Content 7..20

Contents

Foreword XXI Optical properties of seawater 15 Rapid absorption of light in relation to depth 15 Preface and Acknowledgements XXIII Selective absorption of the wavelengths 15 List of Figures XXV Biological and ecological aspects 16 List of Tables XXXV Primary and secondary metabolites 16 Ecomones: vectors of chemical communication 16 Abbreviations, Acronyms, and Cell Lines XXXIX Phenomena of dependence 16 Dependence on light 16 Volume 1 Dependence on temperature 17 Dependence on salinity 17 Main types of interspecific relations 17 Part 1 Commensalism 17 General Aspects and Documentary Symbiosis 17 Resources Parasitism 17 The hierarchy of ecological levels and space 1 distribution of marine organisms 18 Systems of Classification of Living Organisms: Plant biodiversity: phylogeny of the algae 18 Great Steps in Chemical and Biological Animal biodiversity 21 Evolution 3 Biochemical characteristics of sessile animals 23 Estimation of biomass 23 Whittaker’s five kingdoms system 3 Selection of documentary resources 24 Discovery of Archaea(Archaebacteria): References 24 ternary model of living organisms 4 Websites 25 Characteristics of cell membranes 5 Some recent data on terpenes 7 3 Main stages of evolution 8 Chemistry of Marine Natural Substances: Originality, Diversity, Distribution 27 Exceptional resources of marine biodiversity 9 General introduction 27 Selection of documentary resourcess 10 References 10 Distribution of nitrogenous and non-nitrogenous Websites 12 secondary metabolites 27 Distribution of secondary metabolites by chemical class 28 2 General Information on the Marine Characteristics of the secondary metabolites of marine organisms 29 Environment 13 Incorporation of halogens 30 Physicochemical aspects 13 Incorporation of sulfur 31 Chemical composition of seawater 13 Incorporation of silicon 32

Rare chemical elements encountered in marine Part 2 substances: As, B, Ni, V, Zn 32 Archaea (Archebacteria) and Eubacteria Arsenic 32 Boron 32 6 Nickel 33 Archaea (Archaebacteria) 73 Vanadium 33 Zinc 33 General introduction 73 Selection of documentary resources 34 Membrane lipids 74 References 34 Pranylquinones 79 Websites 36 Cyclic polysulfides 80 Bacteriorhodopsin of halophiles 81 4 Basic Marine Pharmacology 37 Extremozymes 82 The hopes of the past 37 Appendix 1: Stereospecific numbering (sn) 83 The realities of the present 39 Selection of documentary resources 83 1. Ethnopharmacology 39 References 83 2. The triptych: biodiversity–chemodiversity– Experimental documentation 85 pharmacodiversity 40 Websites 85 3. Methods 44 Synthesis 86 Future directions 46 Selection of documentary resources 53 7 References 53 Eubacteria – 1 87 Websites 56 Cell walls and Gram reaction 87 Anaerobic and aerobic photosynthesis: bacteriochlorophylls 88 5 Documentary Resources 59 Brief overview of marine bacteria 90 Short historical background 59 Piezophile (barophile) and psychrophile bacteria from extreme environments 91 Printed documentation 60 Chemical Abstracts, Biological Abstracts, Examples of metabolites isolated Current Contents 60 from non-photosynthetic bacteria 91 Basic works 60 Lipopolysaccharides and other characteristics Reference works 61 of some Gram-negative bacteria 106 Articles published in volumes not entirely dedicated to marine organisms 61 Anaerobic photosynthetic bacteria 107 Scientific journals and the impact factor 62 Aerobic photosynthetic bacteria 107 Scientific journals specializing in developments in natural marine products 62 Anammox bacteria and “ladderane lipids” 108 Articles about development published Appendix 2 110 in scientific journals 65 Proceedings of the major international symposia 66 Selection of documentary resources 111 General articles on the synthesis of marine natural References 111 products 66 Websites 116 Synthesis 116 Electronic documentation 67 “Static” databases 68 “Dynamic” databases 68 Searching for information on the Internet 68 Contents IX

