Chlorophyll triplet quenchers

Carotenoids function in photosynthesis as quenchers of chlorophyll triplet states to prevent their harmful reaction with oxygen. Current research has mainly focused on their detection and identification, the determination of kinetic parameters, and the elucidation of the triplet energy transfer pathways in both photosynthetic antenna and reaction centers. Since carotenoids do not take part in the photosynthetic electron transfer reactions, their paramagnetic radical species occur to a lesser extent in vivo, although they may play arole in the photoprotection of Photosystem II. 

Carotenoids function in photosynthetic reaction centers (RC) as triplet quenchers of the primary donor chlorophyll or bacteriochlorophyll triplet states. The best studied RCs are those of purple photosynthetic bacteria where atomic models are available based on X-ray crystallography and optical as well as magnetic resonance spectroscopies have yielded a detailed picture of the flow of triplet energy transfer. Good reviews of these topics can be found in (Frank, 1992, 1993 Frank and Cogdell, 1996). 

Shetlar has derived non-linear relationships of the Stem-Volmer type suitable for systems in which quenching occurs by more than one mechanism. Rate constants for heavy atom fluorescence quenching of polynuclear aromatic hydrocarbons by 1-iodopropane in benzene have been found to decrease exponentially with the energy difference between the fluorescing state and the nearest lower triplet state (Dreeskamp et al.). Bromocyclopropane has been recommended as a heavy-atom quencher of excited singlet states since it is more photostable than simple alkyl bromides (Flemming, Quina, and Hammond). Laser studies with chlorophyll a have provided evidence for the interesting radiationless intermolecular process Tx + Sx -> T2 + S0 (Menzel). 

---