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To assess the biodiversity of symbiotic dinoflagellates (SD) in hydrocorals, we compared the molecular species compositions of four SD lipid classes such as diacylglyceryl-3-O-carboxyhydroxymethylcholine (DGCC), digalactosyldiacylglycerol (DGDG), monogalactosyldiacylglycerol (MGDG), and sulfoquinovosyldiacylglycerol (SQDG) in Millepora dichotoma and M. platyphylla collected in shallow waters of Vietnam. A statistical analysis showed significant differences in the SD lipid composition between the hydrocoral species. These differences were influenced rather by the lipid molecules of outer membrane (DGCC and DGDG) than by the lipids of chloroplast and thylakoid membranes in SD (MGDG and SQDG). As for the fatty acid (FA) composition of lipid molecules that allow discrimination of hydrocoral SDs, the medium-chain FA 18:4 was characteristic of M. dichotoma, while the long- and very-long-chain FAs (20:5, 22:6, and 28:8) were characteristic of M. platyphylla. Thus, two different Millepora species hosted different SD groups, which had similar thylakoid lipidomes, different lipid profiles of outer membrane, and different activities in biosynthesis of n-3 polyunsaturated FAs. The lipidomic approach has shown that the M. dichotoma population is heterogenic, and about 10% of its colonies can be infected with SDs that are common for M. platyphylla.

In shallow tropical seas, hydrocoral colonies are locally abundant and important reef-framework builders. Hydrocorals are rich in lipids, which play an essential role in their physiology, but no data on seasonal variations in lipids of hydrocorals are available to date. In the present study, the profiles of total lipids, fatty acids (FA), storage and structural lipids classes, and molecular species of structural lipids in symbiotic dinoflagellates and the host of the hydrocorals Millepora dichotoma and M. platyphylla were analyzed each month throughout the year. In both hydrocoral species, the twofold increase in total lipids in the summer coincided with the water temperature rise and was caused primarily by the considerable accumulation of storage lipids with insignificant variations in structural lipids. The FA markers confirmed the year-round hydrocorals’ predation on zooplankton and indicated that M. dichotoma can consume more diatoms than M. platyphylla during October–January. The polar lipidomes of the two Millepora species were similar. The remodeling of alkyl and sphingosine groups in three structural lipid classes rather than unsaturation degree of their FA groups may be considered as a seasonal adaptive response of host biomembranes in Millepora. The symbiotic dinoflagellates of the hydrocorals kept the galactolipid ratio stable throughout the year but significantly increased the levels of sulfoquinovosyldiacylglycerol and betaine lipid in winter. The FA markers of the symbionts correlated negatively with galactolipids, thus, indicating a higher transfer of the symbiotic FA to the host in winter. Throughout the year, symbionts controlled their lipid class composition, but their lipid molecular species composition varied in a random manner. The considerable amounts of digalactosyldiacylglycerols with C20–22 polyunsaturated FA distinguished M. platyphylla from M. dichotoma and suggested that different hydrocorals contain different symbiont species. Data on seasonal variations of the lipidomes provide new background information for future studies of ecology, physiology, and biochemistry of hydrocorals.

The cold-water gorgonian coral Paragorgia arborea is considered as a foundation species of deep-sea ecosystems in the northern Atlantic and Pacific oceans. To advance lipidomic studies of deep-sea corals, molecular species compositions of diacylglycerol ethers (DAGE), which are specific storage lipids of corals, and structural glycerophospholipids (GPL) including ethanolamine, choline, inositol and serine GPL (PE, PC, PI, and PS, respectively) were analyzed in P. arborea by HPLC and tandem mass spectrometry. In DAGE molecules, alkyl groups (16:0, 14:0, and 18:1), polyunsaturated fatty acids (PUFA), and monounsaturated FA are mainly substituted the glycerol moiety at position sn-1, sn-2, and sn-3, respectively. The ether form (1-O-alkyl-2-acyl) predominates in PE and PC, while PI is comprised of the 1,2-diacyl form. Both ether and diacyl forms were observed in PS. At position sn-2, C20 PUFA are mainly attached to PC, but C24 PUFA, soft coral chemotaxonomic markers, concentrate in PS, PI, and PE. A comparison of non-polar parts of molecules has shown that DAGE, ether PE, and ether PC can originate from one set of 1-O-alkyl-2-acyl-sn-glycerols. Ether PE may be converted to ether PS by the base-exchange reaction. A diacylglycerol unit generated from phosphatidic acid can be a precursor for diacyl PS, PC, and PI. Thus, a lipidomic approach has confirmed the difference in biosynthetic origins between ether and diacyl lipids of deep-sea gorgonians.

The review is devoted to the chemical diversity of steroids produced by soft corals and their determined and potential activities. There are about 200 steroids that belong to different types of steroids such as secosteroids, spirosteroids, epoxy- and peroxy-steroids, steroid glycosides, halogenated steroids, polyoxygenated steroids and steroids containing sulfur or nitrogen heteroatoms. Of greatest interest is the pharmacological activity of these steroids. More than 40 steroids exhibit antitumor and related activity with a confidence level of over 90 percent. A group of 32 steroids shows anti-hypercholesterolemic activity with over 90 percent confidence. Ten steroids exhibit anti-inflammatory activity and 20 steroids can be classified as respiratory analeptic drugs. Several steroids exhibit rather rare and very specific activities. Steroids exhibit anti-osteoporotic properties and can be used to treat osteoporosis, as well as have strong anti-eczemic and anti-psoriatic properties and antispasmodic properties. Thus, this review is probably the first and exclusive to present the known as well as the potential pharmacological activities of 200 marine steroids.

The structural base of all membranes of symbiotic dinoflagellates (SD) is composed of glycolipids and betaine lipids, whereas triacylglycerols (TG) constitute an energy reserve and are involved in biosynthesis of glycolipids. Since data on the SD lipidome and the host's influence on symbionts' lipidome are scanty, we analyzed and compared the lipidomes of SD isolated from the zoantharian Palythoa tuberculosa and the alcyonarian Sinularia heterospiculata. A sequencing of nuclear gene regions showed that both cnidarians hosted the dinoflagellates Cladocopium sp. (subclades C1 and C3), but the zoantharian also contained the dinoflagellates Durusdinium trenchii (clade D). The presence of the thermotolerant D. trenchii resulted in a higher unsaturation of mono- and digalactosyldiacylglycerols (MGDG and DGDG), but a lower unsaturation of sulfoquinovosyldiacylglycerol (SQDG). The same features were earlier described for same SD from a reef-building coral. Hence, the profile of glycolipid molecules, which form SD thylakoid membranes, seems to be species-specific and does not depend on the host's taxonomic position. In contrast, the betaine lipid molecular species profile of diacylglyceryl-3-O-carboxyhydroxymethylcholine (DGCC), which forms SD cell membranes, can be influenced by the host. The profiles of the TG molecular species from freshly isolated SD have been determined for the first time. These molecular species can be divided on the basis of the acyl group in sn-2 position. The TG with 16:0 acyl group in sn-2 position may enrich total TG of a cnidarian colony and originate from SD cytoplasm. In contrast, TG 18:3/18:4/18:3 may be biosynthetically related with DGDG and concentrated in SD plastoglobules. Our data may be useful for further investigations of natural and technogenic variations in microalgal lipids and symbiont–host interactions in marine ecosystems.