8 Part 3 Eubacteria – 2 121 Photosynthetic Eukaryotes Prochlorophyta 121

Taxonomy of Prochlorophyta 121 9 Unique characteristics of photosynthesis Bacillariophyceae (Diatoms) 173 in Prochlorococcus 122 Frustules: fundamental characteristics of diatoms 173 Biochemical data on Prochloron didemni 123 Bases of classification of diatoms 174 Biochemical data on Prochlorothrix hollandica 123 Primary metabolites 174 Cyanobacteria 124 Photosynthetic pigments 174 Traditional classification of cyanobacteria 124 Membrane lipids 175 Photosynthetic pigments 125 Terpenic hydrocarbons 177 Membrane lipids 128 Other terpenic derivatives: description General characteristics of the secondary of the two biosynthetic pathways 179 metabolites 129 Genera Nitzschia and Pseudo-nitzschia: domoic Malyngamides and other chlorinated derivatives 130 acid 180 Semiplenamides A–G and besarhanamides A–B 133 Other molecules 181 Aplysiatoxin, oscillatoxin-A Appendix 5 183 and other brominated derivatives 134 Appendix 6 184 Other non-peptidic nitrogenous derivatives 135 Selection of documentary resources 185 Lipopeptides, peptides and depsipeptides 137 References 185 Websites 187 Other toxins 147 Synthesis 188 Sulfated compounds 148 Polymethoxyalkenes and poly-b-hydroxybutyric acids (PHBAs) 150 10 Other molecules 151 Chrysophyceae, Raphidophyceae, Haptophyceae 191 Appendix 3 153 Chrysophyceae 191 Appendix 4 154 General presentation: simplified classification 191 Selection of documentary resources 155 Photosynthetic pigments References 155 and storage polysaccharides 191 Websites 162 Fatty acids 191 Synthesis 163 Sterols 191 Other derivatives 192 Raphidophyceae 193 Haptophyceae 193 General presentation: simplified classification 193 Photosynthetic pigments 194 Sterols 194 Fatty acids and other linear derivatives 195 Prymnesins 196 Particular characteristics of Pavlova pinguis and Pleurochrysis carterae 197 X Contents

Appendix 7 198 12 Selection of documentary resources 199 Chlorophyceae (Green Algae) References 199 and Marine Spermatophyta 251 Websites 200 General aspects 251 Synthesis 200 Elements of classification of marine macroalgae 251 11 Classification of Chlorophyceae 252 Dinophyceae (Dinoflagellates) 201 Chlorophylls, carotenes and xanthophylls 252 General aspects 201 Storage polysaccharides: starches 254 Classification of dinoflagellates 202 Cell-wall polysaccharides 255 Photosynthetic pigments 202 Matrix polysaccharides 255 Sulfated exopolysaccharides 203 Membrane lipids: fatty acids and sterols 255 Sterols 204 Oxylipins 258 Fatty acids 204 Background on the secondary metabolites Glycolipids 207 of Chlorophyceae 259 Amphidinols and other polyhydroxylated polyenic Terpenes 259 derivatives 207 Meroterpenes of Dasycladales 262 Toxic proliferations: endo- and exotoxins 211 Aromatic derivatives 263 Main types of dinoflagellate toxins 212 Amino acids, amines, betaines 264 Cyclic polyethers 212 Peptides and depsipeptides: kahalalides 264 Okadaic acid and derivatives 220 Other nitrogen-containing derivatives 265 Toxic macrolides: amphidinolides, caribenolide, gonio- Sulfur-containing derivatives 267 domin A, hoffmanniolide 222 Marine Spermatophyta (phanerogams) 267 Complexity of the biosynthesis of polyketides 225 Selection of documentary resources 268 Saxitoxin and its derivatives 225 References 268 Nitrogenous toxins with imine function 228 Websites 272 Synthesis 273 Zooxanthellatoxins (ZTs) and other nitrogenous toxins 229 Pfiesteria piscicida: a particularly toxic 13 dinoflagellate 232 Rhodophyceae (Red Algae) 275 Sulfur-containing derivatives 232 Special features of red algae 275 Phosphorus derivatives 233 Classification of Rhodophyceae 275 Selection of documentary resources 233 Photosynthetic pigments 277 References 233 Storage monosaccharides and polysaccharides 278 Websites 241 Synthesis 242 Skeleton polysaccharides 278 Matrix polysaccharides: carrageenans and agars 278 Carrageenophytes and agarophytes 281 Gelling agents and thickeners 281 Contents XI

Other types of matrix polysaccharides 282 Cyclic polysulfides of Chondria californica 332 Phospholipids and fatty acids 282 Arsenic-containing derivative of Chondria crassicaulis 332 Oxylipins and prostaglandins 284 Some atypical derivatives of Laurencia species 333 Sterols and ecdysteroids 285 Halogenated derivatives of Nemaliales 333 General comments on the secondary metabolites 286 Acetylenic acids of Liagora farinosa 335 Secondary metabolites of Cryptonemiales 287 Sulfated triterpene alcohols of Tricleocarpa fragilis 336 Secondary metabolites of Gelidiales 290 Cyclic peptide from Galaxaura filamentosa 337 Secondary metabolites of Rhodymeniales 290 Appendix 8 337 Polyhalogenated monoterpenes of Gigartinales 291 Appendix 9 338 Diterpenes of Sphaerococcus coronopifolius (Gigartinales, Sphaerococcaceae) 293 Selection of documentary resources 338 References 338 Macrocyclic pyrones of Phacelocarpus labillardieri Websites 352 (Gigartinales, Sphaerococcaceae) 297 Synthesis 353 Polycavernosides of Polycavernosa tsudai (Gigartinales, Gracilariaceae) 297 14 Brominated meroditerpenes of Callophycus serratus (Gigartinales, Solieriaceae) 298 Phaeophyceae (Brown Algae) 361 Halogenated phloroglucinols of Rhabdonia verticillata General introduction; 361 (Gigartinales, Solieriaceae) 299 Classification of Phaeophyceae 361 Sulfated aromatic derivatives of Tichocarpus crinitus Photosynthetic pigments 363 (Gigartinales, Tichocarpaceae) 299 Laminarans and other storage osides 363 Nitrogen-containing derivatives of Gigartinales 299 Matrix polysaccharides: alginic acids and alginates 364 Halogenated compounds of Ceramiales: general comments 300 Fucoidans (sulfated fucans) 365 Polyhalogenated monoterpenes of Pantoneura Lipids and fatty acids 367 plocamioides (Ceramiales, Delesseriaceae) 301 Oxylipins of Laminariales 367 Sesquiterpenes of Laurencia Epoxy lipids of Notheia anomala (Chordariales) 370 (Ceramiales, Rhodomelaceae) 301 Sterols 371 Halogenated diterpenes of Laurencia 310 Volatile hydrocarbons and sexual chemotaxy 372 Non-halogenated hydroperoxyditerpenes of Laurencia 319 Background on the secondary metabolites 376 Squalenoids of Laurencia species Sesquiterpenes of Dictyotales 376 and Chondria armata 319 Cyclic diterpenes of Dictyotales 377

