WILEY-BLACKWELL - GBV · Archaea (Archaebacteria) 73 General introduction 73 Membrane lipids 74 Pranylquinones 79 Cyclic polysulfides 80 ... Frustules: fundamental characteristics

SUB Hamburg

Jean-Michel Kornprobst B/103659

Encyclopedia of Marine Natural Products

Volume 1: General Aspects, Microorganisms, Algae, and Fungi

Translated from French by

T. B. Tarn Ha

WILEY-BLACKWELL

Contents

Foreword XXI

Preface and Acknowledgements XXIII

List of Figures XXV

List of Tables XXXV

Abbreviations, Acronyms, and Cell Lines XXXIX

Volume 1

PartiGeneral Aspects and DocumentaryResources

lSystems of Classification of Living Organisms:Great Steps in Chemical and BiologicalEvolution 3

Whittaker's five kingdoms system 3

Discovery of Archaea(Archaebacteria):ternary model of living organisms 4

Characteristics of cell membranes 5

Some recent data on terpenes 7

Main stages of evolution 8

Exceptional resources of marine biodiversity 9

Selection of documentary resourcess 10References 10Websites 12

General Information on the MarineEnvironment 13

Physicochemical aspects 13Chemical composition of seawater 13

Optical properties of seawater 15Rapid absorption of light in relation to depth 15Selective absorption of the wavelengths 15

Biological and ecological aspects 16Primary and secondary metabolites 16Ecomones: vectors of chemical communication 16Phenomena of dependence 16

Dependence on light 16Dependence on temperature 17Dependence on salinity 17

Main types of interspecific relations 17Commensalism 17Symbiosis 17Parasitism 17

The hierarchy of ecological levels and spacedistribution of marine organisms 18Plant biodiversity: phylogeny of the algae 18Animal biodiversity 21Biochemical characteristics of sessile animals 23Estimation of biomass 23

Selection of documentary resources 24References 24Websites 25

Chemistry of Marine Natural Substances:Originality, Diversity, Distribution 27

General introduction 27

Distribution of nitrogenous and non-nitrogenoussecondary metabolites 27

Distribution of secondary metabolites by chemicalclass 28

Characteristics of the secondary metabolitesof marine organisms 29Incorporation of halogens 30Incorporation of sulfur 31Incorporation of silicon 32

Encyclopedia of Marine Natural Products. Jean-Michel KornprobstCopyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 978-3-527-327O3-4

VI11 Contents

Rare chemical elements encountered in marinesubstances: As, B, Ni, V, Zn 32

Arsenic 32Boron 32Nickel 33Vanadium 33Zinc 33


Basic Marine Pharmacology 37

The hopes of the past 37

The realities of the present 391. Ethnopharmacology 392. The triptych: biodiversity-chemodiversity-pharmacodiversity 403. Methods 44

Future directions 46


Documentary Resources 59

Short historical background 59

Printed documentation 60Chemical Abstracts, Biological Abstracts,Current Contents 60Basic works 60Reference works 61Articles published in volumes not entirelydedicated to marine organisms 61Scientific journals and the impact factor 62Scientific journals specializing in developmentsin natural marine products 62Articles about development publishedin scientific journals 65Proceedings of the major international symposia 66General articles on the synthesis of marine naturalproducts 66

Electronic documentation 67"Static" databases 68"Dynamic" databases 68Searching for information on the Internet 68

Part 2Archaea (Archebacteria) and Eubacteria

6

Archaea (Archaebacteria) 73


Membrane lipids 74

Pranylquinones 79

Cyclic polysulfides 80

Bacteriorhodopsin of halophiles 81

Extremozymes 82

Appendix i: Stereospecific numbering (sri) 83

Selection of documentary resources 83References 83Experimental documentation 85Websites 85Synthesis 86

Eubacteria - 1 87

Cell walls and Gram reaction 87Anaerobic and aerobic photosynthesis:bacteriochlorophylls 88

