Minor Carotenoids Research Articles

Salmoxanthin, deepoxysalmoxanthin, and 7,8-didehydrodeepoxysalmoxanthin from the Salmon Oncorhynchus keta.

The absolute configuration of salmoxanthin (5,6-epoxy-5,6-dihydro-beta,epsilon-carotene-3,3',6'-triol) (1) first isolated from the salmon Oncorhynchus keta was determined to be 3S, 5R, 6S, 3'S, 6'R. Furthermore, two minor carotenoids, deepoxysalmoxanthin (2) and 7,8-didehydrodeepoxysalmoxanthin (3), were isolated, and their structures were determined to be (3R,3'S,6'R)-beta,epsilon-carotene-3,3',6'-triol and (3R,3'S,6'R)-7,8-didehydro-beta,epsilon-carotene-3,3',6'-triol by (1)H NMR and CD spectroscopy.

Carotenoid composition in the fruits of red paprika (Capsicum annuum var. lycopersiciforme rubrum) during ripening; biosynthesis of carotenoids in red paprika.

The changes in the carotenoid pigments of the Capsicum annuum var. lycopersiciforme rubrum during maturation have been investigated quantitatively by means of a HPLC technique. In all of the chromatograms, 40 peaks were detected; 34 carotenoids were identified. The total carotenoid content of the ripe fruits was about 1.3 g/100 g of dry weight, of which capsanthin constituted 37%, zeaxanthin was 8%, cucurbitaxanthin A was 7%, capsorubin constituted 3.2%, and beta-carotene accounted for 9%. The remainder was composed of capsanthin 5,6-epoxide, capsanthin 3,6-epoxide, 5,6-diepikarpoxanthin, violaxanthin, antheraxanthin, beta-cryptoxanthin, and several cis isomers and furanoid oxides. The possible biosynthetic routes for the formation of minor carotenoids containing 3,5,6-trihydroxy-beta-, 3,6-epoxy-beta-, and 6-hydroxy-gamma-end groups are described.

‘Prenigroxanthin’ [(all-E,3R,3′S,6′S)-β,γ-carotene-3,3′,6′-triol], a novel carotenoid from red paprika (Capsicum annuum)

From the ripe fruits of red paprika (Capsicum annuum) prenigroxanthin, a minor carotenoid was isolated and, based on the spectral data and the proposed biosynthesis, identified as (all-E,3R,3′S,6′S)-β,γ-carotene-3,3′,6′-triol.

Lutein, Zeaxanthin, and the Macular Pigment

The predominant carotenoids of the macular pigment are lutein, zeaxanthin, and meso-zeaxanthin. The regular distribution pattern of these carotenoids within the human macula indicates that their deposition is actively controlled in this tissue. The chemical, structural, and optical characteristics of these carotenoids are described. Evidence for the presence of minor carotenoids in the retina is cited. Studies of the dietary intake and serum levels of the xanthophylls are discussed. Increased macular carotenoid levels result from supplementation of humans with lutein and zeaxanthin. A functional role for the macular pigment in protection against light-induced retinal damage and age-related macular degeneration is discussed. Prospects for future research in the study of macular pigment require new initiatives that will probe more accurately into the localization of these carotenoids in the retina, identify possible transport proteins and mechanisms, and prove the veracity of the photoprotection hypothesis for the macular pigments.

Capsoneoxanthin, a new carotenoid isolated from the fruits of Asparagus falcatus

From the ripe fruits of Asparagus falcatus capsoneoxanthin, a minor carotenoid was isolated and, based on its spectral data, identified as (all- E,3 S,5 R,6 R,3′ S,5′ R)-6,7-didehydro-5,6-dihydro-3,5,3′-trihydroxy-β,κ-caroten-6′-one.