Cyclic halogenated C15 ethers and polyethers Linear diterpenes of Fucales and other derivatives 382 of Laurencia and Chondria 322 Phenols and phlorotannins 385 Bromo- and polybromophenols of Ceramiales 325 Other aromatic derivatives 388 Nitrogen-containing bromophenols of Rhodomela confervoides 328 Meroterpenes: general comments 389 Other nitrogen-containing derivatives Prenylated quinones and hydroquinones 389 of Ceramiales 329 Meromonoterpenes of Sporochnus bolleanus 390 XII Contents

Merosesquiterpenes of Dictyopteris species 391 Uses of algae in cosmetics 434 Meroditerpenes of the genera Taonia Uses of algae in agriculture and livestock and Stypopodium 392 production 435 Meroditerpenes of Cystoseira species: chemotaxonomy Selection of documentary resources 435 of Cystoseiraceae 396 References 435 Proceedings of the latest International Seaweed Nahocols and isonahocols: rearranged linear Symposia 440 meroditerpenes of Sargassum autumnale 401 Websites 440 Derivatives of nitrogen, phosphorus and arsenic 402 Sulfur-containing derivatives 404 Part 4 Iodinated derivatives 405 Fungi and Other Eukaryotic Unicellular Appendix 10 406 Non-photosynthetic Organisms Appendix 11 407 16 Selection of documentary resources 407 Fungi 445 References 407 Websites 417 The Fungal Kingdom: the concept Synthesis 418 of marine fungi 445 Mastigomycetes and Eumycetes (true fungi) 446

15 Elements of classification of Eumycetes 446 Major Uses of Macroalgae 423 Background information on the structure of chitin 446 Overview 423 Fatty acids 446 Estimate of resources 423 Sterols 446 Edible seaweeds 425 Membrane peptides of fungi: peptaibols 448 Dietary properties of marine algae 425 General comments on secondary metabolites Physicochemical aspects of phycocolloids 426 of marine fungi 449 Economic aspects of phycocolloids 428 Substances isolated from fungi collected Major producing countries of phycocolloids 428 from the surface of the sea 449 Main applications of agars 428 Substances isolated from fungi from sediments and other inert substrates 450 Main applications of carrageenans and furcellar- ans 430 Substances isolated from fungi associated with cyanobacteria 454 Main applications of alginic acid and alginates 430 Algicolous fungi: general remarks 454 Summary of research in the field of healthcare 431 Substances isolated from fungi associated Antiviral and immunostimulant sulfated with green algae and marine Spermatophyta 454 polysaccharides of red, brown and green algae 431 Substances isolated from fungi associated Anticoagulant and antithrombotic properties with red algae 458 of fucoidans 432 Substances isolated from fungi associated Antitumoural, immunomodulatory and antiviral with brown algae 459 properties of fucoidans 433 Substances isolated from lignicolous fungi 461 Other examples of biological activities of macroalgae 434 Substances isolated from fungi associated with sponges 465 Contents XIII

Substances isolated from fungi associated 18 with cnidarians 473 Introduction to Marine Biotechnology 503 Substances isolated from fungi associated Introduction 503 with molluscs 474 Recent developments in the culture Substances isolated from fungi associated of invertebrates 503 with bryozoans 476 Lipids and pigments: examples Substances isolated from fungi associated of nutritional applications 504 with echinoderms 476 New substances and biomaterials: examples Substances isolated from fungi associated of biomedical applications 506 with crustaceans 478 Bioremediation and biofouling: examples Substances isolated from fungi associated of environmental applications 507 with tunicates (ascidians) 478 Dialkylphthalates in marine organisms 508 Substances isolated from fungi associated with fish 480 Another type of application: bioadhesives 508 Selection of documentary resources 481 Some examples of biotechnology in Prokaryotes 509 References 481 Selection of documentary resources 510 Websites 488 General references 510 Synthesis 489 References 510 Websites 516

