Cryptoxanthins

Zeaxanthin (135) was synthesized from the salt (133) and the dialdehyde (134) in 1,2-epoxybutane, a reagent superior to ethylene oxide particularly for polyenedialdehydes. The same salt was also used to prepare /3-cryptoxanthin and zeinoxanthin. Phenolic carotenoids from Strep-tomyces mediolani and 1,2-dihydro- and l,2,r,2 -tetrahydro-lycopene have also been obtained by conventional olefin synthesis. 

Most carotenoids have no pro-vitamin A activity with the notable exceptions of P-carotene, and to a lesser extent a-carotene and P-cryptoxanthin. They act as macular pigments (lutein and zeaxanthin) and they have antioxidant and biochemical properties other than pro-vitamin A activity. 

BREITHAUPT D E and BAMEDIA (2001) Carotenoid esters in vegetables and fruits A screening with emphasis on P-cryptoxanthin esters. JAgric Food Chem 49(4) 2064-70. 

Nd = not detected Tr = trace P-cryp = 3-cryptoxanthin lyco = lycopene a-car = a-carotene 3-car = P-carotene zea = zeaxanthin. 

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... 

P-cyclase (CrtL-h) and P-carotene hydroxylase (b-Chy) (fhiit specific) carotene, P-cryptoxanthin and zeaxanthin 2002... 

There are basically two types of carotenoids those that contain one or more oxygen atoms are known as xanthophylls those that contain hydrocarbons are known as carotenes. Common oxygen substituents are the hydroxy (as in p-cryptoxanthin), keto (as in canthaxanthin), epoxy (as in violaxanthin), and aldehyde (as in p-citraurin) groups. Both types of carotenoids may be acyclic (no ring, e.g., lycopene), monocyclic (one ring, e.g., y-carotene), or dicyclic (two rings, e.g., a- and p-carotene). In nature, carotenoids exist primarily in the more stable all-trans (or all-E) forms, but small amounts of cis (or Z) isomers do occur. - ... 

Typically several different carotenoids occur in plant tissues containing this class of pigments. Carotenoids are accumulated in chloroplasts of all green plants as mixtures of a- and P-carotene, P-cryptoxanthin, lutein, zeaxanthin, violaxanthin, and neoxanthin. These pigments are found as complexes formed by noncovalent bonding with proteins. In green leaves, carotenoids are free, nonesterified, and their compositions depend on the plant and developmental conditions. In reproductive... 

It has been established that carotenoid structure has a great influence in its antioxidant activity for example, canthaxanthin and astaxanthin show better antioxidant activities than 3-carotene or zeaxanthin. 3- 3 3-Carotene also showed prooxidant activity in oil-in-water emulsions evaluated by the formation of lipid hydroperoxides, hexanal, or 2-heptenal the activity was reverted with a- and y-tocopherol. Carotenoid antioxidant activity against radicals has been established. In order of decreasing activity, the results are lycopene > 3-cryptoxanthin > lutein = zeaxanthin > a-carotene > echineone > canthaxanthin = astaxanthin. ... 

It is assumed that in order to have vitamin A activity a molecule must have essentially one-half of its structure similar to that of (i-carotene with an added molecule of water at the end of the lateral polyene chain. Thus, P-carotene is a potent provitamin A to which 100% activity is assigned. An unsubstituted p ring with a Cii polyene chain is the minimum requirement for vitamin A activity. y-Car-otene, a-carotene, P-cryptoxanthin, a-cryptoxanthin, and P-carotene-5,6-epoxide aU have single unsubstimted rings. Recently it has been shown that astaxanthin can be converted to zeaxanthin in trout if the fish has sufficient vitamin A. Vitiated astaxanthin was converted to retinol in strips of duodenum or inverted sacks of trout intestines. Astaxanthin, canthaxanthin, and zeaxanthin can be converted to vitamin A and A2 in guppies. ... 

Landrum, J.T., Bone, R.A., and Herrero, C., Astaxanthin, cryptoxanthin, lutein, and zeaxanthin, in Phytochemicals in Nutrition and Health, CRC Press, Boca Raton, FL, 2002. 

Carrots were also the main sonrces of a-carotene, whereas tomatoes and tomato prodncts were the major sources of lycopene. Lutein was mainly provided by peas in the Republic of Ireland and United Kingdom. Spinach was found to serve as the major source in other countries. Lutein and zeaxanthin xanthophylls are found in a wide variety of fruits and vegetables, particularly green leafy vegetables, but also in some animal products such as egg yolks. In all countries, P-cryptoxanthin was obtained primarily from citrus fruits. 

Carotenoids and prostate cancer — Numerous epidemiological studies including prospective cohort and case-control studies have demonstrated the protective roles of lycopene, tomatoes, and tomato-derived products on prostate cancer risk other carotenoids showed no effects. " In two studies based on correlations between plasma levels or dietary intake of various carotenoids and prostate cancer risk, lycopene appeared inversely associated with prostate cancer but no association was reported for a-carotene, P-carotene, lutein, zeaxanthin, or p-cryptoxanthin. - Nevertheless, a protective role of all these carotenoids (provided by tomatoes, pumpkin, spinach, watermelon, and citrus fruits) against prostate cancer was recently reported by Jian et al. ... 