Brief overview of marine bacteria 90

Piezophile (barophile) and psychrophile bacteriafrom extreme environments 91

Examples of metabolites isolatedfrom non-photosynthetic bacteria 91

Lipopolysaccharides and other characteristicsof some Gram-negative bacteria 106

Anaerobic photosynthetic bacteria 107

Aerobic photosynthetic bacteria 107

Anammox bacteria and "ladderane lipids" 108

Appendix 2 110

Selection of documentary resources 111References 111Websites 116Synthesis 116

Contents IX

8

Eubacteria - 2 121

Prochlorophyta 121

Taxonomy of Prochlorophyta 121

Unique characteristics of photosynthesisin Prochlorococcus 122

Biochemical data on Prochloron didemni 123

Biochemical data on Prochlorothrix hollandica 123

Cyanobacteria 124

Traditional classification of cyanobacteria 124

Photosynthetic pigments 125

Membrane lipids 128

General characteristics of the secondarymetabolites 129

Malyngamides and other chlorinated derivatives 130

Semiplenamides A-G and besarhanamides A-B 133

Aplysiatoxin, oscillatoxin-A

and other brominated derivatives 134

Other non-peptidic nitrogenous derivatives 135

Lipopeptides, peptides and depsipeptides 137

Other toxins 147

Sulfated compounds 148Polymethoxyalkenes and poly-/?-hydroxybutyricacids (PHBAs) 150

Other molecules 151

Appendix 3 153

Appendix 4 154


Part 3Photosynthetic Eukaryotes

Bacillariophyceae (Diatoms) 173

Frustules: fundamental characteristics of diatoms 173

Bases of classification of diatoms 174

Primary metabolites 174


Membrane lipids 175

Terpenic hydrocarbons 177

Other terpenic derivatives: descriptionof the two biosynthetic pathways 179

Genera Nitzschia and Pseudo-nitzschia: domoicacid 180

Other molecules 181

Appendix 5 183

Appendix 6 184


10Chrysophyceae, Raphidophyceae,Haptophyceae 191

Chrysophyceae 191General presentation: simplified classification 191Photosynthetic pigmentsand storage polysaccharides 191Fatty acids 191Sterols 191Other derivatives 192

Raphidophyceae 193

Haptophyceae 193General presentation: simplified classification 193Photosynthetic pigments 194Sterols 194Fatty acids and other linear derivatives 195Prymnesins 196Particular characteristics of Pavlova pinguisand Pkurochrysis carterae 197

Contents

Appendix 7 198


11

Dinophyceae (Dinoflagellates) 201

General aspects 201

Classification of dinoflagellates 202


Sulfated exopolysaccharides 203

Sterols 204

Fatty acids 204

Glycolipids 207

Amphidinols and other polyhydroxylated polyenicderivatives 207

Toxic proliferations: endo- and exotoxins 211

Main types of dihoflagellate toxins 212

Cyclic polyethers 212

Okadaic acid and derivatives 220

Toxic macrolides: amphidinolides, caribenolide, gonio-domin A, hoffmanniolide 222