To trace predator‒prey interactions in the marine environment, fatty acids (FAs) were widely applied as qualitative markers. Recently, two tetracosapolyenoic acids (TPA), which are specific markers of soft corals, have been found in the nudibranch mollusk Tritonia tetraquetra collected in the deep waters of the Sea of Okhotsk. This mollusk does not synthesize TPA but preys mostly on the soft coral Gersemia fruticosa. Both invertebrates are common species in Arctic and boreal regions and may be a simple model for the investigation of FA marker transfer from one trophic level to another. A lipidomic approach was applied to study the transfer of the FA markers in this predator–prey system. The structure and content of the molecular species of polar lipids (polar lipidome) of both animal species were analyzed by high-performance liquid chromatography with high-resolution tandem mass spectrometry. The distribution of several principal FA markers in lipid molecular species was determined. C20 monoenoic FAs of the coral were not integrated in the most of nudibranch lipids. Arachidonic and eicosapentaenoic acids mainly esterified ethanolamine and choline glycerophospholipids (PE and PC) in both invertebrates. In the coral polar lipidome, TPA concentrated in serine glycerophospholipids (PS). The nudibranch decomposed coral lipids and reallocated TPA to PS, PE, and PC. We suppose that this reallocation is responsible for the accumulation of TPA in the nudibranch. The nudibranch differed from the coral in biosynthetic relationships of phospholipid classes. The lipidomic approach explains the rearrangement of dietary FAs in the predator lipids. This rearrangement can be important for the trophic uptake and transfer of lipids in polar marine ecosystems.

In the fatty acid composition of total lipid of the soft coral Bebryce sp., the concentration of unsaturated fatty acid predominates. The composition of saturated fatty acids is very diverse, including all saturated fatty acids from C14 to C26. The unsaturated fatty acids with high concentration are C20: 4n-6, 20:5n-3, 22:6n-3, 24:5n-6, 26:3n-6, 26:2n-6, 26:2n-7, 28:3n-6. In the fatty acids composition of the studied coral, there is presence of characterized fatty acids for the existence of sponges C25-C28 (demospongic fatty acids) with total content 29,86%. Most of the Bebryce coral species do not have zooxanthellae, therefore, in the fatty acids composition, either it is lack or contains only a small amount of markers fatty acids for zooxanthellae such as 18:5n-3, 18:4n-3, 18:3n-6, 20:4n-3. In the phospholipid content of the soft coral Bebryce sp., there is presence of characterized classes for Cnidarian animals such as phosphatidylethanolamine (PE), phosphatidylchonline (PC), phosphatidylserine (PS), phosphatidylinositol (PI), phosphonolipid is ceramide aminoethylphosphonate (CAEP). PC account for the highest concentration (37,20% of total phospholipid). The molecular species of phospholipid classes of Bebryce sp. for the first time were investigated. In the results, there we 60 phospholipid molecular species identified in 5 classes. The molecular species with high content in the classes were PE 20:4/18:1e, PE 20:4/19:1, PC 20:4/18:0e, PC 20:4/16:0e, PS 24:5/18:0e, PI 24:5/18:0, CAEP18:2base/16:0 and CAEP 18:1base/16:0.

Gastropod molluscs such as nudibranchs are important members of deep-sea benthic ecosystems. However, data on the trophic ecology and feeding specialization of these animals are limited to date. The method of fatty acid trophic markers (FATM) was applied to determine the dietary preferences of nudibranchs off the Kuril Islands. Fatty acid (FA) compositions of Dendronotus sp., Tritonia tetraquetra, and Colga pacifica collected from deep waters were analyzed and compared with those of Aeolidia papillosa and Coryphella verrucosa from the offshore zone. The high level of FATM such as 22:5n-6 and C20 monounsaturated FAs indicated that Dendronotus sp. preys on sea anemones and/or anthoathecates hydroids similarly to that of shallow-water species A. papillosa and C. verrucosa. The high percentage of tetracosapolyenoic acids and the ratio 24:6n-3/24:5n-6 indicated that T. tetraquetra preys on soft corals such as Gersemia and/or Acanella at a depth of 250 m, but soft corals of the family Primnoidae may be the main item in the diet of T. tetraquetra at a depth of 500 m. The high content of Δ 7,13-22:2 and 22:6n-3 shows that C. pacifica can feed on bryozoans. In C. pacifica, 22:5n-6 may be synthesized intrinsically by the mollusks, whereas odd-chain and branched saturated FAs originate from associated bacteria.

The chemical structures and contents of 68 molecular species of ethanolamine glycerophospholipids (PE), choline glycerophospholipids (PC), serine glycerophospholipids (PS), and inositol glycerophospholipids (PI) were determined in the asymbiotic soft coral Gercemia rubiformis (Ehrenberg, 1834) from the Sea of Okhotsk by the method of tandem high-resolution mass spectrometry. The major molecular species were 16:1e/20:4 PE, 16:0e/20:4 PC, 20:1/24:5 PS, and 16:0/24:5 PI. This study showed a significant similarity of the polar lipidomes of G. rubiformis and tropical species of alcyonarians with symbiotic microalgae and revealed the basic characteristic of the polar lipidome of these alcyonarians. It was found that the 24:5n-6 and 24:6n-3 acids (chemotaxonomic markers of soft corals) concentrate in the acyl groups of the molecular species of PS and PI, which can be used as molecular lipid markers in the study of the symbiotic and trophic relationships of soft corals.

Nudibranch molluscs occur in marine ecosystems worldwide and prey on numerous invertebrate species. During feeding, dietary fatty acids (FAs) unusual for nudibranchs are transferred to their lipids. Normal biomembrane functions require stable composition of structural polar lipids (PL), but the pathways of dietary FA utilization to PL in nudibranchs still remain unknown. A combination of chromatography and tandem high-resolution mass spectrometry was used to determine total lipid, PL, FA, and PL molecular species composition of two cold-water species of Dendronotus, which then were compared with those of Tritonia tetraquetra. The use of FA trophic markers showed that Dendronotus sp. and T. tetraquetra prey on different soft corals, while D. robustus may consumes hydrocorals and bryozoans. Nudibranch FA profiles were strongly modified by dietary FAs but their PL profilers were similar. Dietary FAs are not included in ceramide aminoethylphosphonate and inositol glycerophospholipids, but directed to ethanolamine, choline, and serine glycerophospholipids and, in some cases, form isobaric molecular species with different FA chain lengths. For such isobaric species, nudibranchs reduce the length of alkyl groups when very-long-chain FAs are obtained with diet. This molecular mechanism may explain the adaptation of nudibranch membrane structure to dietary input of unusual FAs.

This study attempted the lipid extraction process from the seeds of Madhuca ellitica, a lipid-rich plant, and conducted a lipidomic analysis on molecular species of the obtained product. Total lipids of the crude seeds were found to contain 11.2% of polar lipids. The major fatty acids (FAs) of the polar lipids were palmitic (16:0), stearic (18:0), oleic (18:1n-9), and linoleic (18:2n-6) acids, which amounted to 28.5, 12.5, 44.8, and 13.2% of total FAs, respectively. The content and chemical structures of individual molecular species of phosphatidylglycerol (PG), phosphatidylethanolamine (PE), phosphatidylcholine (PC), phosphatidylinositol (PI), phosphatidic acid (PA), and sulfoquinovosyldiacylglycerol (SQDG) were determined by HPLC with a tandem high-resolution mass spectrometry (HRMS). The major molecular species were 18:1/18:2 PE, 16:0/18:1 PC, 18:1/18:2 PC, 16:0/18:2 PG, 16:0/18:1 PG, 16:1/18:1 PI, 16:0/18:1 PI, 18:0/18:2 PI, 16:0/18:1 PA, 18:1/18:2 PA, 16:0/18:1 SQDG, and 18:0/18:1 SQDG. The application of a tandem HRMS allows us to determine the content of each isomer in pairs of the monoisotopic molecular species, for example, 18:0/18:2 and 18:1/18:1. The evaluation of the seed polar lipid profile will be helpful for developing the potential of this tree for nutritive and industrial uses.

