Retinol vitamin 0-ionone ring

Vitamin A retinol (P-ionone ring) marine based and marine derived animals Rhodonine,()... 

A small but variable proportion of the carotenoids with one or two P-ionone rings (mainly P-carotene) are cleaved in the enterocytes to produce retinol (vitamin A). This process is very tightly controlled, so that too much vitamin A is not produced, although the control mechanism is not clear. Some cleavage of P-carotene can also occur in the liver, but this does not account for the turnover of P-carotene in the body. Small amounts of carotenoids are subject to enterohepatic circulation, but this does not account for losses. 

Vitamin A (retinol, 6.1) is the parent of a range of compounds known as retinoids, which possess the biological activity of vitamin A. In general, animal foods provide preformed vitamin A as retinyl esters (e.g. 6.5, which are easily hydrolysed in the gastrointestinal tract) while plant foods provide precursors of vitamin A, i.e. carotenoids. Only carotenoids with a /3-ionone ring (e.g. /1-carotene) can serve as vitamin A precursors. /3-Carotene (6.6)... 

The parent vitamin A compound, retinol, has the empirical formula C2oH3oO and a molecular weight (MW) of 286.44. The molecule comprises a cyclohexenyl (/3-ionone) ring attached at the carbon-6 (C-6) position to a polyene side chain whose four double bonds give rise to cis-trans (geometric) isomerism. The predominant isomer, all-trans-retinol (Fig. 1), possesses maximal (100%) vitamin A activity and is frequently accompanied in natural foodstuffs by smaller amounts of 13-ds-retinol, which exhibits 75% relative activity in the rat (6). Other cis isomers of retinol also occur in nature, but they are of low potency, and their contribution to the total vita-... 

From a nutritional viewpoint, the carotenoids are classified as provitamins and inactive carotenoids. To have vitamin A activity, the carotenoid molecule must incorporate a molecule of retinol, i.e., an unsubstituted /3-ionone ring with an 11-carbon polyene chain. /3-carotene (C40H56, MW = 536.88), the most ubiquitous provitamin A carotenoid, is composed of two molecules of retinol joined tail to tail thus the compound possesses maximal (100%) vitamin A activity. The structures of all other provitamin A carotenoids incorporate one molecule of retinol and hence theoretically contribute 50% of the biological activity of /3-carotene. Among the 600 or so carotenoids that exist in nature, only about 50 possess vitamin A activity in varying degrees of potency. 

Vitamin A is found in nature and is available in several forms. Retinol (vitamin A) is an unsaturated alcohol containing an ionone ring and can be obtained from fish liver oil (Table 13-2), egg yolk, milk, and butter. Vitamin A2 (dehydroretinol) is present in freshwater fishes. /3-carotene, a carotenoid, is the most important precursor of this vitamin. 

Structurally, vitamin A and many synthetic retinoids consist of a (3-ionone ring, a polyunsaturated polyene chain, and a polar end group. The polar end group can exist in several oxidation states, as retinol, retinal, or retinoic acid. Retinol and retinyl esters are the most abundant vitamin A forms found in the body (Blaner and Olson, 1994). Retinol can be esterified with long-chain fatty acids (mainly palmitate, oleate, and stearate) to form retinyl esters, which are the body s storage form of vitamin A. Retinol also can undergo oxidation to retinal, which can be oxidized further to retinoic acid. The active... 

A group of compounds described as vitamin A (retinol) includes those that, within their molecules, possess the characteristic (3-ionone ring and the isoprene chain. They are capable of forming molecules of polyene alcohol, aldehyde, acid, and ester (retinal, retinoic acid, and retinyl palmitate, respectively) (Figure 7.1). They can occur in many isomeric forms as groups of compounds possessing diversified prop-... 

Chemical structure (Figure 1). Molecules formally composed of four isoprene units they naturally occur as an alcohol (retinol), an aldehyde (retinal), or as an acid (retinoic acid). From each of the three basic forms two variants exist vitamin A, with a jS-ionone ring and vitamin A2 with a dehydrated S-ionone ring. Native retinoids show cis-trans isomerism of the double bonds. Carotenoids are proforms of vitamin A (Figure 2). 

Lycopene is one of the most widely consumed carotenoids however, it lacks provitamin A activity. Through cyclisation at one or both end groups of lycopene, carotenes are formed, containing one (8 and 7 carotenes) or two a and 3 carotenes) ionone rings. Vitamin A (all-tmns-retinol) consists of a (3-ionone ring with a side chain of three isoprenoid units. Hence a and 3 carotenes provide two molecules of retinol in the human body whereas 8 and 7 carotenes provide only one. In reality, carotenoids are incompletely absorbed and 6 jLg of p carotene is equivalent to 1 pg retinol equivalent (RE). Carotenoids with hydroxylated ionone rings (e.g. lutein) provide no vitamin A activity (Eitenmiller and Landen 1999). 

Vitamin A-active compounds [1] are present in foods of animal origin as retinoids (retinol, retinyl esters, retinylaldehyde, retinoic acid) and in those of plant origin as carotenoids (only carotenoids with one unsubstituted P-ionone ring and with an 11-carbon polyene chain at least are provitamins A). Retinyl palmitate is the main form used as a food supplement [4]. 

The basic and most important biologically active apocarotenoid in animal tissues is aU-trans-retinol also known as axeroftol or vitamin Aj (5-1). Retinol is an isoprenoid with 20 carbon atoms and five conjugated double bonds in the molecule, more precisely a diterpenic ahcychc alcohol with the so- called fl-ionone ring and a side chain of four conjugated double bonds attached to C-6. It is one of 16 possible stereoisomers. 

Retinol, the parent molecule of the vitamin A family, is a fat-soluble lipid alcohol (C20H30O, molecular mass 286.4) composed of a methyl substituted cyclohexenyl (yS-ionone) ring, an 11-carbon conjugated tetraene side chain, and a terminal hydroxyl group (Figure lA, Ri). Most of the double bonds can exist in either trans or cis conformation. All-traws-retinol is the most stable and most prevalent form in foods and tissues, but small amounts of other geometric isomers such as 9-cis- and 13-c/s-retinol are found in some cells. The terminal hydroxyl group of retinol can be free or esterified with a... 

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