Bioavailability of Carotenoids from Vegetables

The term “bioavailability” originated from pharmacology and has been historically used to describe the movement of compounds across the intestine into the circulatory system. Carotenoids have been purported to be associated with an array of biological functions, all requiring intestinal uptake. These functional roles include antioxidant activity, modulation of detoxifying enzymes, enhancing the immune system, upregulating cell-to-cell communication, inducing cellular apoptosis, and regulating gene expression. Given the potential health benefits provided by carotenoids, identification of factors that modulate the bioavailability of these compounds has been of keen scientific interest. Determinants of carotenoid concentrations in circulation encompass controllable factors (e.g., diet and smoking status), at least one factor (fat-free body mass) that is under limited control (Zhu et al., 1997), and uncontrollable factors (e.g., age, gender, hormonal status, and the innate ability to absorb carotenoids). This paper discusses the major dietary factors that have been identified as having influence on the bioavailability of carotenoids in healthy humans. COOKING AND FOOD PROCESSING There is a perception that carotenoids are destroyed by the heat process involved in cooking of vegetables. In fact, carotenoid loss is minimal with moderate cooking, and in many cases, carotenoids become more bioavailable after cooking, probably because heat processing liberates them from cell matrices. Only modest changes in the concentrations of the major carotenoids were found in broccoli ( Brassica oleracea L. Botrytis Group), green (snap) beans (Phaseolus vulgaris L.), and spinach (Spinacia oleracea L.) that had been steamed (3‐5 min), microwaved (1.5‐5 min), or boiled (9 min) (Khachik et al., 1992). These cooking techniques had no effect on β-carotene and lutein (cis and trans) concentrations. Some differences were found for minor carotenoids, particularly the epoxycarotenoids, which do not appear to be absorbed by

Carotenoid pigments in Rosa mosqueta hips, an alternative carotenoid source for foods.

Carotenoid composition has been investigated in Rosa mosqueta hips (Rosa rubiginosa, Rosa eglanteria). Six major carotenoids were identified (beta-carotene, lycopene, rubixanthin, gazaniaxanthin, beta-cryptoxanthin, and zeaxanthin) together with other minor carotenoids (violaxanthin, antheraxanthin, and gamma-carotene). An average composition has been estimated as follows: beta-carotene (497.6 mg/kg of dry wt), lycopene (391.9 mg/kg of dry wt), rubixanthin (703.7 mg/kg of dry wt), gazaniaxanthin (289.2 mg/kg of dry wt), beta-cryptoxanthin (183.5 mg/kg of dry wt), zeaxanthin (266. 6 mg/kg of dry wt), and minor carotenoids (67.1 mg/kg of dry wt). Possible uses in food technology are outlined and discussed including the preparation of highly colored oleoresins as natural colorants of food and beverages and as provitamin A sources.

ChemInform Abstract: Synthesis of Bixin and Three Minor Carotenoids from Annatto (Bixa orellana).

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Three minor carotenoids from annatto (Bixa orellana) seeds

Abstract Three minor carotenoids were isolated from the seed coat of Bixa orellana fruits by chromatographic (CC, TLC, HPLC) methods. The structures were established as 6-geranylgeranyl 8′-methyl-6,8′-diapocaroten-6,8′-dioate, 6-geranylgeranyl 6′-methyl (9′Z)-6,6′-diapocaroten-6,6′-dioate and 6-geranylgeranyl 6′-methyl-6,6′-diapocaroten-6,6′-dioate by means of UV–visible, 1 H - and 13 C -NMR spectroscopy and mass spectrometry. This is the first time that geranylgeraniol has been found esterified with a carotenoid carboxylic acid.