17 Thraustochytrids and Ciliates 493 Volume 2 Taxonomic position of thraustochytrids and overview of the group 493 Part 5 Porifera, Cnidaria, and Ctenophora Carotenoids of thraustochytrids 493 Long-chain (n-3) polyunsaturated fatty acids 19 of thraustochytrids 493 Porifera (Sponges) 521 Long-chain fatty acid composition and phylogeny Overview of the universe of sponges 521 of thraustochytrids 495 Metabolites of Calcarea (calcareous sponges) 524 a -Glucosylceramides of thraustochytrids 495 General characteristics of Calcarea 524 Introduction to the chemistry of ciliates 496 Fatty acids 524 Sterols 524 Terpenes of Euplotes 497 Non-nitrogenous derivatives of species Keronopsins of Pseudokeronopsis rubra 498 of the genus Leucetta 525 Imidazole alkaloids and zinc complexes isolated from Selection of documentary resources 499 the genera Leucetta, Leucosolenia and Clathrina 526 References 499 a,x-Bis long-chain aminoalcohols 528 Websites 501 Nitrogen-containing macrolides and cyclic Synthesis 501 peptides 529 Other nitrogen-containing compounds of Calcarea 529 Metabolites of Hexactinellida 530 Classification and membrane constituents of Demospongiae 531 Classification 531 XIV Contents

Some physical observations on demosponges 532 Bengazoles and bengamides 603 Shape and size 532 Atypical nitrogenous derivatives 605 Consistency 532 Phosphorus-containing derivatives similar Colour and odour 532 to calyculin A 607 Diversity of membrane constituents: Aromatic sulfated derivatives 608 some examples 536 Isotactic polymethoxydienes of Myriastra clavosa 608 Phospholipids and demospongic acids 538 Secondary metabolites of Hadromerida Fatty acids with 5,9 dienic structure 541 and Chondrosida 609 Other mono- and polyunsaturated fatty acids 543 Perforating power of Clionaidae 609 Branched fatty acids 544 lyso-Phospholipids and sulfated sphingosines Isoprenic acids 547 of Spirastrella abata 610 Cyclopropanic acids 548 Brominated acetylenic derivatives of Diplastrella 611 Brominated acids 550 Cyclic peroxides 612 2-O substituted acids 551 Terpenes 613 Sulfur derivatives of demospongic acids 553 Unconventional sterols 614 Intracellular localization and biological activity Macrolactones: latrunculins and spongistatins 615 of demospongic acids 555 Atypical glycosides of Latrunculia corticata 617 Brief reminder about conventional sterols 555 Other nitrogen-free toxins 617 Unconventional sterols produced by changes Peptides and depsipeptides 618 in the tetracyclic system 556 Pyrrole derivatives and other nitrogen-containing Unconventional sterols produced by polymethylation heterocycles 619 of the side chain 561 Atypical nucleosides 621 Sterols with degraded side chains 564 Sterols and stanols with cyclopropanic Secondary metabolites of Lithistida 622 and cyclopropenic side chains 564 Particular characteristics of lithistid sponges 622 Secosterols 566 Nitrogen-containing sesquiterpenes of Theonella 623 Polyhydroxylated steroids and derivatives, Specific glycolipids of Theonella swinhoei, peroxysterols 569 Discodermia calyx and D. dissoluta 623 Sulfated sterols 571 Long-chain polyacetylenic derivatives of Theonella Chlorinated sterols and sterones 574 sp. 624 Nitrogen-containing sterols 576 3b-Methoxysterols of Jereicopsis graphidiophora 624 Glycolipids 577 4-Methylenesterols and sterones of Theonella 624 Macrolides 626 Secondary metabolites of Homoscleromorpha 582 Examples of acetogenins: discodermolide, Fatty acids, polyketides and oxylipins calyculins and onnamides 629 of Plakinastrella and Plakortis 582 Linear peptides 630 Cyclic peroxides and peroxylactones Mono- and bicyclic peptides 632 of Plakinastrella and Plakortis 584 Symbiotic origin of some polypeptides 635 Glycosides 587 Cyclic and linear depsipeptides 635 Polyhydroxylated sterols of Oscarella lobularis 587 Atypical nitrogenous derivatives 639 Alkaloids and other original nitrogen derivatives of Plakortis and Corticium 587 Secondary metabolites of Spirophorida 640 Atypical sterols of Cinachyra, Microscleroderma, Secondary metabolites of Astrophorida 590 and Scleritoderma 640 Acetylenic fatty acids of Stelletta 591 Cinachyrolide A 640 Glycolipids: caminosides and pachymosides 591 Microsclerodermins and aciculitins 641 Triterpenes of malabaricane and isomalabaricane: Examples of atypical derivatives of some sponges sesterterpenes 591 of the Tetillidae 641 Triterpenic glycosides and steroidal glycosides 593 Substituted tetramic acids and derived glycosides 596 Secondary metabolites of Agelasida 642 Erylusamines, erylusine and erylusidine 598 Sterols 642 Cyclic depsipeptides, peptolides Diterpenes and carotenoids 642 and macrolactones 598 Merosesquiterpenes and nitrogen-containing Nitrogen-containing terpenes 602 meroditerpenes 643 Contents XV

