Interaction of radiation-generated radicals with myoglobin in aqueous solution. III. Effects of oxygen and catalase on the product distribution in solutions of ferrimyoglobin containing N2O.

The gamma-radiolysis of aqueous solutions of ferrimyoglobin in the presence of N2O at pH 7.3 has been examined as a function of added catalase and oxygen. Changes in the nature of the heme group have been monitored by visible absorption spectrophotometry and analysed quantitatively by a multiple wavelength method based on Beer's Law. Simple chemical analyses have been used to confirm qualitative identification of the product derivatives. As observed previously, the ferriheme is reduced by indirect globin-mediated action initiated by OH/H. The yield of reduced product decreases as [O2] increases. Conversion to ferrimyoglobin through the participation of H2O2 derived from irradiated water and from protein-mediated processes in oxygenated solution, is eliminated by the presence of catalase. Formation of a hemichrome form of ferrimyoglobin is apparent at higher doses in the presence of O2. These results demonstrate that oxygen plays an important role in controlling the nature and extent of redox that manifests ultimately on the heme group of ferrimyoglobin as a result of the initial interaction of OH/H.

Photochemical precipitation of thorium and cerium and their separation from other ions in aqueous solution.

Thorium was precipitated from homogeneous solution by exposing solutions of thorium and periodate in dilute perchloric acid to 253.7 nm radiation from a low-pressure mercury lamp. Periodate is reduced photochemically to iodate which causes the formation of a dense precipitate of the basic iodate of thorium(IV). The precipitate was redissolved, the iodate reduced, the thorium precipitated first as the hydroxide, then as the oxalate and ignited to the dioxide for weighing. Thorium(IV) solutions containing 8-200 mg of ThO(2) gave quantitative results with a standard deviation (s) of 0.2 mg. Separations from 25 mg each of iron, calcium, magnesium, 50 mg of yttrium and up to 500 mg of uranium(VI) were quantitative (s = 0.25 mg). Separations from rare earths, except cerium, were accomplished by using hexamethylenetetramine rather than ammonia for the precipitation of the hydroxide. Cerium(III) was similarly precipitated and converted into CeO(2) for weighing. Quantitative results were obtained for 13-150 mg of CeO(2) with a standard deviation of 0.2 mg. Separations from 200 mg of uranium were quantitative. Other rare earths and yttrium interfered seriously. The precipitates of the basic cerium(IV) and thorium iodates obtained are more compact than those obtained by direct precipitation and can be handled easily. Attempts to duplicate Suzuki's method for separating cerium from neodymium and yttrium were not successful.

Precipitation from homogeneous solution by photochemical action: determination of thorium.

Thorium was precipitated from homogeneous solution by photochemical reduction of periodate to iodate in a solution containing thorium and perchloric acid, by means of a 2537 A low-pressure mercury vapour lamp. For weighing, the precipitate was redissolved, precipitated once as thorium hydroxide, and finally as thorium oxalate, which was ignited to thorium dioxide. Quantitative results were obtained in the range 35-180 mg of thorium.