Endogenous carotenoid concentrations in cancerous and non‐cancerous tissues of gastric cancer patients in Korea*

Carotenoid concentrations were measured in serum and in both non-cancerous and cancerous gastric mucosal tissues of Korean patients with gastric cancer (n = 18). Carotenoids in serum and gastric tissue were extracted with chloroform/methanol (2:1), and measured using reverse-phase high-performance liquid chromatography with a C30 column. Cryptoxanthin and -carotene were the major carotenoids in the Korean blood and they had a median ratio of non-cancerous tissue/serum levels which was less than 1.0. No significant differences of cryptoxanthin and -carotene levels were found between non-cancerous and cancerous tissues. After incubation of -carotene with gastric tissue, significantly higher levels of -carotene breakdown products were produced in the homogenates of cancerous tissue when compared with non-cancerous tissue. Lutein, zeaxanthin and -carotene were the minor carotenoid constituents in the blood and their median ratio of non-cancerous tissue/serum levels was greater than 1.0. Cancerous tissue had significantly lower levels of lutein, zeaxanthin and -carotene than did non-cancerous tissue. It appears that the increased breakdown of -carotene and cryptoxanthin in cancerous tissue can be compensated for by an increased uptake of circulating carotenoids by cancerous tissue, whereas lutein, zeaxanthin and -carotene levels in cancerous tissue are not able to be maintained.

Synthesis of Bixin and Three Minor Carotenoids from Annatto (Bixa orellana)

The three apocarotenoids methyl (9Z)-8′-oxo-6,8′-diapocaroten-6-oate (2), methyl (9Z)-10′-oxo-6,10′-diapocaroten-6-oate (4), and methyl (9Z)-14′-oxo-6,14′-diapocaroten-6-oate (5), recently isolated from annatto, were synthesized. The key step of all three syntheses was the Wittig reaction of the (Z)-terminus 6 with the phosphonium salts 15, 18, and 24, carrying the polyene chain. Bixin (1) was synthesized from 2 in a Horner-Emmons reaction.

Pigments and fatty acids of marine raphidophytes: A chemotaxonomic re-evaluation

SUMMARY The patterns of occurrence of photosynthetic pigments and fatty acids among seven available species (11 strains) of marine raphidophytes were determined and used as chemotaxonomic markers. All currently recognized genera of marine raphidophytes were included for analysis: that is, Chattonella, Fibrocapsa, Heterosigma, Olisthodiscus and Haramonas. The characteristic pigment composition was shown to be chlorophyll a, chlorophylls c1 and/or c2, fucoxanthin as the major carot-enoid, β,β-carotene and any or all of zeaxanthin, violaxanthin and an auroxanthin-like pigment as the minor carotenoids. The carotenoid composition of all marine raphidophyte genera investigated was virtually the same, except in Fibrocapsa and Haramonas, which differed due to the occurrence of fucoxanthinol and 19′-butanoyloxyfucoxanthin, respectively. These fucoxanthin derivatives, in addition to fucoxanthin, have potential chemotaxonomic use for differentiating the two species. In all 11 strains, 15 fatty acids (saturated, mono-unsaturated and polyunsaturated) were determined. Significant taxonomic distinctions between genera were reflected by their fatty acid profiles. A rapid key for the differentiation of genera, in addition to morphological features, may be the absence of the 18:4 fatty acid in Olisthodiscus; presence of 18:5 in Heterosigma; the presence of fucoxanthinol in Fibrocapsa and presence of 19′-butanoyloxyfucoxanthin in Haramonas.

Nutrient content of tomatoes and tomato products.

During the last half-century, the fruit of the cultivated tomato (Lycopersicon esculentum), commonly considered a vegetable, has become a popular and highly consumed food in the United States. Production of tomatoes in the United States ranks second only to potatoes. As a consequence, tomatoes and tomato-based foods provide a convenient matrix by which nutrients and other health-related food components can be supplied to human beings. Tomatoes and tomato products are rich sources of folate, vitamin C, and potassium. Relative to phytonutrients, the most abundant in tomatoes are the carotenoids. Lycopene is the most prominent carotenoid followed by beta-carotene, gamma-carotene and phytoene as well as several minor carotenoids. The antioxidant activity of lycopene as well as several other carotenoids and their abundance in tomatoes makes these foods rich sources of antioxidant activity. The provitamin A activity of beta- and gamma-carotene, their modest levels in tomato products, and the high consumption of these foods results in a rich supply of vitamin A activity from tomato-based foods. Tomatoes also contain several other components that are beneficial to health, including vitamin E, trace elements, flavonoids, phytosterols, and several water-soluble vitamins.

