Reactive oxygen species are potentially damaging molecules. An important function of antioxidants is to intercept harmful triplet states, in order to prevent the formation of singlet oxygen, or to quench singlet oxygen directly. However, antioxidants are also reactive towards other active oxygen species such as the hydroxyl radical, the superoxide anion and the non-excited oxygen ground state in the presence of radical initiators. It is well known that¯avonoids and carotenoids show strong antioxidant properties. Polyenes and carotenoids are the best known among the compounds that quench singlet oxygen by ef®cient energy transfer. A large number of modi®ed, synthetic analogues and derivatives have been synthesised to prepare even better quenchers than the natural carotenoids. Phenols are also excellent chain-breaking antioxidants. Recently, many indigoid dyes (including bacterial indigoids) were studied, with the remarkable result that most, but not all, members of this class of chromophores quench singlet oxygen at the diffusion limit and some of them are excellent radical traps. It has been shown in this study that a quantitative assessment of antioxidant properties of avonoids, carotenoids, phenols and natural indigoids can be achieved using the following three assays: (1) oxygen pressure dependence; (2) peroxide formation; (3) singlet oxygen quenching. Reactivities towards both excited states and ground state radicals can be properly described by these assays. The remarkable role of b-carotene as an`unusual antioxidant' (Burton GW and Ingold KU, Science 224: 569±573 (1984)) in reactions using various oxygen pressures becomes clearer. The socalled`pro-oxidant effects' concern primarily the antioxidant itself and its degradation, since no or very little damage to the substrate occurs in this type of experiment. Three main categories of antioxidants may be classi®ed: (1) excellent antioxidants that perfectly quench excited states as well as ground state radicals (eg actinioerythrol, astaxanthin); (2) good antioxidants that strongly inhibit peroxide formation but are less ef®cient in quenching excited states (eg¯avonols, tocopherols) or lead to considerable degradation of the antioxidant itself (eg b-carotene, lycopene); (3) moderate antioxidants that fail to excel in both reactivities (eg z-carotene,¯avone).

No abstract

No abstract

We report here on the synthesis and antioxidant properties of novel covalently linked flavonoidcarotenoid hybrids, hereinafter referred to as carotenylflavonoids. By this strategy the essential properties of the protecting systems are improved. Compared with the parent carotenoids or flavonoids, e.g. ß-carotene and a hydroxyflavone, these molecular combinations exhibit improved photoprotective properties, as seen from their UV spectra, and they outperform the individual constituents in their antioxidant properties. The dual functionality is revealed from the time evolution of the peroxidation inhibition assay which clearly displays both phenolic and carotenoidpolyenic contributions to the antioxidant efficiency. Furthermore, these compounds have amphiphilic character, in contrast to symmetrical carotenes and hydroxylated flavones. The antioxidative potential of the carotenylflavonoids is high. They protect cumene against peroxidation more than β-carotene by a factor of about 2.3-2.5, and more than the individual components.

Eine farbgebende Komponente von Rotschimmelkäse ist das bakterielle Carotinoid 3,3′‐Dihydroxyisorenieratin (1). Nun ist es gelungen, 1 sowie dessen Oxidationsprodukt 2 zu synthetisieren; beide Verbindungen haben außergewöhnliche Strukturen mit phenolischen bzw. chinoiden Endgruppen. Anhand von acht Modellsystemen wurden die antioxidativen und photoprotektiven Eigenschaften untersucht, wobei sich 1 als anderen Carotinoiden überlegen erwies.