Year-round fluctuation in environmental conditions have a considerable influence on the level of biomarkers, that are usually applied for monitoring marine invertebrates. To date, no data on annual cycles of fatty acid (FA) biomarkers in tropical soft corals are available. The FA composition of the alcyonarian Sinularia flexibilis containing symbiotic microalgae was studied during a year. Two major FAs, 20:4n-6 and 16:0, determined the level of polyunsaturated and saturated FAs (PUFAs and SFAs). The insignificant variations in PUFA content indicated a relatively stable level of phospholipids that formed the structural base of coral cell biomembranes. No clear relationship between the PUFA markers of photosynthetic symbionts and the solar radiation was found. The three-fold increase in the SFA level in the summer correlated with the water temperature and indicated a rise in the level of neutral lipids that made up the energy reserve of corals. The seasonal changes in FA biosynthesis, membrane fluidity, and coral nutrition are discussed.

The seasonal dynamics of diarrhetic shellfish poisoning (DSP) toxins in the digestive gland of the mussel Crenomytilus grayanus (Dunker, 1853) from Peter the Great Bay in the Sea of Japan have been studied. Toxins in the form of 4-bromomethyl-7-methoxycoumarin derivatives have been analyzed using high-performance liquid chromatography (HPLC) with fluorometric detection. This method allows the determination of the quantitative and qualitative composition of individual toxins. All the C. grayanus samples contained DSP toxins, but their concentration varied substantially during the year. The highest concentration was recorded from the mussels collected in May; the lowest concentration was recorded in February. The toxins were represented predominantly by dinophysistoxin-2; in July-September and December, okadaic acid was detected. An assumption has been made about the relationship between the potential producers of DSP toxins in the waters of the Peter the Great Bay and the dynamics of these toxins in tissues of C. grayanus. The HPLC method, as an alternative to the enzyme-linked immunosorbent assay, was used to assess the quantitative and qualitative composition of DSP toxins in seafood for the first time in the Russian Federation. This method can be recommended for the routine monitoring of toxins conducted by the controlling organizations of the Russian Federal Service for Veterinary and Phytosanitary Surveillance.

A complete or partial loss of symbiotic dinoflagellates (SD) by the corals in response to thermal stress has been described as coral bleaching. A stress damages the photosynthetic apparatus of SD and their thylakoid membranes, and symbiotic alga cells disappear via exocytosis and/or apoptosis resulting in a disturbance of host cell membranes. Lipids play an essential role in coral metabolism and constitute the basis of membranes. At present, studies of coral bleaching typically deal with long-term lipid indices, such as total lipids and fatty acids (FAs), while short-term dynamics of lipidome (full range of all lipid molecular species) has not been considered in the context of bleaching mechanism. To evaluate the lipidomic approach to characterizing coral bleaching, the soft coral Sinularia sp. was exposed to a short-term experimental thermal stress (33 °C). The dynamics of chlorophyll level, the composition of total FAs, the amounts of total lipids and major lipid classes (such as wax esters (WE), triacylglycerols (TAG), and monoalkyldiacylglycerols (MADAG), glycolipids, ethanolamine-, choline-, serine-, inositolglycerophospholipids (PE, PC, PS, PI), and ceramide aminoethylphosphonate (CAEP)) and the variations in the content of lipid molecular species were studied during a 36-h heat exposure. >160 molecular species were identified by tandem high-resolution mass spectrometry. Under the short-term stress, a considerable decline in the levels of chlorophylls, glycolipids, and FA markers of SD was detected, whereas the variations in the content of total lipids, total phospholipids, and major FAs were not significant. The heat exposure immediately disturbed the daily cycle of the composition of glycolipid molecular species. Among the storage lipids, the content of TAG and MADAG decreased, whereas the content of polyunsaturated WE molecular species increased under the stress. The following effects were recorded for the structural lipids: a depletion in the PE, PC, and PI amounts, a conversion of PE into their lyso and oxidized derivatives, an appearance of diacyl form of PE, and a disturbance of transfer of some polyunsaturated FAs from SD to the host. The content of PS was relatively stable. Probably, PE molecular species are a primary target of thermal stress in the Sinularia host. The most dramatical changes in the Sinularia lipidome were detected between 24 h and 36 h of the exposure. A lipidomic approach is important for studies of dynamics of the coral symbiotic association and a resistance of different coral taxa during short-term bleaching events.

To expand our knowledge of lipid and fatty acid (FA) biosynthesis in marine cnidarians, polar lipidomes of hydrocorals were studied for the first time and then compared with those of soft corals from tropical and boreal regions. The structure and content of FAs and molecular species of ethanolamine, choline, serine, and inositol glycerophospholipids (PE, PC, PS, and PI, respectively), and ceramide aminoethylphosphonate (CAEP) in tropical hydrocorals (Millepora platyphylla, M. dichotoma) and the cold-water hydrocoral Allopora steinegeri were determined by chromatography and mass spectrometry. All soft corals and cold-water hydrocorals are characterized by a considerable amount of C20 polyunsaturated FAs (PUFAs) elongated into C22 PUFAs. In the Millepora species, the high level of 22:5n-6 and 22:6n-3 against the background of the extremely low level of C20 PUFAs may be explained by a high activity of rare Δ4 desaturase. In contrast to hydrocorals, soft corals are able to elongate and further desaturate C22 PUFAs into C24 PUFAs. Allopora and soft corals use C20 PUFAs mainly for the synthesis of PE and PC. The molecular species of PS of soft corals concentrate C24 PUFAs, while in Allopora and Millepora the PS molecules are mainly based on 22:4n-6 and 22:5n-6 acyl groups, respectively. Short acyl groups (C14) dominate the CAEP molecules of Allopora. In all the animals compared, most molecular species of PE and PC are ether lipids, but diacyl molecular species dominate PI. Hydrocorals and tropical soft corals contain diacyl and ether PS molecules, respectively, whereas cold-water soft corals contain a mixture of these PS forms. The high similarity of the alkyl/acyl compositions indicates a possible biosynthetic relationship between PS and PI in hydrocorals. The data obtained in our study will provide a resource to further investigate the lipid metabolism in marine invertebrates.

