Xanthophylls oxidation

The oxidation of carotenes results in the formation of a diverse array of xanthophylls (Fig. 13.7). Zeaxanthin is synthesised from P-carotene by the hydroxylation of C-3 and C-3 of the P-rings via the mono-hydroxylated intermediate P-cryptoxanthin, a process requiring molecular oxygen in a mixed-function oxidase reaction. The gene encoding P-carotene hydroxylase (crtZ) has been cloned from a number of non-photosynthetic prokaryotes (reviewed by Armstrong, 1994) and from Arabidopsis (Sun et al, 1996). Zeaxanthin is converted to violaxanthin by zeaxanthin epoxidase which epoxidises both P-rings of zeaxanthin at the 5,6 positions (Fig. 13.7). The... 

The maximum spectrometric absorption of lutein (C40H56O2, mol wt 568.9, xanthophyll, (3R,3.S,6.R)-p,8-carotene-3,3.-diol) is found between 453 and 481 nm. Its solubihty in ethanol is greater than that of the carotenoids. It is somewhat less sensitive to oxidation and heat degradation than P-carotene. It contributes yellow color." ... 

Stndies of the antoxidation of carotenoids in liposomal suspensions have also been performed since liposomes can mimic the environment of carotenoids in vivo. Kim et al. stndied the antoxidation of lycopene," P-carotene," and phytofluene" " in liposomal snspensions and identified oxidative cleavage compounds. Stabilities to oxidation at room temperature of various carotenoids incorporated in pig liver microsomes have also been studied." The model took into account membrane dynamics. After 3 hr of reactions, P-carotene and lycopene had completely degraded, whereas xanthophylls tested were shown to be more stable. 

As already mentioned, macular zeaxanthin comprises two stereoisomers, the normal dietary (3/(,37()-/caxanthin and (3f ,3 S)-zeaxanthin(=(meyo)-zeaxanthin), of which the latter is not normally a dietary component (Bone et al. 1993) and is not found in any other compartment of the body except in the retina. The concentration of (tneso)-zeaxanthin in the retina decreases from a maximum within the central fovea to a minimum in the peripheral retina, similar to the situation with (3/ ,37 )-zeaxanthin. This distribution inversely reflects the relative concentration of lutein in the retina and gave rise to a hypothesis (Bone et al. 1997) that (meso)-zeaxanthin is formed in the retina from lutein. This was confirmed by an experiment in which xanthophyll-depleted monkeys had been supplemented with chemically pure lutein or (3/ ,37 )-zeaxanthin (Johnson et al. 2005). (Meyo)-Zeaxanthin was exclusively detected in the retina of lutein-fed monkeys but not in retinas of zeaxanthin-fed animals, demonstrating that it is a retina-specific metabolite of lutein only. The mechanism of its formation has not been established but may involve oxidation-reduction reactions that are mediated photochemically, enzymatically, or both. Thus, (meso)-zeaxanthin is a metabolite unique to the primate macula. 

Lim, B. P., A. Nagao et al. (1992). Anti-oxidant activity of xanthophylls on peroxyl radical-mediated phospholipid peroxidation. Biochim. Biophys. Acta 1126 178-184. 

As mentioned previously, the ability of carotenoids to inhibit oxidative stress was tested in vitro in many different cell types. In the retina only lutein and zeaxanthin accumulate in sufficient concentrations to exert direct antioxidant effects, therefore our further discussion of these antioxidant effects will be focused mainly on those two xanthophylls. 

It has been shown in many studies that protective effects of carotenoids can be observed only at small carotenoid concentrations, whereas at high concentrations carotenoids exert pro-oxidant effects via propagation of free radical damage (Chucair et al., 2007 Lowe et al., 1999 Palozza, 1998, 2001 Young and Lowe, 2001). For example, supplementation of rat retinal photoreceptors with small concentrations of lutein and zeaxanthin reduces apoptosis in photoreceptors, preserves mitochondrial potential, and prevents cytochrome c release from mitochondria subjected to oxidative stress induced by paraquat or hydrogen peroxide (Chucair et al., 2007). However, this protective effect has been observed only at low concentrations of xanthophylls, of 0.14 and 0.17 pM for lutein and zeaxanthin, respectively. Higher concentrations of carotenoids have led to deleterious effects (Chucair et al., 2007). 

However, the metabolic pathways of lutein and zeaxanthin are only beginning to be discovered. Several derivatives of dietary xanthophylls have been identified in the retina, such as 3 -epilutein, meso-zeaxanthin, 3 -oxolutein, and 3-methoxyzeaxanthin, and it has been suggested that they may be formed as a result of nonenzymatic oxidative modifications (Bernstein et al., 2001,2002b Bhosale et al., 2007b Khachik et al., 1997). The macula lutea contains predominantly meso-zeaxanthin (Figure 15.1), which is believed to originate from either oxidative modification or double bond isomerization of dietary lutein (Khachik et al., 1997, 2002). 

Fresh peppers are excellent sources of vitamins A and C, as well as neutral and acidic phenolic compounds (Howard and others 2000). Levels of these can vary by genotype and maturity and are influenced by growing conditions and processing (Mejia and others 1988 Howard and others 1994 Lee and others 1995 Daood and others 1996 Simmone and others 1997 Osuna-Garcia and others 1998 Markus and others 1999 Howard and others 2000). Peppers have been reported to be rich in the provitamin A carotenoids (3-carotene, a-carotene, and (3-cryptoxanthin (Minguez-Mosquera and Hornero-Mendez 1994 Markus and others 1999), as well as xanthophylls (Davies and others 1970 Markus and others 1999). Bell peppers have been shown to exert low antioxidant activity (Al-Saikhan and others 1995 Cao and others 1996 Vinson and others 1998) or may even act as pro-oxidants (Gazzani and others 1998). 

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