The qualitative composition of carotenoids and their seasonal dynamics in tissues of the bivalve <Emphasis Type="Italic">Anadara kagoshimensis</Emphasis> (Tokunaga, 1906)

A total of six carotenoids, viz., β-carotene, pectenol A, pectenolone (trans- and cis-isomers), zeaxanthin, diatoxanthin, and alloxanthin, as well as esters of alloand diatoxanthin, have been detected in total carotenoid extracts from the tissues of the bivalve Anadara kagoshimensis (Tokunaga, 1906) using the methods of thin-layer chromatography, high-performance liquid chromatography, mass spectrometry, UV-VIS spectroscopy, and characteristic reactions for the identification of chemical groups. The major group (over 90% of the total carotenoids) is comprised of alloxanthin, pectenolone, and allo- and diatoxanthin esters. Tissues of A. kagoshimensis are typically characterized by cyclic variations in the level of carotenoids over the period from winter to summer, with the maxima in February and June and the minimum in April. The largest contribution to the seasonal carotenoid dynamics is made by the major group of pigments (R ² = 0.75–0.99), which depends on the pattern of succession of diatomic microalgae during the annual cycle. The pathways of metabolic transformation of the carotenoids in tissues of this bivalve are discussed.     

Qualitative composition of carotenoids, catalase and superoxide dismutase activities in tissues of the bivalve mollusc Anadara inaequivalvis (Bruguiere, 1789)

Using high performance liquid chromatography, UV-VIS spectra and mass-spectra (FAB MS), 7 carotenoid species were identified in tissues of the bivalve mollusc Anadara inaequivalvis (Bruguiere, 1789): trans- and cis-pectenolon, alloxanthin, pectenol A, β-carotene, zeaxanthin, and diatoxanthin. Their quantitative ratio in hepatopancreas, gills and foot of animals were determined. A negative correlation (R ² is about 0.9) was revealed between tissues content of a series of carotenoids (trans- and cis-pectenolon, zeaxanthin, alloxanthin, and diatoxanthin) and activity of antioxidant enzymes (catalase and superoxide dismutase). The existence of competitive interrelations between these molecular systems is proposed and underlying causes are discussed.     

Carotenoids in the Gonads of the Bivalved Mollusk <Emphasis Type="Italic">Anadara kagoshimensis</Emphasis> (Tokunaga, 1906)

We report here the outcomes of studies on the total carotenoid composition in tissues of sexually mature and immature bivalves A. kagoshimensis. Gonadal maturation was found to be accompanied by a redistribution of total carotenoids across the body. In the prespawn period, a highest level of total carotenoids (TC) was detected in the gonads (3.97 ± 1.25 mg/100 g wet weight), however, allowing for mass-dimensional tissues characteristics, the molluscan foot still accounted for a major portion of TC (26 ± 3.9%). The spectra and concentrations of gonadal and total nongonadal carotenoids were analyzed. In all molluscan tissues, the dominant carotenoid fractions were those of pectenolon and alloxanthin, with the latter being quantitatively inferior to pectenolon in generative tissue.     

The Composition of Carotenoids in Tissues of the Ascidian <Emphasis Type="Italic">Botryllus schlosseri</Emphasis> (Pallas, 1766) from the Black Sea

The composition of carotenoids was investigated in tissues of the colonial sea squirt Botryllus schlosseri (Pallas, 1766), which inhabits the Crimean coast near the city of Sevastopol. The total carotenoid amount of B. schlosseri was found to be 8.7 ± 4.6 mg/100 g of wet weight. Eleven carotenoids, that is, ß-carotene, 7,8-didehydroastaxanthin, 7,8,7',8',-tetradehydroastaxanthin, pectenolone, 4-ketoalloxanthin, diatoxanthin, diadinoxanthin, fucoxanthin, astaxanthin, alloxanthin, and halocynthiaxanthin, were identified in B. schlosseri with the use of the chromatographic and mass-spectrophotometric methods (UV/Vis, ESITOF/MS, and partially ¹H-NMR). Among these, halocynthiaxanthin (20.8% of the total content of carotenoids), alloxanthin (15.2%), and astaxanthin (12.1%) were found to be the major carotenoids. A comparative analysis of the composition of carotenoids in tissues of B. schlosseri was carried out for different regions of the World Ocean.     