A null lesion in the rhodopin 3,4-desaturase of Rhodospirillum rubrum unmasks a cryptic branch of the carotenoid biosynthetic pathway.

The carotenoids accumulated by a mutant Rhodospirillum rubrum ST4, containing a single Tn5 lesion in the pathway for carotenoid biosynthesis, were analyzed by HPLC, 1H NMR spectroscopy, and field desorption mass spectrometry. The main carotenoid was identified as 3,4,3',4'-tetrahydrospirilloxanthin, and the four minor carotenoids were identified as rhodopin, 3,4-dihydroanhydrorhodovibrin, 3', 4'-dihydrorhodovibrin, and 1,1'-dihydroxylycopene. The C-3,4 and C-3',4' bonds of all 5 carotenoids are saturated, and they have 11 conjugated double bonds. With the exception of rhodopin, which is a normal intermediate of the wild-type pathway, all of the carotenoids are not naturally occurring. The Tn5 lesion was assigned to rhodopin 3,4-desaturase which is proposed to catalyze dehydrogenation at both ends of the symmetrical spirilloxanthin derivative. An unexpected finding was that the enzymes following rhodopin 3,4-desaturase are still able to end-modify the 3,4-, and 3',4'-saturated precursors and that the order of methylation and hydroxylation is not obligatory. It is proposed that the observed nonnatural carotenoids can be explained by the inclusion of a cryptic branch, unmasked by the absence of rhodopin 3,4-desaturase, in the established linear pathway for spirilloxanthin biosynthesis. This is the first example of latent branching of the carotenoid biosynthesis pathway exhibited by a carotenoid mutant of a phototrophic bacterium.

ChemInform Abstract: Carotenoids from Annatto. Part 3. Isolation and Structure Elucidation of Minor Carotenoids from Annatto (Bixa orellana L.) Seeds.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The occurrence of retinol and carotenoids in human subretinal fluid

PURPOSE. To investigate if retinol and carotenoids are present in the subretinal space following rhegmatogenous retinal detachment. METHODS. Blood and subretinal fluid were collected from patients at the time of surgical repair of retinal detachment. After removal of cellular contents in a specimen by centrifugation, the supernatant fraction was analyzed by liquid chromatography using a silica column eluted by 16% dioxane in hexane. Retinol and carotenoids were identified in the chromatograms based on their retention time and absorption spectrum. RESULTS. The retinol concentrations (mean ± SD) in the serum and subretinal fluid were 305 ± 144 and 166 ± 96 ng/ml respectively. The 450 nm chromatogram had 7 peaks with the characteristic absorption spectrum of carotenoids. Peak 1 and 7 coincided with the retention time of ß-carotene (1.8 min) and lutein (10.8 min) respectively. The concentrations of ß-carotene and lutein in serum were 161 ± 63 and 142 ± 98 ng/ml respectively. There was very little ß-carotene in subretinal fluid (4.7 ± 2.4 ng/ml). Lutein was the major carotenoid peak in subretinal fluid (41.4 ± 14.1 ng/ml). The minor carotenoid peaks of serum were not observed in subretinal fluid. CONCLUSION. There is a substantial amount of retinol and lutein in subretinal fluid. The high proportion of lutein and very low amount of ß-carotene in the subretinal fluid support the occurrence of a highly selection transport mechanism of lutein from the blood to the retina.