1-O-alkylglycerols (AKG) are a class of natural ether lipids derived from 1-O-alkyl-2,3-diacyl-sn-glycerols by deacylation. In this study, 1-O-alkylglycerol (AKG) composition was investigated in the hepatopancreas lipids of the crab Paralithodes camtschaticus and the liver lipids of the squid Berryteuthis magister and the skate Bathyraja parmifera. One of the principal AKG in marine organisms was 1-O-hexadecyl-sn-glycerol (AKG 16:0). To assess AKG influence on melanoma, we evaluated the cytotoxicity and antiproliferative actions of natural AKG 16:0 and synthetic 1-O-octyl-sn-glycerol (AKG 8:0) on three human melanoma cell lines SK-Mel-5, SK-Mel-28, and RPMI-7951. Natural AKG 16:0 in concentration up to 20 µM was not toxic to all cell lines. AKG 8:0 showed no toxicity to cells SK-Mel-5 and SK-Mel-28 in concentrations up to 20 µM but had moderate cytotoxicity to RPMI-7951 cells with an IC

Fatty acid (FA) markers are used to trace predator–prey relationships in the marine environment. Soft corals contain tetracosapolyenoic acids (TPA), namely 24:5n-6 and 24:6n-3, which are considered as octocoral FA markers. The nudibranch mollusks are known to feed on soft corals. To check whether TPA are transferred from soft corals to nudibranch mollusks during their nutrition, we determined and compared FA compositions of total lipids of Tochuina tetraquetra and soft corals (Acanella sp., Anthomastus rylovi, Gersemia fruticosa, and Paragorgia arborea) collected together near the Kuril Islands (the depths of 80–550 m). FA compositions of T. tetraquetra, Acanella sp. and A. rylovi were described for the first time. In Acanella sp., G. fruticosa, A. rylovi, and P. arborea, the average contents of TPA were 6.5, 13.4, 5.9, and 12.0 % of total FAs, whereas the 24:5n-6/24:6n-3 ratio was 1.0, 1.4, 5.4, and 2.6, respectively. The high level of TPA (21.7 %) found in T. tetraquetra indicates that 24:5n-6 and 24:6n-3 are transferred from soft corals to the mollusks during their feeding and accumulated in mollusk tissues. The most possible feed source of the mollusk is suggested to be G. fruticosa and/or Acanella sp., because the 24:5n-6/24:6n-3 ratios in T. tetraquetra and these soft corals were similar. Thus, the TPA could be used as FA markers to estimate a proportion of soft corals in feeding of cold-water nudibranch mollusks.

A method that uses marker fatty acids (FAs) is widely applied in investigations of trophic and symbiotic relationships. In a search for new lipid markers, we determined the total lipid FA composition, as well as the composition of molecular species of mono- and digalactosyl diacylglycerols (MGDGs and DGDGs), which are specific galactolipids of thylakoid membranes, in zooxanthellae (endosymbiotic dinoflagellates) of the tropical soft coral Capnella sp. Some FAs of zooxanthellae were suggested for use as marker polyunsaturated FAs (PUFAs). Thirteen molecular species of MGDGs and ten molecular species of DGDGs were detected using the method of high-resolution tandem mass spectrometry. All marker PUFAs of zooxanthellae were found in acyl groups of galactolipids. The major molecular species of DGDGs (18:4/18:4, 18:4/20:5, and 16:2/22:6) and the unique molecular species of MGDGs (16:4/18:5) were described. The identification of several polyunsaturated molecular species of galactolipids that contain marker FAs allowed us to propose that this lipid group be used as molecular lipid markers of zooxanthellae for the study of symbiont–host interactions in soft corals.

The soft corals of the genus Xenia are common for Indo-Pacific reef ecosystems. Lipid class, fatty acid (FA), phospho- and phosphonolipid molecular species compositions were identified for the first time in the soft coral Xenia sp. from Vietnam. Total lipids consisted predominantly of waxes, monoalkyl diacylglycerols, triacylglycerols, sterols, and polar lipids (21.4, 7.7, 14.2, 10.5, and 36.7 %, respectively). Sesquiterpene alcohol, valerenenol, was found. Acids 16:0, 18:3n-6, 20:4n-6, and 20:5n-3 dominated in total FA. The markers of zooxanthellae (18:4n-3 and 18:5n-3) and octocorals (24:5n-6 and 24:6n-3) were detected. Acids 18:5n-3, 20:4n-6, 22:4n-6, and 24:5n-6 concentrated in FA of polar lipids, whereas 14:0, 16:0, 16:1n-7, 18:2n-6, and 18:3n-6 were the major FA of neutral lipids. ChoGpl, EtnGpl, SerGpl, CAEP, PtdIns, and lyso ChoGpl constituted 39.5, 20.8, 20.5, 9.7, 4.3, and 5.3 %, respectively, of the sum of phospho- and phosphonolipids. Thirty-two molecular species of phospholipids and ceramide aminoethylphosphonate (CAEP) were determined by high resolution tandem mass spectrometry. Lyso 18:0e PakCho (4.1 %), 18:0e/20:4 PakCho (20.5 %), 18:1e/20:4 PlsEtn (18.0 %), 18:0e/24:5 PakSer (14.0 %), and 16:0 CAEP (9.6 %) were the major molecular species. EtnGpl and PtdIns mainly consisted of alkenyl acyl and diacyl forms, respectively. Alkyl acyl forms predominated in ChoGpl and SerGpl. Acid 24:5n-6 was a principal FA in SerGpl, whereas 20:4n-6 was more abundant in ChoGpl and EtnGpl. PtdIns contained various C20-24 PUFA. In the context of chemotaxonomy of corals, Xenia sp. has the lipid composition typical for soft corals and the FA profile similar to that of alcyonarians with the high level of 18:3n-6.

Lipid class and fatty acid (FA) compositions of the zoanthid Palythoa caesia from the South China Sea (Vietnam) were determined and compared with those of zooxanthellate reef-building and soft corals from the same region to clarify chemotaxonomic relations between zoanthids and corals. Total lipids of P. caesia and corals were formed by the same lipid classes. The lipids of P. caesia contained specific for cnidarians monoalkyldiacylglycerols and phosphonolipids. The proportion between reserve and structural lipid classes of P. caesia was similar to that of alcyonarians (soft corals), but significantly differed from reef-building corals. This similarity may be caused by the similar energy budget of cnidarian colonies without hard exoskeleton. The distribution of polyunsaturated FAs (PUFAs), such as 22:4n-6 and 22:5n-3, indicated pathways of biosynthesis of PUFAs in Palythoa to be closer to those in reef-building corals than in soft corals. The differences in the profiles of common FAs between P. caesia and reef-building corals were showed. Zoanthid lipids contained rare Δ5,9 non-methylene-interrupted (NMI) PUFAs (with two and three double bounds), which probably originated from microorganisms associated with P. caesia. Trienoic acids Δ5,9,15–24:3 and Δ5,9,17–24:3 were found in Palythoa for the first time. NMI PUFAs, as well as total FA profile, can be used for chemotaxonomy of Palythoa.

High diversity of fatty acid (FA) composition of endosymbiotic dinoflagellates of the Symbiodinium group (zooxanthellae) isolated from different cnidarian groups has been found. To explain this diversity, FA composition of the total lipids of pure symbiont fractions (SF) and host cell tissue fractions (HF) isolated from one hydrocoral, two soft coral, and seven hard coral species inhabiting the shallow waters of the South China Sea (Vietnam) were compared. Symbiodinium phylogenetic clade designation for each SF was also determined, however, the relationship between the clade designation and FA composition of Symbiodinium was not found. The profiles of marker polyunsaturated FAs (PUFAs) of symbionts (18:4n-3, 18:5n-3, 20:5n-3) did not depend on taxonomic designation of the host and reflected only a specimen-specific diversity of the SF lipids. Several FAs such as 20:0, C24 PUFAs, 22:5n-6, and 18:2n-7 concentrated in HF lipids but were also found in SF lipids. For ten cnidarian species studied, the principal components analysis of total FAs (27 variables) of the symbiotic fractions was performed. The clear division of the symbiotic dinoflagellates according to the host systematic identity was found on a subclass level. This division was mainly caused by the FAs specific for the host lipids of each cnidarian subclasses such as hard corals, soft corals, and hydrocorals. Thus, the coral hosts affect the FA profile of their symbionts and cause the diversity of FA composition of Symbiodinium. The transfer of FAs from the coral host to their symbiotic dinoflagellates and modulation of PUFA biosynthesis in symbionts by the host are considered as possible reasons of the diversity studied.