Effect of food deprivation on transformation of carotenoids in the bivalve mollusc <Emphasis Type="Italic">Anadara kagoshimensis</Emphasis> (Tokunaga, 1906)

The composition and content of carotenoids in tissues of Anadara kagoshimensis (Tokunaga, 1906) were analyzed under food deprivation over 30 days. By the end of the experiment, a little and uneven decrease in the total carotenoid level was observed in the foot, hepatopancreas, gills, and tissue remainder. Initially, β-carotine, pectenolon, zeaxanthine, diatoxanthine, alloxanthine and the ethers of the latter four carotenoids were detected in tissue extracts. The qualitative carotenoid composition in the tissues under study was similar. During the experiment, changes common to all tissues were found both in the composition and content of carotenoids. β-carotene disappeared on days 3–4, the level of pectenolon, zeaxanthine, diatoxanthine and alloxanthine ethers decreased over 30 days, while the pectenolon and alloxanthine levels increased. Tissue specificity was revealed. Specifically, in the foot and hepatopancreas, a considerable increase was observed in the pectenolon and alloxanthine levels parallel to the decreasing total level of carotenoid esthers and increasing level of diatoxanthine and zeaxanthine; in the gills and lump of the remaining tissues, at the similar increase in the pectenolon and alloxanthine levels, those of diatoxanthine and zeaxanthine remained intact or even a little below the initial level. The diagram of carotenoid transformation in Anadara kagoshimensis is supplemented.     

Carotenoids of cryptophyceae

The carotenoids of selected Cryptophyceae, Rhodomonas D3 and Cryptomonas ovata, have been examined by methods including HPLC, mass spectrometry ¹H NMR and circular dichroism. $\text{3′R,6′R-}\text{Chirality}$ has been assigned to monadoxanthin from ¹H NMR and CD data; β,?-carotene possessed the common $\text{6′R-}\text{chirality}$. The quantitative distribution pattern of carotenoids in Cryptophyceae established here and previously, totalling five species' is discussed in chemosystematic context. β,?-Carotene (3–8% of total) is the major carotene, accompanied by ?,?-carotene (0.2%), β,β-carotene (0–1%) and lycopene (0-trace). Zeaxanthin (2%) was identified in C. ovate. The diacetylenic alloxanthin is the major carotenoid (70–88%), and the monoacetylenic crocoxanthin (5–15%) and monadoxanthin (0–16%) less abundant. No epoxidic or allenic carotenoids could be detected. The biosynthetic precursor of acetylenic carotenoids in this primitive algal class is discussed. The significance of Cryptophyceae in the marine food chain is commented on, using alloxanthin as an indicator.     

Comparative biochemical studies of carotenoids in fish—XXVII. Carotenoidsin the eggs of three species of cyprinidae

• 1.1. The carotenoids in the eggs of three species of freshwater fish, carp Cyprinus carpio, silver crucian carp Carassius gibelio langsdorfi and oily gudgeon Sarocheilichthys variegatus belonging to Cyprinidae were investigated from the comparative biochemical point of view.
• 2.2. Lutein A (3), (3R,3′R)-zeaxanthin (4), diatoxanthin (5) and alloxanthin (6) were found to be dominant and their corresponding 4-keto and/or 4′-keto derivatives, i.e. fritschiellaxanthin (10), (3S,3′R)-4-ketozeaxanthin (11), (3S,3′S)-astaxanthin (12), (3S,3′S)-7,8-didehydroastaxanthin (13) and (3S,3′S)-7,8,7′,8′-tetradehydroastaxanthin (14) were also found in all species examined.

     

Carotenoids of clam,coral and nudibranch zooxanthellae in aposymbiotic culture

The carotenoids of unialgal cultures originating from symbiotic zooxanthellae of two molluscan (Tridacna crocea, a giant clam, and Pteraeolidia ianthine a nudibranch) and one cnidian (Pseudopterogorgia bipinnata, a gorgonian coral) host have been analysed by HPLC or TLC procedures combined with several spectroscopic techniques including MS and NMR. A high total carotenoid content (0.45-0.63% of the dry wt) was obtained. The carotenoid pattern with C₃₇-norcarotenoids (peridinin and pyrrhoxanthin) comprising around 80% of total carotenoids, and β,β-carotene (2%), the ailenic dinoxanthin (3–4%) and the acetylenic diatoxanthin (1–3%) and diadinoxanthin (7–9%) representing minor C₄₀-carotenoids, corresponds to that of peridinin-producing free-living dinoflagellates. Supplementary ¹H NMR and ¹³C NMR data are reported for peridinin and pyrrhoxanthin. A polar, minor carotenoid, P447, was partly characterized as containing a disaccharide glycosidically bound to an allenic carotenoid aglycone. Re-evaluation of previous reports suggests the wide-spread occurrence of related carotenoid disaccharides in Dinophyceae for which they are considered a new chemosystematic marker.     