Isolation and structure elucidation of minor carotenoids from annatto ( Bixa orellana L.) seeds

From the seed coat of Bixa orellana fruits, six minor carotenoids and one C 14-carotenoid derivative were isolated by chromatography (CC, TLC, HPLC) and their structures elucidated by means of spectroscopy (UV-visible, MS, 1H and 13C NMR). Dimethyl (9 Z,9′ Z)-6,6′-diapocarotene-6,6′-dioate, methyl (9 Z)-10′-oxo-6,10′-diapocaroten-6-oate, methyl (9 Z)-6′-oxo-6,5′-diapocaroten-6-oate and methyl (4 Z)-4,8-dimethyl-12-oxo-dodecyl-2,4,6,8,10-pentaenoate are new compounds, whereas methyl bixin and methyl (9 Z)-8′-oxo-6,8′-diapocaroten-6-oate have previously been found in annatto.

Characterization of Carotenoid Triplet States in the Light-Harvesting Complex B800–850from the Purple Bacterium Rubrivivax gelationsus

The carotenoid triplet states in the light-harvesting complex B800–850from purple bacterium Rubrivivax gelatinosus were characterized by absorption-detected magnetic resonance in zero magnetic field (ADMR) spectroscopy. Detailed HPLC analysis of carotenoids from B800–850demonstrated the presence of several carotenoids bound to the complex: the major ones are hydroxyspheroidene and spheroidene (together 80%), followed by neurosporene and hydroxyneurosporene (7%), spheroidenone and hydroxyspheroidenone (7.5%) and two other minor carotenoids that could be 3,4-dihydrospheroidenone and 3,4-dihydrohydroxyspheroidenone (5.5%). Three triplet states originating from carotenoids present in the B800–850were observed. The identical T-S spectra recorded at selectively chosen 2|E| transitions of carotenoids indicated that all these triplet states can be attributed to three different populations of one carotenoid family, probably to spheroidene and to hydroxyspheroidene, with different out-of-plane distortions of their polyene chain due to a different protein environment. Triplet states of the neurosporene and the spheroidenone families are probably not observed because of the low signal amplitude.

Deposition and metabolism of dietary canthaxanthin in different organs of arctic charr ( salvelinus alpinus L.)

A diet containing 65 μg canthaxanthin (Carophyll red, Hoffmann-La Roche) per kg diet was fed to post-juvenile, immature Arctic charr, weighing approximately 150 g each, for a 24 week period. Fish flesh was the major tissue for storing carotenoids, followed by skin, liver and gonads. Canthaxanthin was the main carotenoid deposited in the flesh and its content reached 4.3 μg g −1 of wet tissue after 24 weeks of feeding. The flesh also contained lutein (0.2 μg g −1) and some reductive metabolites of canthaxanthin, namely, echinenone (0.7 μg g −1) and 4′-hydroxyechinenone (0.7 μg g −1). β-Carotene, the final product of canthaxanthin reduction, was only present in the skin at 4.6 μg g −1, corresponding to 48% of the total pigments present. Other carotenoids found in charr skin were isocryptoxanthin, echinenone, canthaxanthin, 4′-hydroxyechinenone and lutein/lutein esters. The content of carotenoids in the charr liver was 5.23 μg g −1, which consisted mainly of echinenone (2.9 μg g −1) and 4′-hydroxyechinenone (1.3 μg g −1). The gonads of charr contained 2.2 μg g −1 carotenoids, only 17.8% of which was canthaxanthin and was dominated by 4′-hydroxyechinenone (33.5%) and lutein/lutein esters (37.7); isocryptoxanthin was a minor carotenoid (11.0%) present.

Carotenoid Composition in the Fruits ofCapsicumannuumCv. Szentesi Kosszarvú during Ripening

The changes in the carotenoid pigments of Capsicum annuum cv. Szentesi Kosszarvú during maturation have been investigated quantitatively by means of a HPLC technique. In all of the chromatograms, 56 peaks were detected; 34 carotenoids were identified. In this study, special attention is paid to the formation of minor carotenoids with 3,6-epoxy-β- (oxabicyclo[2.2.1]) and 3,5,6-trihydroxy-β- end groups. The possible biosynthetic route and the identity of capsolutein with the cucurbitaxanthin A are described. Keywords: Capsicum annuum; carotenoids; analysis; biosynthesis