Galactosylceramides and glycolipids 644 Secondary metabolites of Poecilosclerida 724

Oroidin and related C11N5 bromopyrrole alkaloids 646 Sterols, steroids and sterosides 725 Agelastatin A series 649 Terpenes and triterpenic glycosides 727 Other series 650 Polybrominated acetogenins and oxylipins 732 Pyrrole-2-carboxylic acid derivatives 650 Long-chain acetynenic derivatives: raspailynes 732 Other examples of nitrogen-containing Glycolipids 733 heterocycles 650 Brominated aromatic derivatives Betaines 651 of Hamigera tarangaensis 733 Macrolides 734 Secondary metabolites of Halichondrida 652 Chondropsins: cyclic depsipeptides A-nor-steroids and other non-conventional sterols 652 of Chondropsis sp. 736 Conventional terpenes 654 Eurypamides (Microciona eurypa), microcionamides Nitrogen-containing terpenes: isonitriles (Clathria abietina) and other cyclic peptides 737 and related derivatives 659 Linear amides 738 Other terpenes 666 Examples of some atypical sulfur-containing Long-chain linear polyamines derivatives 739 and a,x-bis-isothiocyanates 668 Pyrrole and indole derivatives 741 Polyethers: halichondrins, okadaic Pyridines, quinolizines and pyridoacridines 742 and glycookadaic acids 668 Guanidine derivatives 743 Various lipids 670 Pyrroloiminoquinones and pyrroloquinones 747 Linear peptides of the genera Auletta Azasugars 748 and Cymbastela 672 Other examples of polycyclic alkaloids 748 Depsipeptides and cyclic peptides 672 Phosphorus and arsenic-containing derivatives, Pyrrole, imidazole, pyridine, isoquinoline betaines 750 and indole derivatives 678 Pyrrole derivatives 678 General information on the metabolites Imidazole derivatives 678 of sponges lacking mineral spicules 751 Pyridine and isoquinoline derivatives 679 Secondary metabolites of Dendroceratida 753 Indole derivatives 679 Terpenes and meroterpenes 754 Heterocycles related to the oroidin family 681 Sterols 760 Atypical halogenated and sulfur-containing Polybromophenols and polybromodiphenyl ethers derivatives 682 of Dysidea 761 Secondary metabolites of Haplosclerida 683 Nitrogen compounds 763 Acetylenic derivatives 685 Secondary metabolites of Dictyoceratida 768 Atypical fatty acids 691 Terpenes and meroterpenes 768 Terpenes and meroterpenes 693 Sterols 788 Triterpenic glycosides 699 Glycolipids 789 Hopanoids, steroids and sterosides 701 Polybromodiphenyl ethers and other halogenated Macrolides, depsipeptides and cyclic peptides 704 aromatic derivatives 789 Amino alcohols and glycosphingolipids Macrolides: laulimalide, altohyrtins, chondropsins (cerebrosides) 705 and haterumalides 790 Manzamines and related derivatives 707 Linear and cyclic peptides, depsipeptides 791 Quinolizidine and 1-oxaquinolizidine derivatives 707 Alkaloids and other nitrogen-containing Pyridine derivatives and 3-alkylpyridinium salts 714 compounds 793 Pyridoacridine alkaloids 716 Phosphorus derivatives 795 Pyrroloquinones and other examples Atypical sulfur derivatives 796 of nitrogen-containing heterocycles 717 Quinones and sulfated hydroquinones 721 Secondary metabolites of Verongida 796 Very long-chain linear sulfated derivatives 722 3,5-Dibromotyrosine derivatives 797 Thiocyanatins: a,x-dithiocyanates Other nitrogen-containing compounds 805 of Oceanapia sp. 722 Glycerol ethers and glycosphingolipids 807 Some information on freshwater haplosclerid Sulfated aromatic compounds 807 sponges 723 Metabolites specific to the family Ianthellidae 808 XVI Contents