Chlorophylls and carotenoids of the marine alga Eutreptiella gymnastica

Monoalgal cultured Eutreptielia gymnastica contained chlorophyll a and b. The acetylenic carotenoids diatoxanthin and diadinoxanthin were among the main xanthophylls while their non-acetylenic analogues zeaxanthin and antheraxanthin were absent. The structurally most complex carotenoid was identical with neoxanthin. Three of the xanthophylls isolated could not be positively correlated with carotenoids previously reported from the Euglenophyceae. The ketocarotenoids astaxanthin, canthaxanthin and echinenone were absent.     

Coccomyxa sp. (Chlorophyta: Chlorococcales), a new pathogen in mussels (Mytilus galloprovincialis) of Vigo estuary (Galicia, NW Spain)

In this work, we describe the occurrence of irregular shaped green aggregations in the mantle, gill filaments, adductor muscle, visceral mass and haemolymph of wild mussels (Mytilus galloprovincialis) collected from the Vigo estuary (Galicia, NW Spain). Microscopic examination of these masses revealed that they consist of intracellular green algae which are spherical to oval in shape, 5 μm in length and 3 μm in width, without flagella and with a smooth surface. The algal cells present a small single nucleus, a mitochondrion, 1-2 parietal chloroplasts and lack pyrenoids. Reproduction is by formation of 2-4 autospores or daughter cells. Pigment analysis reveals the presence of photopigments typical of green algae in addition to alloxanthin, diadinoxanthin and diatoxanthin. These carotenoids are noted for the first time in a parasitic chlorophyte. The signs of infection, together with the morphological observations, suggest that this parasitic algae may be Coccomyxa parasitica. However, further molecular studies are required for confirmation. This is the first report of Coccomyxa algae parasitizing the species M. galloprovincialis.     

Factors influencing the variability of pigments in the surface sediments of mountain lakes

1. Surface sediment biofilm samples from 82 Pyrenean lakes were analysed for marker pigment composition using high performance liquid chromatography (HPLC). 2. Variability in the pigment composition among lakes was investigated by multivariate statistical analyses using a large data set of factors describing lake chemical, physical, morphological and catchment characteristics. 3. Due to the widely varying light penetration in the lakes, the most significant gradient of pigment composition extended from a benthic to a planktonic signal. The most important pigments in the gradient were alloxanthin (cryptophytes marker pigment, planktonic signal) and diatoxanthin (diatoms marker pigment, benthic signal). The molar ratio between these two marker pigments was positively correlated with lake depth. 4. Chlorophyll‐a preservation was found to be positively related to light penetration and the development of an autothrophic biofilm on the surface sediment and negatively related to decreasing pH and the percentage of alpine meadows in the lake catchments. 5. Zooplankton marker pigments in the surface sediment, including grazing by‐products (e.g. phaeophorbides) and carotenoids (astaxanthin, canthaxanthin, echinenone) incorporated into their tissues, were correlated with the areal abundance of zooplankton. 6. Marker pigments for photosynthetic bacteria, BChl‐e and okenone, were found mainly in relatively shallow lakes with large catchments that are forested, probably because of their higher loading of allochthonous organic matter. 7. The evaluation of a preservation index (Chl‐a expressed as a percentage of a‐phorbins) and the alloxanthin/diatoxanthin ratios throughout the sediment record of mountain lakes can provide evidence of historical changes in the relative importance of planktonic versus benthic primary production and might ultimately be interpreted in terms of climatic or environmental changes.     

Glutathione antioxidant complex and carotenoid composition in tissues of the bivalve mollusk <Emphasis Type="Italic">Anadara kagoshimensis</Emphasis> (Tokunaga, 1906)

The correlation of the state of glutathione complex composed of reduced glutathione (GSH), glutathione reductase (GR) activity and glutathione peroxidase (GP) and the qualitative composition of carotenoids was investigated in the bivalve mollusk Anadara kagoshimensis (Tokunaga, 1906). Using high-performance liquid chromatography, UV-Vis and mass spectra, 7 types of carotenoids (trans- and cis-pectenolon, alloxanthine, pectenol A, β-carotene, zeaxanthin and diatoxanthin) were identified in tissues of this species and their quantitative ratio was determined. A positive correlation (R ² > 0.9) was established between GSH and most carotenoid levels. A negative correlation was found for the GR–carotenoids (R ² > 0.75) and GP–pectenol A (R ² > 0.988) systems. The cause-and-effect relations of these regularities are discussed.     

