Towards a vibrational analysis of spheroidene. Resonance Raman spectroscopy of 13C-labelled spheroidenes in petroleum ether and in the Rhodobacter sphaeroides reaction centre

Abstract

We report resonance Raman spectra of the carotenoid spheroidene and its 14'-13C and 15'-13C substituted analogues in petroleum ether and bound to the reaction centre of Rhodobacter sphaeroides R26. The spectra in petroleum ether correspond to planar all-trans spheroidene while those of the reaction centres are consistent with a nonplanar 15,15'-cis spheroidene. The effect of 13C labelling is largest in the carbon-carbon double-bond stretching region. The 15'-13C substitution of the reaction centre bound spheroidene, however, hardly changes the C=C band as compared to that for the natural abundance spheroidene apart from a new weak band at 1508 cm(-1). This observation has been interpreted as a decoupling of the C15=C15' stretch from the other double-bond stretches in combination with a small intrinsic Raman intensity of this local mode for 15,15'-cis spheroidene.