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The antioxidant activities-expressed as the electron-donating properties-of five hydrophilic carotenoids (carotenoid surfactants) and three related hydrophobic carotenoids were investigated by flash photolysis. The electron-transfer rates of the carotenoids to the triplet state of the sensitizer 2-nitronaphthalene and the energy transfer rates of triplet 2-nitronaphthalene to the carotenoids were determined. The results demonstrate that the electron-donating effects of the hydrophilic and hydrophobic carotenoids were comparable when evaluated in acetonitrile. In the presence of water, however, electron transfer (i.e., antioxidant efficiency) was enhanced by a factor of four for the hydrophilic carotenoids. The increased hydrophilicity of carotenoids, therefore, could expand their antioxidant properties, thus facilitating their use as aqueous-phase radical scavengers. At the same time, it was shown that supramolecular assembly ("aggregation") of the amphiphilic carotenoids prevented electron transfer, thus deactivating the antioxidant function. Modulation of the biophysical properties of carotenoids through synthetic modification is capable of increasing the biological and medical utility of this natural class of predominantly hydrophobic antioxidant compound.

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The surface and aggregation properties of the naturally occurring carotenoid crocin (1), examined through measurements of surface tension and UV/VIS absorption, have been used to determine the following parameters: critical aggregate concentration, surface-saturation concentration, molecular area, free energy of adsorption and micellation, adsorption-micellar energy relationship, equilibrium constants, and aggregate size. On structural grounds and based on the determined molecular area at the interface, the digentiobiosyl ester of the conjugated, highly unsaturated carotenoid diacid crocetin C20 : 7 should be classified as a bolaamphiphile. Crocin forms true monomolecular solutions in H 2 O; only at rather high concentrations aggregation occurs.

A microwave assisted Wittig reaction allowed the synthesis, in good yields, of the longest polyene so far recorded with 27 conjugated double bonds. The synthesis of this stable, well-soluble polyene represents a noteworthy step in the direction of ultimate λ(max).

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Three zeaxanthin homologues with conjugation lengths N of 15, 19, and 23 denoted as Z15, Z19, and Z23 were studied by femtosecond transient absorption spectroscopy, and the results were compared to those obtained for zeaxanthin (Z11). The energies of S2 decrease from 20 450 cm(-1) (Z11) to 18 280 cm(-1) (Z15), 17 095 cm(-1) (Z19), and 16 560 cm(-1) (Z23). Fitting the N dependence of the S2 energies allowed the estimation of [Formula: see text], the S2 energy of a hypothetical infinite zeaxanthin, to be ∼14 000 cm(-1). Exciting the 0-0 band of the S2 state produces characteristic S1-Sn spectral profiles in transient absorption spectra with maxima at 556 nm (Z11), 630 nm (Z15), 690 nm (Z19), and 740 nm (Z23). The red shift of the S1-Sn transition with increasing conjugation length is caused by a decrease in the S1 state energy, resulting in S1 lifetimes of 9 ps (Z11), 0.9 ps (Z15), 0.35 ps (Z19), and 0.19 ps (Z23). Essentially the same lifetimes were obtained after excess energy excitation at 400 nm, but S1-Sn becomes broader, indicating a larger conformation disorder in the S1 state after 400 nm excitation compared to excitation into the 0-0 band of the S2 state. An S* signal was observed in all samples, but only for Z15, Z19, and Z23 does the S* signal decay with a lifetime different from that of the S1 state. The S* lifetimes are 2.9 and 1.6 ps for Z15 and Z19, respectively. In Z23 the S* signal needs two decay components yielding lifetimes of 0.24 and 2.3 ps. The S* signal is more pronounced after 400 nm excitation.

Multi-channel, flash kinetic spectroscopy with microsecond time resolution has been used for investigating the interactions between carotenoids and the following photoproducts of alpha-tocopherol (EH) in hexane, methanol, acetonitrile, and dimethyl sulfoxide: (a) the lowest triplet, (b) the tocopherol radical cation, which could be seen only in the polar aprotic solvents acetonitrile and dimethyl sulfoxide, and (c) the neutral tocopheroxyl radical. The first two species reconvert to EH by transferring triplet excitation and positive charge (respectively) to the carotenoid; the third is unreactive. The relevance of these observations to photoprotection and the photoionisation of sterically hindered phenols is pointed out.