Complexity of the biosynthesis of polyketides 225

Saxitoxin and its derivatives 225

Nitrogenous toxins with imine function 228

Zooxanthellatoxins (ZTs) and other nitrogenoustoxins 229

Pfiesteria piscicida: a particularly toxicdinoflagellate 232

Sulfur-containing derivatives 232

Phosphorus derivatives 233


12Chlorophyceae (Green Algae)and Marine Spermatophyta 251

General aspects 251

Elements of classification of marine macroalgae 251

Classification of Chlorophyceae 252

Chlorophylls, carotenes and xanthophylls 252

Storage polysaccharides: starches 254

Cell-wall polysaccharides 255

Matrix polysaccharides 255

Membrane lipids: fatty acids and sterols 255

Oxylipins 258

Background on the secondary metabolitesof Chlorophyceae 259

Terpenes 259

Meroterpenes of Dasycladales 262

Aromatic derivatives 263

Amino acids, amines, betaines 264

Peptides and depsipeptides: kahalalides 264

Other nitrogen-containing derivatives 265


Marine Spermatophyta (phanerogams) 267


13

Rhodophyceae (Red Algae) 275

Special features of red algae 275

Classification of Rhodophyceae 275


Storage monosaccharides and polysaccharides 278

Skeleton polysaccharides 278

Matrix polysaccharides: carrageenans and agars 278

Carrageenophytes and agarophytes 281

Gelling agents and thickeners 281

Contents X I

Other types of matrix polysaccharides 282

Phospholipids and fatty acids 282

Oxylipins and prostaglandins 284

Sterols and ecdysteroids 285

General comments on the secondary metabolites 286

Secondary metabolites of Cryptonemiales 287

Secondary metabolites of Gelidiales 290

Secondary metabolites of Rhodymeniales 290

Polyhalogenated monoterpenes of Gigartinales 291

Diterpenes of Sphaerococcus coronopifolius(Gigartinales, Sphaerococcaceae) 293

Macrocydic pyrones of Phacelocarpus labillardieri(Gigartinales, Sphaerococcaceae) 297

Polycavernosides of Polycavernosa tsudai(Gigartinales, Gracilariaceae) 297

Brominated meroditerpenes of Calhphycus serratus(Gigartinales, Solieriaceae) 298

Halogenated phloroglucinols of Rhabdonia verticillata(Gigartinales, Solieriaceae) 299

Sulfated aromatic derivatives of Tichocarpus crinitus(Gigartinales, Tichocarpaceae) 299

Nitrogen-containing derivatives of Gigartinales 299

Halogenated compounds of Ceramiales:general comments 300

Polyhalogenated monoterpenes of Pantoneuraplocamioides (Ceramiales, Delesseriaceae) 301

Sesquiterpenes of Laurenda(Ceramiales, Rhodomelaceae) 301

Halogenated diterpenes of Laurenda 310

Non-halogenated hydroperoxyditerpenesof Laurenda 319

Squalenoids of Laurenda speciesand Chondria armata 319

Cyclic halogenated C,5 ethers and polyethersof Laurenda and Chondria 322

Bromo- and polybromophenols of Ceramiales 325

Nitrogen-containing bromophenolsof Rhodomela confervoides 328

Other nitrogen-containing derivativesof Ceramiales 329

Cyclic polysulfides of Chondria californica 332

Arsenic-containing derivativeof Chondria crassicaulis 332

Some atypical derivatives of Laurenda spedes 333

Halogenated derivatives of Nemaliales 333

Acetylenic acids of Liagora farinosa 335

Sulfated triterpene alcohols of Trideocarpa fragilis 336

Cyclic peptide from Galaxaura filamentosa 337

Appendix 8 337

Appendix 9 338


14

Phaeophyceae (Brown Algae) 361

General introduction; 361

Classification of Phaeophyceae 361


Laminarans and other storage osides 363

Matrix polysaccharides: alginic acids and alginates 364

Fucoidans (sulfated fucans) 365

Lipids and fatty acids 367

Oxylipins of Laminariales 367

Epoxy lipids of Notheia anomala (Chordariales) 370

Sterols 371

Volatile hydrocarbons and sexual chemotaxy 372

Background on the secondary metabolites 376

Sesquiterpenes of Dictyotales 376

Cyclic diterpenes of Dictyotales 377

Linear diterpenes of Fucales and other derivatives 382

Phenols and phlorotannins 385

Other aromatic derivatives 388

Meroterpenes: general comments 389

Prenylated quinones and hydroquinones 389

Meromonoterpenes of Sporodinus bolleanus 390

X I I Contents

Merosesquiterpenes of Dictyopteris species 391

Meroditerpenes of the genera Taoniaand Stypopodium 392

Meroditerpenes of Cystoseira species: chemotaxonomyof Cystoseiraceae 396

Nahocols and isonahocols: rearranged linearmeroditerpenes of Sargassum autumnale 401

Derivatives of nitrogen, phosphorus and arsenic 402


Iodinated derivatives 405

Appendix io 406

Appendix n 407


15

Major Uses of Macroalgae 423

Overview 423

Estimate of resources 423

Edible seaweeds 425

Dietary properties of marine algae 425

Physicochemical aspects of phycocolloids 426

Economic aspects of phycocolloids 428

Major producing countries of phycocolloids 428

Main applications of agars 428

Main applications of carrageenans and furcellar-ans 430

Main applications of alginic acid and alginates 430

Summary of research in the field of healthcare 431

Antiviral and immunostimulant sulfatedpolysaccharides of red, brown and green algae 431

