Neurosporene

The desaturation of l5-cis phytoene into lycopene occurs in four stepwise dehydrogenations, yielding phytofluene, ( -carotene, neurosporene and lycopene... 

Fig. 2.16. HPLC profile of carotenoids in an extract of vegetable soup. An expansion of the profile from 30 to 39 is shown in the inset (A). Monitored wavelengths were 436, 440, 464, and 409 nm for peaks 9,10,11,12, and 14, respectively, in the inset (A). Peak identification 1 + 1" = all-trans-lutein and cw-lutein 2 = 5,6-dihydroxy-5,6-dihydrolycopene (lycopene-5,6-diol) 3 = j3-apo-8 -carotenal (internal standard) 4 = lycopene 1,2-epoxide 5 = lycopene 5,6-epoxide 6 = 1,2-dimethoxyproly-copene (tentative identification) 7 = 5,6-dimethoxy-5,6-dihydrolycopene 8 = lycopene 9 = pheo-phytin b 10 = neurosporene 11 = (-carotene 12 = pheophytin a 13 = (-carotene 14 = pheophytin a isomer and (-carotene 15 = a-carotene 16 and 16" = all-trans-/fcarotene, cis-/J-carotene 17 and 17" = all-trans- or cA-phytofluene 18 and 18" = all-trans- or cw-phytoene. Reprinted with permisson from L. H. Tonucci et al. [40].

The incorporation of " C-labelled neurosporene (138), lycopene, and y-carotene (141) into /3-carotene by cell extracts of Phycomyces blakesleeanus mutants has been demonstrated.Addition of unlabelled lycopene or /3-zeacarotene (140) caused approximately equal reduction of the incorpsration of [ C]neurosporene into /3-carotene, indicating that the alternative routes of Scheme 3 are of equivalent importance. The absolute configuration of C-6 of natural /3,y-carotene (55) is opposite to that of all C40 carotenoids with an e-ring end-group. " Opposite foldings of the aliphatic precursor are therefore required for cyclization to produce the y- and e-end-groups. 

For example, the ion of [M-69]+, which is observed in the tandem mass spectra of lycopene, neurosporene, and y-carotene but not a-carotene, p-carotene, lutein, or zeaxanthin, indicates the presence of a terminal acyclic isoprene unit. Elimination of a hydroxyl group or a molecule of water, [M-17]+ or [MH-18]+, from carotenoids such as astaxanthin or zeaxanthin is characteristic of the presence of a hydroxyl group. Also, tandem mass spectrometry can be used to distinguish between isomeric carotenoids such as a-carotene and p-carotene, or lutein and zeaxanthin. For example, the ring of a-carotene containing the double bond that i s not conj ugated to the rest of the polyene chain shows unique retro-Diels-Alder fragmentation to form the ion of [M-56]+. In a similar manner, isomeric lutein and zeaxanthin differ by the... 

FIGURE 63.1 Starting with mevalonate, carotenoids are biosynthesized by a special branch of the terpenoid pathway. The first C-40 hydrocarbon unit formed is phytoene, a carotenoid with three conjugated double bonds, which then is enzymatically desaturated to successively yield (3-carotene, neurosporene, and lycopene. Other carotenoids such as (3-carotene and oxocarotenoids are produced from lycopene following cyclization and hydroxylation reactions. Thus, lycopene is a central molecule in the biosynthesis pathway of carotenoids. 

UO. Cyts h and c BChl a or b Intracyloplasmic membrane Spirilloxanthin, okenone, (/3-carotene), spheroidene, rhodopin, lycopene, neurosporene... 

In the photosynthetic bacteria Rhodomicrobium vannielii, which normally contains acyclic carotenoids with tertiary hydroxy- and methoxy-groups at C-1 and C-T, phytoene only accumulated when diphenylamine was present, but the occurrence of hydroxy-derivatives of phytofluene, 7,8,11,12-tetrahydrolycopene, neurosporene, and lycopene in the presence of the inhibitor indicated that hydroxylation could take place at any level of desaturation although only the more desaturated half of the molecule was so substituted. 

Lycopene is the major carotenoid pigment found in tomatoes, along with lesser amounts of a-, P-, y-, and -carotene, phytoene, phytofluene, neurosporene, and lutein (Trombly and Porter, 1953 Kargl et al., 1960). The basic physicochemical information on lycopene is fairly well established and is outlined in Table 4.1. Lycopene is dispersible in edible oils and soluble in apolar organic solvents. In aqueous systems, lycopene tends to aggregate and to precipitate as crystals this behavior is suspected to inhibit the bioavailability of lycopene in humans (Zumbrunn et al., 1985). In fresh tomatoes, the crystalline form of lycopene is responsible for the typical bright red of the ripe fruits. 

Two new acyclic end-groups have been found. Phytoene-1,2-oxide (15) was isolated from tomatoes. In the bacteria Rhodopseudomonas viridis it was found that although neurosporene and lycopene (16) were present, most of the carotenoids previously thought to be these two compounds, were in fact the corresponding 1,2-dihydro-derivatives [e.g. (17)]. In addition, l,2-dihydro-3,4-dehydrolycopene (18) was present. 

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