Selection of documentary resources 811 General account of tricyclic diterpenes 1014 References 811 Pseudopterosins, other amphilectane derivatives Some Proceedings of the International Sponge and analogues 1014 Conferences 875 Other examples of tricyclic and tetracyclic Websites 875 diterpenes 1019 Synthesis 875 Comments on the origin of terpenes 1023 Non-terpenic nitrogenous derivatives of Octocorallia 1023 20 Membrane constituents and secondary metabolites Cnidaria and Ctenophora 925 of Hexacorallia (Anthozoa) 1027 General introduction 925 Fatty acids, oxylipins and acetylenic derivatives 1027 Sterols and ecdysteroids 1029 Simplified classification of Cnidaria 925 Terpenes 1031 Hermatypic and ahermatypic corals: Carotenoids of sea anemones 1033 coral bleaching 928 Aromatic derivatives 1033 Ceramides 1033 General information on metabolites of Cnidaria 929 Examples of nitrogenous pigments: Membrane constituents and secondary metabolites zoanthoxanthins and calliactin 1034 of Octocorallia (Anthozoa) 930 Palytoxins 1034 Prostaglandins and prostanoids 930 Mycosporines 1036 Phospholipid fatty acids, glycolipids Betaines, phosphobetaines, purines and other lipidic derivatives 935 and other nitrogen-containing derivatives 1037 General remarks on the sterols of Octocorallia 939 Zoanthamine alkaloids 1039 Gorgosterol and other cyclopropane-containing Cytolysins, neuropeptides and other venoms sterols 940 of sea anemones 1042 Polyoxygenated steroids 944 Venoms and other metabolites of Medusozoa 1042 Sterones and chlorinated sterones 948 Some data on the Cubozoa and other jellyfish 1043 Sulfur-containing steroids 951 Bioluminescence of jellyfish and other Cnidaria 1044 Cyclized side-chain sterols 951 Some results on the secondary metabolites Secosterols 952 of other Hydrozoa 1045 Sterosides, pregnane and nor-pregnane derivatives 955 Sesquiterpenic hydrocarbons 958 Ctenophora 1049 Halogenated and nitrogen-containing Selection of documentary resources 1049 sesquiterpenes 959 References 1049 Sesquiterpenes with original carbon skeletons 962 Websites 1082 Examples of sesquiterpenes Synthesis 1083 with a classical carbon skeleton 968 General account of diterpenes 974 Linear and monocyclic diterpenes 975 Volume 3 General information on bicyclic diterpenes 991 Chlorinated diterpenes 995 Part 6 Other examples of briarane derivatives 996 Nitrogen-containing diterpenes of cladiellane/ Protostomes eunicellane: eleutherobin and analogues, labiatamides 999 21 Other examples of cladiellane/eunicellane Worm-like Organisms: 1 1097 diterpenes 1004 Platyhelminthes 1097 Diterpenes of serrulatane and other bicyclic carbon Macrolides and other compounds from symbiosis skeletons 1005 with Amphidinium sp. 1097 Bicyclic C5/C11 diterpenes 1005 Staurosporine derivatives and other metabolites Bicyclic diterpenes containing a cyclopropane 1006 from Platyhelminthes 1100 Some other examples of bicyclic diterpenes 1011 Contents XVII

Nemertea 1101 Toxic salivary secretions: tetrodotoxin, surugatoxin and neosurugatoxin 1151 Background on Annelida and Echiura 1102 Lipids and sexual pheromones of polychaetes 1103 Metabolites of opisthobranch gastropods 1152 Pigments of polychaetes and echiurans 1104 General characteristics of the order Anaspidea 1153 Bromophenols of polychaetes Examples of food chains between sea hares and of the phoronid Phoronopsis viridis 1105 and algae 1153 Examples of nitrogen- and sulfur-containing derivatives Aplysioviolin and carotenoid pigments 1159 from polychaetes 1105 Nitrogen-containing meroterpenes 1159 Macrolactones: aplyolides, aplysiatoxins, aurisides, Selection of documentary resources 1107 dolabelides, aplyronines and syphonoside 1160 References 1107 Peptides and depsipeptides: dolastatins Websites 1112 and aurilides 1162 Synthesis 1113 Other examples of nitrogenous derivatives of Anaspidea 1166 Antimicrobial and anti-tumour glycoproteins 22 of the genera Aplysia and Dolabella 1168 Polypropionates of Dolabella auricularia Bryozoa, Phoronida and Brachiopoda 1115 and Dolabrifera dolabrifera 1168 Bryozoans (Bryozoa, Ectoprocta) 1115 General information on the secondary metabolites Background and classification 1115 of Cephalaspidea 1169 Lipids and aromatic compounds 1116 Alkylbenzenes and 2- and 3-alkylpyridines Bryostatins 1118 of Cephalaspidea 1170 Pyrrole and pyrrolidine alkaloids 1121 Peptides and depsipeptides of Philinopsis speciosa 1171 Indole and physostigmine alkaloids 1123 Polyketides of Clione antarctica 1172 Quinoline, isoquinoline and b-carboline Secondary metabolites of Notaspidea 1173 derivatives 1124 Background on the chemistry of nudibranchs 1175 Original heterocyclic systems 1126 Terpenes, terpenoids and steroids Nitro compounds 1126 of nudibranchs 1175 Sulfoxonium salts and “Dogger Bank itch” 1126 Prostaglandin lactones of Tethys fimbria 1187 Cytotoxic macrolides of nudibranchs 1188 Phoronida and Brachiopoda 1127 Chlorinated polyacetylenic derivatives Selection of documentary resources 1127 of Diaulula sandiegensis 1189 References 1127 Relations between nudibranchs and calcareous Websites 1131 sponges: amino-2-imidazole derivatives 1190 Synthesis 1131 Relations between nudibranchs and bryozoans: pyrrole derivatives 1190 Guanidine derivatives and other alkaloids of nudibranchs 1191 23 Nucleosides and peptides of nudibranchs 1192 Molluscs 1135 Simplified assessment of nudibranch chemistry 1193 General remarks on metabolites of sacoglossans 1193 General characteristics and classification 1135 Terpenes of sacoglossans 1194 General information on lipids: hydrocarbons, Polypropionate derivatives of sacoglossans 1194 fatty acids, oxylipins and sterols 1136 Kahalalides: cytotoxic depsipeptides of the coupled Elysia/Bryopsis sp. 1196 Metabolites of prosobranch gastropods 1140 Some chemical data on Archaeogastropoda 1140 Metabolites of pulmonate gastropods 1197 Keyhole limpet haemocyanin 1143 Sesquiterpenes and diterpenes of the genera Chemical data on Mesogastropoda 1143 Onchidella and Trimusculus 1197 Secondary metabolites of Neogastropoda 1145 Polypropionate derivatives of pulmonates 1198 A brief history of Tyrian Purple 1146 Cytotoxic depsipeptides of Onchidium sp. 1199 Indirubins 1147 Conopeptides and conotoxins 1148 XVIII Contents