1-O-alkylglycerols (AKG) are a class of natural ether lipids derived from 1-O-alkyl-2,3-diacyl-sn-glycerols by deacylation. In this study, 1-O-alkylglycerol (AKG) composition was investigated in the hepatopancreas lipids of the crab Paralithodes camtschaticus and the liver lipids of the squid Berryteuthis magister and the skate Bathyraja parmifera. One of the principal AKG in marine organisms was 1-O-hexadecyl-sn-glycerol (AKG 16:0). To assess AKG influence on melanoma, we evaluated the cytotoxicity and antiproliferative actions of natural AKG 16:0 and synthetic 1-O-octyl-sn-glycerol (AKG 8:0) on three human melanoma cell lines SK-Mel-5, SK-Mel-28, and RPMI-7951. Natural AKG 16:0 in concentration up to 20 µM was not toxic to all cell lines. AKG 8:0 showed no toxicity to cells SK-Mel-5 and SK-Mel-28 in concentrations up to 20 µM but had moderate cytotoxicity to RPMI-7951 cells with an IC50 of 13 µM. Both investigated substances inhibited the proliferation, formation, and growth of cell colonies of RPMI-7951. PRACTICAL APPLICATIONS: AKG exhibit a variety of biological activities, including anticancer effects. In this study, the liver lipids of the skate B. parmifera and the hepatopancreas lipids of crab P. camtschaticus were shown to be sources of AKG. Our data showed that AKG can be used to prevent the formation of new colonies of malignant cells in combination therapy against melanoma. The results will be useful for future studies involving marine ether lipids and the examination of their anticancer properties against malignant cells.

This paper reviews the literature data on the composition, structure, and distribution of the main lipid classes and their fatty acids in reef-building and soft corals and in hydrocorals of the genus Millepora. The review presents information about more than 150 coral species from tropical and cold waters of the World Ocean, as well as data on the influence of environmental factors on the lipid compositions of corals. The possible pathways of polyunsaturated fatty acid biosynthesis in corals are discussed.

Fatty acid (FA) markers are widely used for tracking trophic relationships in cold-water benthic ecosystems, but data on the lipid composition of soft corals and hydrocorals, which are important components of these ecosystems, are very limited. Lipid class and FA profiles of four soft coral families (eleven species) and one hydrocoral family (four species) from the northeastern part of the Sea of Okhotsk were studied for the first time and compared with their tropical counterparts. Among cold-water cnidarians, soft corals contained much more monoalkyldiacylglycerols but less triacylglycerols than hydrocorals. The lipid class profile of all azooxanthellate soft corals did not differ, whereas FA profiles of these corals from cold-water and tropical regions differed. The key FAs were arachidonic (20:4n-6) and eicosapentaenoic (20:5n-3) acids, followed by 24:5n-6 and 24:6n-3. Within the cold-water corals, a sharp difference in polyunsaturated FA (PUFA) profiles between Primnoidae species and other families (Nephtheidae, Paragorgiidae, and Acanthogorgiidae) was found. The high level of n-3 PUFAs (20:5n-3 and 24:6n-3) in Primnoidae and the high level of n-6 PUFAs (20:4n-6 and 24:5n-6) in other cold-water coral families indicated the substantial difference in a feeding behavior between these corals inhabiting the same biotope. Based on the FA markers, a dietary predomination of herbivorous zooplankton is assumed for Primnoidae. An opportunistic feeding on various food sources is supposed for other cold-water coral families studied. The lipid and FA profiles were found to be characteristic for tropical zooxanthellate reef-building and soft corals, azooxanthellate soft corals from tropical and cold-water regions, and Primnoidae among cold-water coral families.

Monoalkyldiacylglycerol (MADAG) is an important lipid class in mollusks, corals, starfishes, and some species of zooplankton. Up to 80% of liver oils of squids and sharks are comprised of MADAG. Except for one fish species, there are no data on the composition of MADAG molecular species of marine organisms. The molecular species of MADAG obtained from digestive glands of the deep-sea squid Berryteuthis magister were identified. High-performance liquid chromatography (HPLC) and tandem high-resolution mass spectrometry (HRMS) with atmospheric pressure chemical ionization (APCI) were applied. The mass spectra of each molecular species contained positive quasi-molecular ion [M+H]+ with fragment ions [M–R′CO2]+, [M–R′′CO2]+, and [M–OR′′′]+, as well as negative cluster ion [M + 2H2O H]− without fragments. The exact masses of the negative ions allowed determination of the molecular formulas and the number of double bonds; the positive fragment ions were used to determine the location of acyl and alkyl groups in MADAG molecules. Ninety molecular species of MADAG were revealed. The regiospecific composition was identified for 72 individual molecular species. Eleven pairs of positional isomers of acyl groups were found. Four molecular ions were produced by a mixture of acyl/alkyl isomers. Most of molecular species contained 16:0e or 18:1e alkyl groups in the sn-1 position, whereas polyunsaturated fatty acids mainly esterified the sn-2 position of MADAG from B. magister. These structural features are supposed to be characteristic for biologically active MADAG.

Fatty acids (FAs) composition of eight zooxanthellate soft corals,Sinularia leptoclados, S. flexibilis, S.aff.deformis, S. lochmodes, S. cf.muralis, S. densa, S. notandaandS. cruciatacollected in Van Phong Bay (Vietnam) were studied to identify possible origin of unsaturated FAs. The main FAs were 14:0, 16:0, 7-Me-16:1n-10, 16:1n-7, 16:2n-7, 18:0, 18:1n-9, 18:4n-3, 20:4n-6, 20:5n-3, 22:6n-3, 24:5n-6 and 24:6n-3. On the average, saturated, monounsaturated, and polyunsaturated FAs (PUFAs) contributed 35.6, 6.2 and 54.0% of total coral FAs, respectively. PUFAs of n-6 series predominated in all animals (n-6/n-3 > 1.6). The content of 20:4n-6 varied from 10.2 to 23.8%. The main n-3 PUFA was 18:4n-3 (on the average, 5.4%); the contribution of 20:5n-3 and 22:6n-3, typical PUFAs of marine organisms, was not more than 2.4 and 3.9%, respectively. InSinularia, PUFAs were produced by endosymbiotic dinoflagellates (zooxanthellae) and the coral host tissue, or obtained with food. Zooxanthellae can be considered as the source of C16PUFAs and 18:4n-3. The coral host synthesized 18:2n-7, 24:5n-6 and 24:6n-3 acids. The low content of 18:1n-7, saturated odd-chain FAs and saturated methyl-branched FAs indicated a negligible contribution of bacteria to total lipids ofSinularia. A comparison of the levels of diatom and dinoflagellate FA markers in coral and plankton lipids showed eukaryotic microalgae to play a secondary role in feeding ofSinularia. The high level of 20:4n-6 may be considered as an indicator of heterotrophic feeding ofSinularia.