Carotenoids of the dinophyceae

The carotenoids of the photosynthetic dinofiagellates Amphidinium carterae (two strains), Glenodinium sp.,Gymnodinium splendens, G. nelsoni and Gyrodinium dorsum have been investigated, quantitatively and qualitatively. Peridinin is the principal carotenoid in all species; also present are β-carotene, diadinoxanthin, dinoxanthin, pyrrhoxanthin, astaxanthin, peridininol, diatoxanthin and pyrrhoxanthinol. New structures have been assigned to dinoxanthin and pyrrhoxanthin while peridininol and pyrrhoxanthinol are new carotenoids not previously reported. A carotenoid glycoside, P-457, found in four species, is a hexoside. Dinoxanthin is the only, plausible biosynthetic precursor of peridinin that could be detected.     

Carotenoids of land-locked and sea-run types of masu salmon Oncorhynchus masou ishikawae inhabiting in the Nagara River,Japan, from the perspective of chemical ecological study

Carotenoids of the land-locked type (Amago) and sea-run type (Satsukimasu) of masu salmon Oncorhynchus masou ishikawae inhabiting the Nagara River, Gifu Prefecture, Japan were investigated from the perspective of the chemical ecological point of view. Yellow xanthophylls, 3′-epilutein, lutein, zeaxanthin, and diatoxanthin were major carotenoids in wild Amago. They were also present in the flesh of wild Amago. These carotenoids originated from aquatic insects, which wild Amago fed on. On the other hand, tunaxanthin, zeaxanthin, and salmoxanthin were major carotenoids in the integument of Satsukimasu, which migrated from the Ise Bay to the Nagara River. Astaxanthin was a major carotenoid in the flesh of Satsukimasu. These carotenoids accumulated from marine fish and crustaceans, which Satsukimasu fed on during migration in the sea. Carotenoids of Amago and Satukimasu well-reflect their ecological life history.     

Carotenoids of Eriobotrya japonica

The carotenoids of the loquat fruit Eriobotrya japonica Golden Nugget variety, were investigated. They were identified according to their chromatographic, spectrophotometric and chemical properties and compared with standard pigments. For some of the carotenoids, MS were determined. Pulp and peels were investigated separately. The main pattern of the pulp carotenoids was β-carotene (33%), γ-carotene (6%), cryptoxanthin (22%), lutein, violaxanthin and neoxanthin, each about 3–4%. The peel, with a carotenoid content 5 times as high, had a similar pattern, but the ratio between the main pigments differed: β-carotene (50%); γ-carotene (5%); cryptoxanthin (5%); lutein (13%); violaxanthin, neoxanthin, 3–4%. The carotenoids of the loquat (subfamily Maloideae) were very similar to those of the apricot (Prunus armeniaca-subfamily Prunoideae) both of the family of Rosaceae. The intergeneric differences are more pronounced, which is of possible taxonomic significance. The lower concentration of cryptoxanthin and the high concentration of lutein in the peels is noteworthy and of biosynthetic interest.     

Carotenoids of Prymnesiophyceae (Haptophyceae)

A quantitative study, including mass spectrometric identification, of the carotenoids isolated from some selected prymnesiophytes harvested in exponential growth phase has been carried out. Isochrysis galbana, Hymenomonas carterae, Prymnesium parvum, Pavlova (Monochrysis) lutheri and a Pavlova sp. all produce β,β-carotene, diatoxanthin, diadinoxanthin and fucoxanthin (major carotenoid) in various proportions, in addition to several minor carotenoids were found characteristic of each alga. 19'-Hexanoyloxyfucoxanthin, previously shown to be the major carotenoid in the prymnesiophyte Emeliana (Coccolithus) huxleyi, was not encountered in the Prymnesiophyceae studied here, and we conclude that this carotenoid should be critically looked for in other members of the Gephyrocapsaceae to which E. huxleyi belongs. We further conclude that the carotenoid complement of the Chrysophyceae (in the narrow sense) should be compared with that of the Prymnesiophyceae.     