Metabolites of Bivalvia (Lamellibranchiata) 1200 Defence allomones in associations Degradation products of chlorophyll a between microorganisms and invertebrates 1267 of Ruditapes phillipinarum 1201 Elicitors and defence allomones of algae 1271 Carotenoids 1203 Substances inducing metamorphosis of larvae 1272 Some data on polar lipids (plasmalogens Formation of epibiosis (biofouling) and cardiolipids) 1203 and antifouling substances 1273 Polar sterols of Patinopecten yessoensis Food attractants and stimulants 1274 and 20-isosterols of Macoma balthica 1204 Selection of documentary resources 1274 Fatty acids and other lipid derivatives 1206 References 1274 Azaspiracids and other toxins 1206 Websites 1280 Polyamines, alkaloids Synthesis 1280 and various nitrogen-containing derivatives 1211 Arsenic-containing derivatives of Tridacna maxima 1213 Examples of biopolymers 1213 Part 7 Metabolites of cephalopods 1213 Deuterostomes Selection of documentary resources 1215 26 References 1215 Echinoderms 1283 Websites 1237 General remarks and classification 1283 Synthesis 1238 General comments on the chemistry of echinoderms 1284 24 Metabolites of crinoids Arthropoda 1249 (feather stars and sea lilies) 1287 Chitin and chitosans 1249 Quinonic pigments 1287 Sterols, glycolipids and phosphoceramides 1288 Carotenoid pigments 1251 3,5-Dibromotyrosine derivatives 1289 Lipid derivatives 1253 Metabolites of echinids (sea urchins) 1290 Hormones controlling crustacean moulting Echinochrome A, spinochromes and carotenoids 1290 and other steroids 1253 Fatty acids, prostaglandins, glycosphingolipids and other lipids 1292 Some examples of sulfur-, nitrogen- and arsenic- Nitrogen- and sulfur-containing metabolites 1296 containing metabolites of crustaceans 1256 Sulfated fucans and galactans 1297 Some data on marine cheliceriforms 1257 Metabolites of ophiuroids Selection of documentary resources 1258 (brittle stars and basket stars) 1297 References 1258 Lipids 1298 Websites 1261 Sulfated carotenoids 1299 Synthesis 1261 Sterols and sulfated sterols 1300 Alkaloids 1301

25 Metabolites of asteroids (sea stars and starfish) 1304 Introduction to chemical ecology 1263 Sterols and sulfated sterols 1304 Free and sulfated polyhydroxysterols 1309 Examples of intraspecific relations 1264 Nitrogen- and phosphorus-containing Sexual pheromones: sperm-activating peptides polyhydroxysterols 1313 of urchins and molluscs 1264 Steroidal glycosides and asterosaponins 1313 Examples of alarm pheromones 1265 Carotenoids 1328 Examples of interspecific relationships 1265 Fatty acids and oxylipins 1328 Predator-prey relationships: defence allomones Glycolipids, ceramides, cerebrosides of algae and invertebrates 1266 and gangliosides 1329 Nitrogen-containing derivatives 1329 Contents XIX