Data concerning gastric cancer are scarce. The prospective Netherlands Cohort Study found no correlation between lutein dietary intake and gastric cancer risk, whereas findings from the Physicians Health Study and the ATBC study reported no effect of P-carotene on gastric cancer incidence. Two case-control studies and three intervention trials (ATBC, CARET, and the Physicians Health Study ) showed no association of P-carotene, lycopene, lutein, zeaxanthin, and P-cryptoxanthin. 

Some prospective and case-control studies also investigated the relationship of carotenoids and the evolution of CCA-IMT. Although the EVA study showed no association between total carotenoids and IMT, others like the ARIC study, the Los Angeles Atherosclerosis Study, " and the Kuopio Ischaemic Heart Disease Risk Factor Study demonstrated the protective role of isolated carotenoids such as lycopene, lutein, zeaxanthin, and P-cryptoxanthin on IMT. Thus, findings from prospective and case-control studies have suggested that some carotenoids such as lycopene and P-carotene may present protective effects against CVD and particularly myocardial infarcts and intima media thickness, a marker of atherosclerosis. 

The degree of linkage of a compound may also affect its bioaccessibility in the gut. It is generally admitted that a compound linked with other molecules (e.g., via esterification, glycosylation, etc.) is not absorbed as well as its free form and thus it must be hydrolyzed in the gut in order to be taken up by enterocytes. Due to the presence of hydroxyl or keto groups on their molecules, the xanthophylls (lutein, zeaxanthin, and P-cryptoxanthin) are found in both free and esterified (monoester or diester) forms in nature, but few studies have been conducted to date to assess the bioavailabilities of these esters. 

More than 600 carotenoids have been isolated from natural sources, but only about 60 have been detected in the human diet — about 20 in human blood and tissues. P-Carotene, a-carotene, lycopene, lutein, and P-cryptoxanthin are the five most prominent carotenoids present in the human body. 

In order to exhibit provitamin A activity, the carotenoid molecule must have at least one unsubstituted p-ionone ring and the correct number and position of methyl groups in the polyene chain. Compared to aU-trans P-carotene (100% provitamin A activity), a-carotene, P-cryptoxanthin, and y-carotene show 30 to 50% activity and cis isomers of P-carotene less than 10%. Vitamin A equivalence values of carotenoids from foods have been recently revised to higher ratio numbers (see Table 3.2.2) due to poorer bioavailability of provitamin A carotenoids from foods than previously thought when assessed with more recent and appropriate methods. 

Breithaupt, D.E. et al.. Plasma response to a single dose of dietary (3-cryptoxanthin esters from papaya (Carica papaya L.) or non-esterified (3-cryptoxanthin in adult human subjects a comparative study, Br. J. Nutr., 90, 795, 2003. 

The speed of autoxidation was compared for different carotenoids in an aqueous model system in which the carotenoids were adsorbed onto a C-18 solid phase and exposed to a continnons flow of water saturated with oxygen at 30°C. Major products of P-carotene were identified as (Z)-isomers, 13-(Z), 9-(Z), and a di-(Z) isomer cleavage prodncts were P-apo-13-carotenone and p-apo-14 -carotenal, and also P-carotene 5,8-epoxide and P-carotene 5,8-endoperoxide. The degradation of all the carotenoids followed zero-order reaction kinetics with the following relative rates lycopene > P-cryptoxanthin > (E)-P-carotene > 9-(Z)-p-carotene. 

Many countries have food composition databases but only a few present the compositions of some carotenoids. The U.S. Department of Agriculture s NCC Carotenoid Database covers 215 foods and cites levels of a-carotene, P-carotene, lycopene, P-cryptoxanthin, lutein plus zeaxanthin, and also zeaxanthin in a more limited number of foods. An electronic version of this database is available at http //www.ars.usda.gov/nutrientdata. 

Tables 4.2.1 and 4.2.2 show, respectively, major sources of P-carotene and other provitamin A carotenoids, especially a-carotene and P-cryptoxanthin. Since cis isomers have different biological and physical-chemical properties than their corresponding dll-trans carotenoids, whenever available, their distribution was included in the tables. The structures of P-carotene cis isomers are shown in Figure 4.2.1, whereas the structures of the other provitamin A carotenoids are presented in Figure...

In processed products of the tropical fruit caja and in some cultivars of persimmons, all-tran P-cryptoxanthin was found to be the major carotenoid, contributing to 31 to 38% of the total carotenoid contents in both fruits (Table... 

Although p-cryptoxanthin was not the major carotenoid in three cultivars of sea buckthorn berries, their contents were higher than those found in other fruits (Table 4.2.2). 

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