Eine Suche nach 3′‐Epilutein ( = (3R,3′S,6′R)‐β,ε‐Carotin‐3,3′‐diol) und 3′, O‐Didehydrolutein (=(3R, 6′R)‐3‐Hydroxy‐β,ε‐carotin‐3′‐on) in Eigelb, in Blüten von Caltha palustris und in Herbstblättern

Abstract

Search for the Presence in Egg Yolk, in Flowers of Caltha palustris and in Autumn Leaves of 3′‐Epilutein ( =(3R,3′S,6′R)‐β,ε‐Carotene‐3,3′‐diol) and 3′,O‐Didehydrolutein ( =(3R,6′R)‐3‐Hydroxy‐β,ε‐carotene‐3′‐one) 3′.O‐Didehydrolutein ( =(3R, 6′R)‐3‐hydroxy‐β,ε‐carotene‐3′‐one; 2) has been detected in egg yolk and in flowers of Caltha palustris. This is the first record for its occurrence in a plant. The compound shows a remarkable lability towards base; therefore, it may have been overlooked til now, because it is destroyed under the usual conditions of saponification of the carotenoid‐esters. One of the many products formed from 2 with 1% KOH in methanol has been purified and identified as the diketone 3 ( =(3R)‐3‐hydroxy‐4′, 12′‐retro‐β,β‐carotene‐3′,12′‐dione). The identification of this transformation product from lutein might throw a new light on the metabolism of this important carotenoid in green plants. 3′‐Epilutein ( =(3R,3′S,6′R)‐β,ε‐carotene‐3,3′‐diol; 1) was not detected in egg yolk, but is present besides lutein in flowers of C. palustris, thus confirming an earlier report of the occurrence of an isomeric (possibly epimeric) lutein (‘calthaxanthin’) in that plant [21]. We were not able to detect even traces of 1 or 2 in the carotenoid fraction from autumn leaves of Prunus avium (cherry), Parrotia persica, Acer montanum (maple) and yellow needles of Larix europaea (larch). α‐Cryptoxanthin (4), a very rare carotenoid, was isolated in considerable quantity for the first time from flowers of C. palustris.

3′-Oxolutein, a Metabolite of Lutein in Chickens ,

“…The present data confirmed the finding of 3'-oxolutein in egg yolk by von Buchecker and Eugster (1979) and extended it by demonstrating a nondietary origin. The ability of chickens to oxidize dihydroxycarotenoids, which had not been demonstrated previously, may be an evolutionary remnant of the fairly widespread ability of avian species to oxidize carotenoids, even the hydrocarbon carotenes (Brush, 1967).…”

“…Because. 3' -oxolutein was first detected in egg yolks (von Buchecker and Eugster, 1979), chicken hens were fed a diet containing free lutein for 5 weeks to permit equilibration before collecting eggs and removing the intestinal contents, serum, and liver for analysis. The ratios of lutein to 3'-oxolutein (Table 5) in descending order were intestinal contents > serum > liver ~ yolk.…”

“…In addition to this important acyl metabolism, chickens have the ability to reduce oxocarotenoids to the corresponding alcohols (Tyczkowski and Hamilton, unpublished data). The finding of 3'-oxolutein (3-hydroxy-3'-oxo-|3,e-carotene) in egg yolks of hens receiving a diet containing lutein (von Buchecker and Eugster, 1979), although implying a dietary contaminant as a possibility, also implies that chickens possess the ability to oxidize hydroxycarotenoids (e.g., lutein). The ability to oxidize carotenoids is a metabolic capability accounting for the reddish plumage of certain species of wild birds (Brush, 1967).…”

Confirmation of the Absolute (3R,3′S,6′R)‐Configuration of (all‐E)‐3′‐Epilutein

“…In the fatty acid ester form, 1 is widely distributed in fruits, flowers, and yellow autumn leaves [1]. The 3'-epimer of lutein, i.e., 3'-epilutein (2), with the (all-E,3R,3'S,6'R)-configuration, was isolated from the flowers of Marsh Marigold (Caltha palustris) [2] [3] and from goldfish (Carassius auratus), together with a-doradexanthin ( (all-E,3S,3'S,6'R)-3,3'-dihydroxy-4',5'-didehydro-5',6'-dihydro-b,bcaroten-4-one; 3) [4]. Compound 2 was also detected in the anthers of flowers such as Rosa gallica −officinalis× Thory and Paeonia officinalis [5].…”

Epimerisation of lutein to 3′-epilutein in processed foods

“…The UV-vis, CD and MS data as well as the proton chemical shift 11 and proton-proton coupling constant values determined from the NMR spectra of isolated compounds were identical to the corresponding data from both our previous works 12, 13 and literature. 7,14 The main carotenoids of fresh spinach (Spinacia oleracea L.) were proved to be lutein, b-carotene and violaxanthin. In addition, the presence of neoxanthin and various (Z)-isomers, such as (9 0 Z)-neoxanthin, (9Z)-violaxanthin, (13Z)-violaxanthin, (9Z)-and/or (9 0 Z)-lutein, (13Z)-and/or (13 0 Z)-lutein as minor components was observed.…”