Resonance Raman scattering and optical absorption of adrenodoxin and selena-adrenodoxin

Raman spectra have been recorded for native and selenium substituted adrenodoxin in dilute solution. Adrenodoxin shows three bands at 397, 350 and 297 cm^?1, all polarized, which can be associated with the iron-sulfur core. Selenium substitution leaves the 350 cm^?1 band essentially unshifted, but the other two bands disappear and are replaced by new bands at 355 and 263 cm^?1. The 350 cm^?1 band is assigned to stretching of iron-sulfur (cysteine) bonds, while the 397 and 297 cm^?1 bands are associated with vibrations of the labile sulfur atoms. The iron-selenium charge transfer bands were observed at 438 and 480 nm for the oxidized form and at 580 nm for the reduced form. The reduced selena-adrenodoxin displayed absorption maxima at 4, 450 and 5, 550 cm^?1, which can be assigned to the d-d transitions of high-spin ferrous ion. From this data and the reported g-values of electron paramagnetic resonance signals, the spin-orbit coupling constants were calculated to be 170 and 210 cm^?1 for the respective d-d transitions.