Anticoagulant and antithrombotic propertiesof fucoidans 432

Antitumoural, immunomodulatory and antiviralproperties of fucoidans 433

Other examples of biological activitiesof macroalgae 434

Uses of algae in cosmetics 434

Uses of algae in agriculture and livestockproduction 435

Selection of documentary resources 435References 435Proceedings of the latest International SeaweedSymposia 440Websites 440

Part 4Fungi and Other Eukaryotic UnicellularNon-photosynthetic Organisms

16Fungi 445

The Fungal Kingdom: the conceptof marine fungi 445

Mastigomycetes and Eumycetes (true fungi) 446

Elements of classification of Eumycetes 446

Background information on the structureof chitin 446

Fatty acids 446

Sterols 446

Membrane peptides of fungi: peptaibols 448

General comments on secondary metabolitesof marine fungi 449

Substances isolated from fungi collectedfrom the surface of the sea 449

Substances isolated from fungi from sedimentsand other inert substrates 450

Substances isolated from fungi associatedwith cyanobacteria 454

Algicolous fungi: general remarks 454

Substances isolated from fungi associatedwith green algae and marine Spermatophyta 454

Substances isolated from fungi associatedwith red algae 458

Substances isolated from fungi associatedwith brown algae 459

Substances isolated from lignicolous fungi 461

Substances isolated from fungi associatedwith sponges 465

Contents X I I I

Substances isolated from fungi associatedwith cnidarians 473

Substances isolated from fungi associatedwith molluscs 474

Substances isolated from fungi associatedwith bryozoans 476

Substances isolated from fungi associatedwith echinoderms 476

Substances isolated from fungi associatedwith crustaceans 478

Substances isolated from fungi associatedwith tunicates (ascidians) 478

Substances isolated from fungi associatedwith fish 480


17Thraustochytrids and Ciliates 493

Taxonomic position of thraustochytridsand overview of the group 493

Carotenoids of thraustochytrids 493

Long-chain (n-3) polyunsaturated fatty acidsof thraustochytrids 493

Long-chain fatty acid composition and phylogenyof thraustochytrids 495

o-Glucosylceramides of thraustochytrids 495

Introduction to the chemistry of ciliates 496

Terpenes of Euplotes 497

Keronopsins of Pseudokeronopsis rubra 498


18Introduction to Marine Biotechnology 503

Introduction 503

Recent developments in the cultureof invertebrates 503

Lipids and pigments: examplesof nutritional applications 504

New substances and biomaterials: examplesof biomedical applications 506

Bioremediation and biofouling: examplesof environmental applications 507

Dialkylphthalates in marine organisms 508

Another type of application: bioadhesives 508

Some examples of biotechnology in Prokaryotes 509

Selection of documentary resources 510General references 510References 510Websites 516

Volume 2

Part5Porifera, Cnidaria, and Ctenophora

19

Porifera (Sponges) 521

Overview of the universe of sponges 521

Metabolites of Calcarea (calcareous sponges) 524General characteristics of Calcarea 524Fatty acids 524Sterols 524Non-nitrogenous derivatives of speciesof the genus Leucetta 525Imidazole alkaloids and zinc complexes isolated fromthe genera Leucetta, Leucosolenia and Clathrina 526a,co-Bis long-chain aminoalcohols 528Nitrogen-containing macrolides and cyclicpeptides 529Other nitrogen-containing compounds of Calcarea 529

Metabolites of Hexactinellida 530

Classification and membrane constituentsof Demospongiae 531Classification 531

X I V Contents

Some physical observations on demosponges 532Shape and size 532Consistency 532Colour and odour 532