Metabolites of holothuroids (sea cucumbers) 1335 Sulfated polysaccharides of ascidian tunics 1386 Fatty acids 1336 Nitrogenous biopolymers and lectins 1387 Sterols, 4a-methylsterols and triterpenes 1336 Holothurins 1336 Metabolites of Didemnidae 1388 Carotenoids 1347 Didemnaketals and chlorinated diterpenes Trepang 1348 of Lissoclinum species 1388 Cerebrosides and gangliosides 1348 Aromatic polysulfanes and other atypical Atypical nitrogen-containing derivatives sulfur derivatives 1390 of Cucumaria frondosa 1351 Lamellarins and other pyrrole alkaloids 1392 Oligosaccharides and sulfated polysaccharides 1352 Derivatives of quinoline, pyridoacridine and pyrroloacridine 1394 Selection of documentary resources 1352 Derivatives of tyramine, tryptophan, indole References 1353 and b-carboline 1396 Websites 1366 Cytotoxic linear amides: bistratene A Synthesis 1367 and bistramides 1400 Linear peptides and 1,4-diketopiperazines 1401 Cyclic peptides 1402 27 Macrolides: patellazoles 1408 ® Worm-like Organisms: 2. Chaetognatha Cyclic depsipeptides: didemnins, Aplidin (plitidepsin) and Hemichordata (Enteropneusta and other derivatives 1409 and Pterobranchia) 1369 Purines, nucleosides and analogues 1413 Short description of Chaetognatha 1369 Metabolites of Polycitoridae 1414 Terpenes of Cystodytes sp. Short description of Hemichordata 1369 and Polycitor adriaticus 1414 Aromatic and heteroaromatic derivatives Aromatic polysulfanes of Polycitor adriaticus 1414 of enteropneusts 1370 Nitrogenous macrolides: iejimalides 1415 Simple pyrrole and indole alkaloids 1415 Cephalostatins of Cephalodiscus gilchristi b-Carboline alkaloids: eudistomins (Pterobranchia) 1372 and related derivatives 1416 Selection of documentary resources 1373 Decahydroquinoline alkaloids: lepadins 1418 References 1373 Quinolizidine and indolizine alkaloids 1420 Websites 1374 Perhydropyrrolo[2,1-j] and perhydropyrido[2,1-j] Synthesis 1374 quinoline alkaloids: cylindricines 1420 Pyridoacridine alkaloids and related derivatives 1421 Other types of alkaloids 1424 Cyclic peptides 1426 28 Metabolites of Polyclinidae 1426 Ascidians (Tunicates) 1377 Long-chain sulfated alkanes and terpenes Reminder about the concept of the chordate 1377 of Sidnyum turbinatum 1427 Terpenes and meroterpenes 1427 Description of tunicates and classification Para- and metacyclophanes: longithorones of the Ascidiacea 1377 and related derivatives 1427 General information on the chemistry Simple aromatic derivatives 1430 of ascidians 1379 Nitrogenous and non-nitrogenous macrolides 1430 Long-chain amines and amino alcohols, Lipids: fatty acids, acyltunichlorins, polyketides sphingosines 1432 and oxylipins 1380 Piperidine alkaloids: pseudodistomins 1433 Amino alcohols, sphinganines, serinolipids, Indole and b-carboline alkaloids 1434 ceramides and cerebrosides 1382 Quinoline and pyridoacridine alkaloids 1436 Bis-steroidal alkaloids of Ritterella tokioka: Sterols and steroids 1384 ritterazines 1436 Carotenoids 1386 Purines and nucleosides 1437 XX Contents

Miscellaneous nitrogenous derivatives 1439 29 Metabolites of Ascidiidae 1441 Vertebrates: Fish, Reptiles Vanadium, intracellular acidity of blood cells and Mammals 1489 and peptide ligands 1441 Fish 1489 Metabolites of Cionidae 1445 Squalene and other lipid derivatives of Chondrichthyes and Agnatha 1489 Metabolites of Diazonidae 1446 Bile steroids of sharks and hagfish: Metabolites of Perophoridae 1447 scymnol, myxinol and derivatives 1490 Metabolites isolated from species Squalamine and other aminosterols of sharks 1491 of the genus Perophora 1447 Migratory pheromones and sex hormones Tetrahydroisoquinoline alkaloids: ecteinascidins 1447 of lampreys 1493 Inhibition of angiogenesis by shark cartilage: Metabolites of Molgulidae and Pyuridae 1449 Neovastat® 1494 Lipids and non-nitrogenous derivatives 1449 General account of lipid derivatives of Nitrogenous derivatives, antimicrobial peptides Osteichthyes 1494 and proteins 1450 Venoms and toxins: defence substances of fish 1497 Metabolites of Styelidae 1453 Antifreeze proteins of polar fish 1501 Non-nitrogenous derivatives 1453 Sulfated glycosaminoglycans of the extracellular Phenylethylamine derivatives, various alkaloids 1453 matrix 1502 Antibacterial purines and peptides 1456 Reptiles 1502 Selection of documentary resources 1456 Mammals 1503 References 1456 Lipid composition and residues of chlorinated Websites 1477 pesticides 1503 Synthesis 1477 Ambergris, ambrein and ambrox 1504 Selection of documentary resources 1504 References 1504 Websites 1511 Synthesis 1511

Index 1515