Xanthophyll

The chemical structure of cryptoxanthin

The color of an egg yolk is from the xanthophyll carotenoids lutein and zeaxanthin

Xanthophylls (originally phylloxanthins) are yellow pigments that occur widely in nature and form one of two major divisions of the carotenoid group; the other division is formed by the carotenes. The name is from Greek xanthos (ξανθός, "yellow")^[1] and phyllon (φύλλον, "leaf"),^[2] due to their formation of the yellow band seen in early chromatography of leaf pigments.

Molecular structure

The molecular structure of xanthophylls is similar to that of carotenes, but xanthophylls contain oxygen atoms, while carotenes are purely hydrocarbons with no oxygen. Xanthophylls contain their oxygen either as hydroxyl groups and/or as pairs of hydrogen atoms that are substituted by oxygen atoms acting as a bridge (epoxide). For this reason, they are more polar than the purely hydrocarbon carotenes, and it is this difference that allows their separations from carotenes in many types of chromatography. Typically, carotenes are more orange in color than xanthophylls.

Thin layer chromatography is used to separate components of a plant extract, illustrating the experiment with plant pigments that gave chromatography its name. Plant xanthophylls form the bright yellow band next to the green

Occurrence

Like other carotenoids, xanthophylls are found in highest quantity in the leaves of most green plants, where they act to modulate light energy and perhaps serve as a non-photochemical quenching agent to deal with triplet chlorophyll (an excited form of chlorophyll), which is overproduced at high light levels in photosynthesis. The xanthophylls found in the bodies of animals, and in dietary animal products, are ultimately derived from plant sources in the diet. For example, the yellow color of chicken egg yolks, fat, and skin comes from ingested xanthophylls (primarily lutein, which is often added to chicken feed for this purpose).

The yellow color of the human macula lutea (literally, yellow spot) in the retina of the eye results from the lutein and zeaxanthin it contains, both xanthophylls again requiring a source in the human diet to be present in the eye. These xanthophylls protect the eye from ionizing blue and ultraviolet light, which they absorb. These two specific xanthophylls do not function in the mechanism of sight, since they cannot be converted to retinal (also called retinaldehyde or vitamin A aldehyde). Their arrangement is believed to be the cause of Haidinger's brush, an entoptic phenomenon that allows to perceive the polarization of light.

Example compounds

The group of xanthophylls includes (among many other compounds) lutein, zeaxanthin, neoxanthin, violaxanthin, flavoxanthin, and α- and β-cryptoxanthin. The latter compound is the only known xanthophyll to contain a beta-ionone ring, and thus β-cryptoxanthin is the only xanthophyll that is known to possess pro-vitamin A activity for mammals. Even then, it is a vitamin only for plant-eating mammals that possess the enzyme to make retinal from carotenoids that contain beta-ionone (some carnivores lack this enzyme). In species other than mammals, certain xanthophylls may be converted to hydroxylated retinal-analogues that function directly in vision. For example, with the exception of certain flies, most insects use the xanthophyll derived R-isomer of 3-hydroxyretinal for visual activities, which means that β-cryptoxanthin and other xanthophylls (such as lutein and zeaxanthin) may function as forms of visual "vitamin A" for them, while carotenes (such as beta carotene) do not.

Xanthophyll cycle

The xanthophyll cycle

The xanthophyll cycle involves the enzymatic removal of epoxy groups from xanthophylls (e.g. violaxanthin, antheraxanthin, diadinoxanthin) to create so-called de-epoxidised xanthophylls (e.g. diatoxanthin, zeaxanthin). These enzymatic cycles were found to play a key role in stimulating energy dissipation within light-harvesting antenna proteins by non-photochemical quenching- a mechanism to reduce the amount of energy that reaches the photosynthetic reaction centers. Non-photochemical quenching is one of the main ways of protecting against photoinhibition.^[3] In higher plants, there are three carotenoid pigments that are active in the xanthophyll cycle: violaxanthin, antheraxanthin, and zeaxanthin. During light stress, violaxanthin is converted to zeaxanthin via the intermediate antheraxanthin, which plays a direct photoprotective role acting as a lipid-protective anti-oxidant and by stimulating non-photochemical quenching within light-harvesting proteins. This conversion of violaxanthin to zeaxanthin is done by the enzyme violaxanthin de-epoxidase, while the reverse reaction is performed by zeaxanthin epoxidase.^[4]

In diatoms and dinoflagellates, the xanthophyll cycle consists of the pigment diadinoxanthin, which is transformed into diatoxanthin (diatoms) or dinoxanthin (dinoflagellates) under high-light conditions.^[5]

Wright et al. (Feb 2011) found that, "The increase in zeaxanthin appears to surpass the decrease in violaxanthin in spinach" and commented that the discrepancy could be explained by "a synthesis of zeaxanthin from beta-carotene", however they noted further study is required to explore this hypothesis.^[6]

Food Sources

Xanthophylls are found in all young leaves and in etiolated leaves. Examples of other rich sources include papaya, peaches, prunes, and squash, which contain lutein diesters.^[7][8][9]

References

1. ξανθός. Liddell, Henry George; Scott, Robert; A Greek–English Lexicon at the Perseus Project
2. φύλλον. Liddell, Henry George; Scott, Robert; A Greek–English Lexicon at the Perseus Project
3. Falkowski, P. G. & J. A. Raven, 1997, Aquatic photosynthesis. Blackwell Science, 375 pp
4. Taiz, Lincoln and Eduardo Zeiger. 2006. Plant Physiology. Sunderland, MA: Sinauer Associates, Inc. Publishers, Fourth edition, 764 pp
5. Jeffrey, S. W. & M. Vesk, 1997. Introduction to marine phytoplankton and their pigment signatures. In Jeffrey, S. W., R. F. C. Mantoura & S. W. Wright (eds.), Phytoplankton pigments in oceanography, pp 37-84. – UNESCO Publishing, Paris.
6. Wright; et al. "The interrelationship between the lower oxygen limit, chlorophyll fluorescence and the xanthophyll cycle in plants".
7. Factors That Influence the Bioavailablity of Xanthophylls, Susan Zaripheh, John W. Erdman Jr.
8. UCLA College of Life Sciences, General Botany:Leaf Color: Xanthophylls
9. Michele Turcotte, MS, RD, Foods That Contain Zeaxanthin, February 18, 2014

• Demmig-Adams, B & W. W. Adams, 2006. Photoprotection in an ecological context: the remarkable complexity of thermal energy dissipation, New Phytologist, 172: 11–21.

External links

• Xanthophylls at the US National Library of Medicine Medical Subject Headings (MeSH)