The fatty acid (FA) composition and the content of the prostaglandin PGE2 were determined in the red algae Gracilaria vermiculophylla and G. austramaritima from Peter the Great Bay (Sea of Japan), as well as in G. tenuistupitata, G. nhangii, and G. bailiniae from lagoons in southern Vietnam (in the South China Sea). Polyunsaturated FA (PUFA) comprised 49–56% of the total FAs in algae from the Sea of Japan, while in algae from the South China Sea their share was 20% at most. The content of arachidonic acid (20:4n-6) in the total FAs of G. vermiculophylla was as high as 45.4%, while the level of 20:4n-6 in Gracilaria from coastal waters of Vietnam did not exceed 12.5%. G. austramaritima stood out for its high content of eicosapentaenoic acid 20:5n-3 (33.5%). The ratios of 20:4n-6/20:5n-3 in G. vermiculophylla, G. austramaritima, G. tenuistupitata, G. changii, and G. bailiniae were 10.6, 0.3, 3.9, 4.0, and 1.5, respectively. The content of PGE2 was the highest (286 μg/g dry weight) in G. vermiculophylla from the Sea of Japan and did not exceed 20 μg/g dry weights in other Gracilaria species. This study showed that it is possible to introduce G. vermiculophylla from the Sea of Japan into the mariculture of northern Vietnam. In the experiment, during 3 weeks of cultivation, the biomass of introduced Gracilaria increased 1.2–1.3 times in a sea lagoon in Vietnam and 1.5–2 times in an aquarium; the algal growth rates were 1.57 ± 0.21% per day. In cultivated Gracilaria, the level of 20:4n-6 decreased to 5.9% (20:4n-6/20:5n-3 = 2.3) and the level of PGE2 decreased to 12 μg/g in dry weight. The PUFA compositions of G. vermiculophylla from various natural populations differed insignificantly; however, the stress caused by introduction led to a sharp reduction in the content of 20:4n-6, which was probably connected with a decreased biosynthesis rate of PUFAs of the n-6 series. At the same time, approximately equal amounts of PGE2 methyl ester were extracted from natural and cultivated G. vermiculophylla after treatment by a method proposed for obtaining prostaglandins. Thus, the cultivation conditions evidently did not influence the prostaglandin biosynthesis enzyme complex in G. vermiculophylla; this species, when grown in mariculture, can be used as a source of prostaglandins.

Literature data for the period from 1969 to 2010 on the distribution and chemical structures of prostaglandins, prostanoids, eicosanoids, and other cyclic and acyclic oxylipins from corals are summarized. The chemical structures of 97 compounds are given.

Coral bleaching induces changes in lipid and fatty acid composition that result in low lipid content, reducing the likelihood of coral survival. Species-specific differences in the metabolism of lipid reserves may contribute to the differential resistance of corals under acute heat exposures. Here, we examined the dynamics of lipids and fatty acid abundance in corals subjected to short-term heat stress. The stony corals Acropora intermedia, Montipora digitata, and the soft coral Sinularia capitalis all showed a 60–75% decline in both storage and structural lipids. However, S. capitalis and M. digitata exhibited no significant change in the percentages of structural lipids (i.e., polar lipids and sterols) until they had lost 90–95% of their endosymbionts, whereas A. intermedia showed a rapid decline in structural lipids after a 50% loss of symbionts. After a 90–95% loss of symbionts under heat stress, all three corals showed a relative depletion of polyunsaturated fatty acids that had symbiont biomarkers, suggesting that polyunsaturated fatty acids were translocated from the symbiont to the coral host tissue.

The fatty acid (FA) composition of zooxanthellae, polyp tissue, and intact colonies was determined in soft coral Sinularia sp. and hard coral Acropora sp. Analysis of the distribution of polyunsaturated fatty acids (PUFAs) among the zooxanthellae and the host organism showed that 18: 3n-6 and C18–22 PUFAs of the n-3 series (18: 4n-3, 20: 5n-3, 22: 5n-3, and 22: 6n-3) were mainly synthesized by the zooxanthellae and that C20–22 PUFAs of the n-6 series (20: 3n-6, 20: 4n-6, and 22: 4n-6) were synthesized in the polyp tissue. Soft coral polyps were able to synthesize tetracosapolyenoic FAs (24: 5n-6 and 24: 6n-3) and 18: 2n-7, their zooxanthellae synthesized C16 PUFAs (16: 2n-7, 16: 3n-4, and 16: 4n-1). It is supposed that the biosynthesis of 16: 2n-7 in Sinularia sp. and 18: 3n-6 in Acropora sp. is catalyzed by Δ6 desaturase. The relatively even distribution of three FAs (18: 2n-6, 18: 3n-6, and 16: 2n-7) among lipids of zooxanthellae and coral polyps indicates the possible transport of these FAs between symbionts and the host organism.

The lipid class and fatty acid (FA) composition for 93 species of reef-building and soft corals from the South China Sea (Vietnam) were analyzed and statistically compared to study system- atic patterns of the distribution of lipids in corals and the influence of zooxanthellae on the lipids of symbiont-host association. The lipid and FA compositions of hexacorals and octocorals significantly correlated with their taxonomic position, but the lipid features of species within each of these system- atic groups mainly depended on the presence of zooxanthellae. The hexacorals had lower content of polar lipids (PL), sterols (ST), and monoalkyldiacylglycerols (MADAG), but higher content of triacyl- glycerols (TG) and wax esters (WE) than the octocorals. On average, zooxanthellate species contained less structural lipids (PL+ST), but more MADAG when compared to azooxanthellate species. Tetracos- apolyenoic acids 24:5n-6 and 24:6n-3 were chemotaxonomic markers for octocorals, whereas 22:5n-6 was a marker for Milleporidae. A strong correlation was apparent between zooxanthellate coral fam- ily and/or genus and the content of the unsaturated FA; 12 FAs were significant for the separation of azooxanthellate and zooxanthellate specimens. The latter had lower concentrations of 7-Me-16:1n-10, 18:1n-7, and six C20 -24 polyunsaturated FA, but higher concentrations of 16:0, 16:2n-7, 18:3n-6, and 18:4n-3. The presence of >2% of 18:3n-6 and 18:4n-3 of total FA is characteristic of zooxanthellate corals. An inverse correlation was established between the content of 18:3n-6 and 16:2n-7 in zoo- xanthellate soft corals. The present study highlights the importance of zooxanthellae in coral lipid metabolism, especially when compared with symbiont-host exchanges in reef-building and soft corals.

The fatty acid (FA) composition of Demospongiae species from the Sea of Okhotsk was studied. Fifteen sponge species were investigated for the first time, and the previously studied species Desmacella rosea and Myxilla incrustans were reexamined for their FA composition. Gas chromatography-mass spectrometry revealed 150 different fatty acids, of which 15 have not been identified in sponge lipids previously. The relative content of saturated FAs varied from 7.6 in Melonachora kobjakovae to 29.6% in Amphilectus digitata, with an average of 14.6% of total FAs. The relative content of monoenic FAs ranged from 12.8 in T. dirhaphis to 27.0% in Polymastia sp., with an average of 20.6% of total FAs. Non-methylen-interrupted, primarily unsaturated Δ5,9-FAs contributed a significantly to the amount of polyunsaturated fatty acids of sponges; this being a distinguishing feature of the FA composition of the investigated group of organisms.