Pigment alterations in the brown mussel Perna perna

Potential sex and/or gametogenic stage differences in the metabolism of chlorophyll-a and carotenoids in the brown mussel Perna perna of southern Brazil were studied using high performance liquid chromatography (HPLC). Carotenoids derived directly from diet (phytoplankton) were fucoxanthin plus diatoxanthin (diatoms), alloxanthin (cryptophytes) and zeaxanthin (mainly cyanobacteria). Females accumulated carotenoid-diols and epoxides (~ 3–4 mg/g-dry wt.) while males had much lower concentrations (~ 0.7 mg/g-dry wt.). An antioxidant/free radical scavenging role is proposed for carotenoids in females. Mean ratios of chlorophyll plus derivatives (Chlns-a) to carotenoids for male and female P. perna were 50:1 and 4:1, respectively. The higher ratio in males relates to both higher carotenoid contents in females plus higher total Chlns-a in males (~ 22 mg/g-dry wt.), relative to the females (~ 4 mg/g-dry wt.). Chlorophyll-a metabolism in both sexes followed two distinct pathways. First, cyclization of pyropheophorbide-a gave 13², 17³-cyclopheophorbide-a-enol (CPPaE) which was further oxidized to hydroxy-chlorophyllone. Second, chlorophyll-a derivatives retaining the 13²-carbomethoxy moiety were oxidized to purpurin-18 which was hydrolyzed to chlorin-p₆. In both cases, metabolism of dietary chlorophyll-a was oxidative and derivatives could either serve as antioxidants or merely be the results of non-specific digestive processes.     

Seasonal changes in the content of lipids and photosynthetic pigments in a brown alga Saccharina cichorioides

Seasonal changes in the contents of lipids and photosynthetic pigments (PSP) were investigated in a brown alga Saccharina cichorioides Miyabe (Phaeophyceae, the family Laminariaceae). The content of lipids varied from 0.27 to 0.60% of the algal fresh weight. The content of glyceroglycolipids (GL) was much greater in the time of spore formation (June–July and September–October), phospholipids — in the spring and in September–October, and the content of neutral lipids — in the spring and in November. In the period of spore release (August and October), the level of GL and polyunsaturated fatty acids (PUFA) sharply decreased. A high level of PUFA was observed from March to July and in November. In August and October, the same as in the spring, the proportion of saturated fatty acids (FA) was great. The content of chlorophylls from March to November varied from 20.3 to 26.9%, and the level of carotenoids — from 10.7 to 16.1%. Total content of PSP was relatively high in March and in August–September. Free sterols accounted for 3.4–7.3% of total lipids; their proportion was greater in spring than in summer and autumn.     

Carotenoids in petals of some perennial Medicago species

The petal carotenoids of several Medicago species, some of them considered as intermediate between the genera Medicago L. and Trigonella L. were investigated. Characteristics common to all species were: (a) the carotene fraction was small (0·2–4·4%) compared with the xanthophylls and their epoxy derivatives, (b) lutein, lutein-5,6-epoxide and violaxanthin constituted 83·7–98·1% of total content and thus were the prominent group in all species, (c) no single carotenoid of appreciable amount was characteristic to any species, (d) groups of related species tended to have similar quantities of major carotenoids.     

LIPOPHILIC PIGMENTS FROM CYANOBACTERIAL (BLUE-GREEN ALGAL) AND DIATOM MATS IN HAMELIN POOL,SHARK BAY,WESTERN AUSTRALIA1

Lipophilic pigments were examined in microbial mat communities dominated by cyanobacteria in the intertidal zone and by diatoms in the subtidal and sublittoral zones of Hamelin Pool, Shark Bay, Western Australia. These microbial mats have evolutionary significance because of their similarity to lithified stromatolites from the Proterozoic and Early Paleozoic eras. Fucoxanthin, diatoxanthin, diadinoxanthin, β-carotene, and chlorophylls a and c characterized the diatom mats, whereas cyanobacterial mats contained myxoxanthophyll zeaxanthin, echinenone, β-carotene, chlorophyll a and, in some cases, sheath pigment. The presence of bacteriochlorophyll a with in the mats suggest a close association of photosynthetic bacteria with diatoms and cyanobacteria. The high carotenoids: chlorophyll a ratios (0.84–2.44 wt/wt) in the diatom mats suggest that carotenoids served a photoprotective function in this high light environment. By contrast, cyanobacterial sheath pigment may have largely supplanted the photoprotective role of carotenoids in the intertidal mats.