridine orange (NAO), a dye with specific affinity for the mitochondrial lipid cardiolipin, and dihexa-oxacarbocyanine iodide (DiOC6), an agent that labels the endoplasmic reticulum (ER). FRET spectra indicated energy transfer between DiOC6 and CPO but no significant transfer between NAO and CPO. These results confirm data obtained by fluorescence microscopy, suggesting a similar pattern of subcellular localization by CPO and DiOC6 but not by CPO and NAO. However, when cells containing CPO were irradiated and then loaded with NAO, FRET between the two fluorophores was observed. Hence, a relocalization of CPO can occur during irradiation. These data provide an explanation for recent studies on CPO-catalyzed photodamage to both ER and mitochondrial Bcl-2.     

Weak-Link Versus Active Carbon Degradation Routes in the Oxidation of Aromatic Heterocyclic Systems. III

A polybenzimidazolone prepared by the condensation of 1,45,8-naphthalene tetracarboxylic acid and 3,3′-diaminobenzidine and several model compounds were thermally degraded (300-500°C) under inert and oxidative conditions. In every case only small fragments, i.e., carbon oxides, cyanogen (trace), and water, were detected by spectroscopic and chromatographic analysis of all phases of the pyrolysis products. The significance of these results is discussed in light of the mechanism by which this aromatic heterocyclic system undergoes oxidative degradation.     

An Improved Synthesis of Ethylidenecyclobutane

In our studies of the chemistry of small rings, it was necessary to synthesize ethylidenecyclobutane 1. Repetition of the only method in the literature^2,3 was attempted, namely, the reaction of 1,1,1-tris-(hydroxymethyl)-propane 2 with phosphorus tribromide to give 1,1,1-tris-(bromomethyl)-propane 3 and the subsequent conversion of 3 to 1 with zinc. The reaction of 2 with phosphorus tribromide is exceedingly hazardous. In spite of the careful adherence to the conditions specified by Derfer, et. al.² there were several fires in the effluent gases and the reaction produced precipitates which ignited spontaneously in air.