The relationship between taxonomic position and the lipid composition of octocorals from coastal waters of Vietnam was investigated. The principal component analysis of the total fatty acid (FA) composition of 64 coral specimens showed that total FAs are markers at the family level. A good distinction was obtained between antipatarians, gorgonians, and alcyonarians. Azooxanthellate corals of the genus Dendronephthya formed a separate group. The alcyonarian genera Sinularia, Lobophytum, and Sarcophyton were distinguished only by the composition of polyunsaturated FAs. The taxon-specific composition of FAs in octocorals is likely to be determined by differences in the nutrition of food sources, symbiont composition, and the enzymatic activity of FA biosynthesis.

The fatty acid compositions and stable isotope ratios of carbon, nitrogen, and sulfur were analyzed in the bivalve mollusks Mactra chinensis, Pandora pulchella, Felaniella usta, and Megangulus zyonoensis, the polychaete Chaetopterus cautus, and the main sources of organic matter in a subtidal sand bottom community in Vostok Bay (Sea of Japan). The fatty acid composition and stable isotope ratios of some bivalves is likely to be indicative of substantial inputs from benthic microalgae and an important role of microbial food chains. Only the filter-feeding polychaete C. cautus showed similarity in these characteristics to suspended particulate organic matter synthesized by phytoplankton. It is suggested that the contribution of benthic microalgae to the diet of a consumer organism, inferred solely from the carbon stable isotope analysis, can be significantly overestimated.

Sixteen scleractinian species of six coral families (Acroporidae, Pocilloporidae, Poritidae, Faviidae, Pectiniidae, and Fungiidae) from Vietnam were analyzed for fatty acid (FA) composition. Except for the Poritidae species, total lipids of the corals had the same set of FAs, about 50% of them being unsaturated acids. Some coral families had high levels of characteristic FAs: 20:3(n-6), 20:4(n-3), and 22:6(n-3) in Pocilloporidae; 18:1(n-9) and 22:6(n-3) in Poritidae; and 18:3(n-6) and 22:5(n-3) in Faviidae. For the first time in hexacorals, unsaturated C(24) FAs (24:1(n-9), 24:2(n-6), 24:2(5,9), 24:3(5,9,17), and 24:4(n-3)) were discovered in the Poritidae species. The highest level of 18:1(n-7), odd-chain and branched FAs (7.5% in total) was detected in Sandalolitha robusta. The data obtained on the contents of ten principal C(18)-C(22) polyunsaturated FAs (PUFAs) for the 16 specimens were combined with data on the 19 reef-building coral specimens investigated previously and subjected to multidimensional scale analysis (MSA). The representative coral families (Acroporidae, Pocilloporidae, Poritidae, Faviidae, Dendrophylliidae, and Milleporidae) were separated by MSA according to the composition of their principal PUFAs. Therefore, PUFAs may serve as chemotaxonomic markers for reef-building corals at the family level. Family-specific compositions of coral zooxanthellae characterized by different PUFA profiles, which affect the PUFA content of whole coral colonies, were supposed to be the probable cause of the discovered chemotaxonomic distinctions between reef-building corals.

The intra-and interspecific variability of fatty acid (FA) composition of soft corals was examined in the tropical alcyonarian Sarcophyton sp., tropical gorgonian Euplexaura erecta, and boreal alcyonarian Gersemia rubiformis. Characteristic significant differences in the FA composition were found between these species belonging to different taxonomic groups and habitats. We assume that the FA groups 14: 0 + 16: 0 + 18: 3n-6, 16: 2 + 20: 4n-6 + 24: 5n-6, and 18: 1n-7 + 20: 1n-7 + 20: 5n-3 + 24: 6n-3 are characteristic of Sarcophyton sp., E. erecta, and G. rubiformis respectively. There were no significant differences (p > 0.05) between the three soft coral species in the content of oleic, linoleic, and docosahexaenoic acids. The relative content of more than 45% of individual FA did not significantly differ (p > 0.05) between the pairs of species, i.e., intraspecific variations exceeded interspecific ones. The reasons for intraspecific variability of soft coral FA composition are discussed. Control of this variability is needed when using individual FA as chemotaxonomic and food markers.

Total lipid, phospholipid, and FA composition and distribution of FA between polar lipids (PL) and neutral lipids (NL) were investigated in the boreal soft coral Gersemia rubiformis from the Bering Sea. The total lipids were mostly hydrocarbons and waxes (33.7%) and PL (33.1%). The content of monoalkyldiacylglycerols (9.7%) exceeded the content of TAG (6.7%). PC and PE constituted 31.4% and 25.6% of total phospholipids, respectively. Principal FA were 16:0, 16:1n-7, 18:0, 18:1n-9, 18:1n-7, 20:1n-7, 20:4n-6, 20:4n-3, 20:5n-3, 22:5n-3, 22:6n-3, 24:5n-6, and 24:6n-3. Most n-6 PUFA (52% of total FA) were associated with the PL fraction; this was especially true for arachidonic and tetracosapentaenoic acids. The NL were enriched with mono-, di-, trienoic, and n-3 PUFA. The variation in EPA levels in both NL and PL suggests an origin of this acid from lipids of diatoms consumed by the corals.

Several unusual overlong-chain unsaturated aldehydes (22:1, 22:2, 23:1, 24:1, 24:2, and 25:2) were found in total lipids of the endemic sponge Lubomirskia baicalensis from Baikal Lake. Tetracos-17-enal was identified as the major aldehyde of the mixture using GC-MS and 1H and 13C NMR spectroscopy. A procedure for the isolation of total overlong-chain aldehydes was suggested. We think that the overlong-chain aldehydes defend the sponge from fouling and predators. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2005, vol. 31, no. 6; see also http://www.maik.ru.

Reinvestigation of the current FA composition of the regional freshwater sponge Baicalospongia bacillifera showed that the main measured isomer of EPA (14% of the total FA now detected) is, in fact, an unusual 5Z,8Z,11Z,14Z,18E-EPA. Two other isomers of this acid also present were identified as a novel 5Z,8Z,11Z,15Z,18E-EPA and the common methylene-interrupted 5Z,8Z,11Z,14Z,17Z-EPA (usually written simply as EPA). Isolation of these acids as their methyl ester derivatives was accomplished with the use of a combination of silver-ion column chromatography and HPLC. The structure of the two new compounds was deduced from GC-MS and detailed NMR data. Partial hydrazine reduction of all three isolated EPA esters followed by separation of cis/trans isomers of the resulting monoenoic acids and GC-MS analysis of their dimethyl disulfide adducts were used for determination of the configuration and position of the double bonds. We may assume that the sponge B. bacillifera cannot receive these unusual EPA isomers directly from food sources (e.g., algal diatoms), and accordingly restructuring of ordinary EPA to novel acids may take place in the sponge tissue.

In order to study the biomarker fatty acids of symbionts in the marine sponge Halichondria panicea, purification and structural identification of two new 2-methyl branched monoenoic very long fatty acids (2-Me-24:1 n-7 and 2-Me-26:1 n-9) were performed for the first time. These acids amounted to 7.1% of total sponge FAs, but our attempts to determine their structures by one-step GC-MS analysis were unsuccessful because of low yields of the correspondent N-acyl pyrrolidide derivatives. Silver-ion thin-layer chromatography isolated enriched fractions of monoenoic fatty acids extracted from the sponge. Further purification of unknown fatty acid methyl esters was carried out by reversed-phase high-performance liquid chromatography. Determination of the chain length, degree and position of unsaturations was achieved by gas chromatography-mass spectrometry on methyl esters and dimethyldisulfide adducts. Structures, position of methyl substitution, and double bonds cis isomery were confirmed by 1H nuclear magnetic resonance.

