The bimolecular rate constants k(q) for quenching of singlet oxygen ((
1) Delta(g) state) by 26 different natural and novel synthetic caroten
oids were determined at 37 degrees C in a mixture of chloroform and et
hanol. The steady-state technique used involves the generation of O-1(
2) by thermal decomposition of disodium 3,3'-naphtalene-1,4-diyl-dipro
pionate endoperoxide (NDPO2) and the detection of its luminescence int
ensity at 1270 nm. Excitation energies (pi, pi, 1(1)A(g) --> 1(1)B(u)
) and absorption maxima (430-590 nn) vary in the broadest range. Deepl
y coloured blue carotenoids are also included in the studies for the f
irst time. An empirical correlation between the pi,pi (1(1)A(g) --> 1
(1)B(u)) excitation energy and carotenoid structure (effective chain l
ength N-eff) was found: E(S) = 12642 cm(-1) + 92027 cm(-1) x 1/N-eff.
The quenching ability of the investigated carotenoids depends on the e
xcitation energy of their transition at long wavelengths in a characte
ristic way showing as Limiting factors either the thermal Arrhenius ac
tivation or the diffusion-controlled rate. This dependence and the sus
pected relationship between singlet E(S) and triplet E(T) energies, re
spectively, are discussed.