The fatty acid (FA) composition of total lipids isolated from the marine sponge Halichondriapanicea inhabiting Peter the Great Bay of the Sea of Japan was studied. GC and GC-MS techniques were used in identification of 63 FAs, with the main attention being paid to FAs with 14–22 carbon atoms. 4,8,12-Trimethyl-13:0 FA was for the first time identified as a main saturated FA, along with the branched FAs br-25:1, br-27:1, and br-27:2. The contents of arachidonic, eicosapentaenoic, docosapentaenoic, and the major demospongic acids [26:3(5,9,19), 26:3(5,9,17), 27:3(5,9,20), and 28:3(5,9,21)] considerably differed from those previously found for H. panicea, which may be due to seasonal changes in the species composition of organisms consumed by the sponge.

Fatty acids (FAs) of soft corals contain two very-long-chain tetracosapolyenoic acids (TPA, 24:5n-6 and 24:6n-3), which are chemotaxonomic markers of all species of the subclass Octocorallia. The distribution of TPA in molecular species of different phospholipid (PL) classes was investigated for the first time in the soft corals Sinularia macropodia and Capnella sp. From shallow waters of Vietnam. Phosphatidylethanolamine (PE), phosphatidylcholine (PC), phosphatidylserine (PS), and phosphatidylinositol (PI) were the major PL classes of S. macropodia and Capnella sp. More than thirty two molecular species of these four PL classes were determined by high resolution tandem mass spectrometry. 18:1e/20:4 PE, 18:0e/20:4 PC, 18:0e/24:5 PS, and 18:0/24:5 PI were the major molecular species of PL in both coral species. PE, PC, and PS mainly consisted of alkyl acyl and alkenyl acyl forms, but diacyl forms predominated in PI. TPA were the principal FAs in PS and PI, whereas 20:4n-6 was more abundant in PE and PC. Selective incorporation of TPA in the molecules of PS and PI are supposed to be a specific feature of the biosynthesis of PL in alcyonarians. To study the trophic and symbiotic relationships of soft corals, some molecular species of PS and PI with TPA may be applied as lipid molecular markers of coral polyps.

Carbon and sulfur stable isotope ratios, as well as fatty acid composition of tissues, of dominant consumer species were determined and compared to those of potential food sources in an isolated community of Zostera marina in a shallow, semi-enclosed inlet of the Sea of Japan. Of the 6 dominant species of invertebrates, 4 species were enriched in 13 C, compared to all sampled carbon sources alternative to Z. marina. Among them, the grazing gastropods Littorina squalida and Homa- lopoma sangarense exhibited the most enriched δ 13 C values. On the dual δ 13 C versus δ 34 S plot, these mollusks occupy an intermediate position between Z. marina and epiphytes, suggesting nearly equal proportions of organic carbon from both nutritional sources. In lipids of H. sangarense there was a high content of the 18:1(n-7) acid characteristic of aerobic bacteria; however, another grazer (L. squalida) showed the lowest content of bacterial fatty acids among all consumers. Other highly 13 C-enriched consumers were the surface-deposit-feeding mollusks, the gastropod Batillaria cumingii and the bivalve Macoma incongrua; however, their δ 34 S values were markedly lower than those of any of the primary producers sampled, including Z. marina. Although the high δ 13 C values of grazers and surface-deposit feeders are suggestive of a great contribution of Z. marina organic car- bon, no substantial concentrations of seagrass marker fatty acids were detected. Significant interspe- cific variations of both the sulfur isotope ratios and the fatty acid composition of these consumers sug- gest that there are a variety of pathways by which seagrass organic matter reaches invertebrates at lower trophic levels of the community food web. Dominant filter feeders, the bivalves Ruditapes philippinarum and Pillucina pisidium, had carbon drastically different in isotopic composition from Z. marina organic matter. Body tissues of P. pisidium and especially its gills, which bear symbiotic bacteria, were dramatically depleted both in 13 C and 34 S compared to all sources of photosyntheti- cally fixed carbon in the bay. Very low δ 13 C and δ 34 S values of P. pisidium body together with a high content of 18:1(n-7) acid suggest a leading role of sulfur-oxidizing symbiotic bacteria in the nutrition of this species. R. philippinarum was only slightly 13 C-enriched, compared to POM, and was the only consumer which had the high concentration of fatty acids characteristic of plankton, particularly 22:6(n-3). At the same time, it was much more 34 S-depleted than would be expected, assuming neg- ligible contribution of Z. marina detritus to its food. This mollusk showed a high content of branched fatty acids, especially the iso17:0 and anteiso17:0 acids characteristic of bacteria from sediment; this suggests that R. philippinarum assimilated notable amounts of bacteria from resuspended sediment. Furthermore, the contribution of 34 S-depleted bacteria, which inhabit reduced sediment, to R. philip- pinarum nutrition was high enough to result in the observed depletion of 34 S in mollusks. Further progress in food web studies of seagrass ecosystems using a complex of multiple stable isotope and fatty acid analyses would appear possible on the basis of analysis of separate components of the sea- grass epiphytic community and micro- and meiobenthic organisms, inhabiting surface sediments.

The influence of diet on lipid and fatty acid composition of the brine shrimp Artemia salina nauplii was investigated. Various diets with different lipid composition and fatty acid profiles were fed to nauplii for 2 weeks. The lipid composition of microalgal diets, Isochrysis galbana, Phaeodactylum tricornutum and Nannochloropsis oculata and baker's yeast was analyzed. Newly hatched nauplii were examined before the feeding experiment. It was shown that Artemia was able to incorporate and selectively concentrate some dietary lipids. Depot lipids were more sensitive to changes in the dietary lipid composition than the main structural lipids, polar lipids and sterols. Variations in the content of the lipid classes correlated with stage of development of the animal. The fatty acid composition of the animal varied with that of diet. The concentrations of saturated fatty acids were apparently supported in the nauplii by biosynthesis de novo. The acid 16:1(n-7) originated from the food. The concentration range of n-6 polyunsaturated fatty acids (PUFAs) remained constant through the accumulation from the diet. The proportion of n-3 PUFAs varied with their level in the diet. The dynamics of alteration of 20:5(n-3) content in Artemia fed on Isochrysis, which is poor in this acid, suggested a limited capacity for elongation and desaturation of 18:3(n-3) to 20:5(n-3). None of the diets provided dietary input of 22:6(n-3). (C) 1998 Elsevier Science Inc. All rights reserved.

The composition of Δ5(Δ4) unsaturated medium- and long-chain fatty acids (FAs) of the freshwater sponge Baicalospongia bacilifera was selectively determined by means of the analytical iodolactonization reaction and the structures of FAs were identified by gas chromatography-mass spectrometry (GC-MS), spectrophotometry, and particular chemical degradation. The presence of several unusual monoenoic branched-chain FAs iso -15:1 Δ4, anteiso -15:1 Δ4, iso -17:1 Δ4, anteiso -17:1 Δ4, non-methylen interrupted tetraenoic acid 18:4 Δ5,9,12,15 and isomeric eicosapentaenoic acid (IEPA) with a trans double bond (20:5 Δ5 c ,8 c ,11 t ,14 c ,17 c ) was shown.