Diversity of membrane constituents:some examples 536Phospholipids and demospongic acids 538Fatty acids with 5,9 dienic structure 541Other mono- and polyunsaturated fatty acids 543Branched fatty acids 544Isoprenic acids 547Cyclopropanic acids 548Brominated acids 5502-O substituted acids 551Sulfur derivatives of demospongic acids 553Intracellular localization and biological activityof demospongic acids 555Brief reminder about conventional sterols 555Unconventional sterols produced by changesin the tetracyclic system 556Unconventional sterols produced by polymethylationof the side chain 561Sterols with degraded side chains 564Sterols and stanols with cyclopropanicand cyclopropenic side chains 564Secosterols 566Polyhydroxylated steroids and derivatives,peroxysterols 569Sulfated sterols 571Chlorinated sterols and sterones 574Nitrogen-containing sterols 576Glycolipids 577

Secondary metabolites of Homoscleromorpha 582Fatty acids, polyketides and oxylipinsof Plakinastrella and Plakortis 582Cyclic peroxides and peroxylactonesof Plakinastrella and Plakortis 584Glycosides 587Polyhydroxylated sterols of Oscarella lobularis 587Alkaloids and other original nitrogen derivativesof Plakortis and Cortidum 587

Secondary metabolites of Astrophorida 590Acetylenic fatty acids of Stelletta 591Glycolipids: caminosides and pachymosides 591Triterpenes of malabaricane and isomalabaricane:sesterterpenes 591Triterpenic glycosides and steroidal glycosides 593Substituted tetramic acids and derived glycosides 596Erylusamines, erylusine and erylusidine 598Cyclic depsipeptides, peptolidesand macrolactones 598Nitrogen-containing terpenes 602

Bengazoles and bengamides 603Atypical nitrogenous derivatives 605Phosphorus-containing derivatives similarto calyculin A 607Aromatic sulfated derivatives 608Isotactic polymethoxydienes of Myriastra davosa 608

Secondary metabolites of Hadromeridaand Chondrosida 609Perforating power of Clionaidae 609lyso-Phospholipids and sulfated sphingosinesof Spirastrella abata 610Brominated acetylenic derivatives of Diplastrella 611Cyclic peroxides 612Terpenes 613Unconventional sterols 614Macrolactones: latrunculins and spongistatins 615Atypical glycosides of Latrunculia corticata 617Other nitrogen-free toxins 617Peptides and depsipeptides 618Pyrrole derivatives and other nitrogen-containingheterocycles 619Atypical nucleosides 621

Secondary metabolites of Lithistida 622Particular characteristics of lithistid sponges 622Nitrogen-containing sesquiterpenes of Theonella 623Specific glycolipids of Theonella swinhoei,Discodermia calyx and D. dissoluta 623Long-chain polyacetylenic derivatives of Theonellasp. 6243/9-Methoxysterols of Jereicopsis graphidiophora 6244-Methylenesterols and sterones of Theonella 624Macrolides 626Examples of acetogenins: discodermolide,calyculins and onnamides 629Linear peptides 630Mono- and bicyclic peptides 632Symbiotic origin of some polypeptides 635Cyclic and linear depsipeptides 635Atypical nitrogenous derivatives 639

Secondary metabolites of Spirophorida 640Atypical sterols of Cinachyra, Microscleroderma,and Scleritoderma 640Cinachyrolide A 640Microsclerodermins and aciculitins 641Examples of atypical derivatives of some spongesof the Tetillidae 641

Secondary metabolites of Agelasida 642Sterols 642Diterpenes and carotenoids 642Merosesquiterpenes and nitrogen-containingmeroditerpenes 643

Contents XV

Galactosylceramides and glycolipids 644Oroidin and related CnN5 bromopyrrole alkaloids 646

Agelastatin A series 649Other series 650

Pyrrole-2-carboxylic acid derivatives 650Other examples of nitrogen-containingheterocycles 650Betaines 651

Secondary metabolites of Halichondrida 652A-nor-steroids and other non-conventional sterols 652Conventional terpenes 654Nitrogen-containing terpenes: isonitrilesand related derivatives 659Other terpenes 666Long-chain linear polyaminesand a,co-bis-isothiocyanates 668Polyethers: halichondrins, okadaicand glycookadaic acids 668Various lipids 670Linear peptides of the genera Aulettaand Cymbastela 672Depsipeptides and cyclic peptides 672Pyrrole, imidazole, pyridine, isoquinolineand indole derivatives 678

Pyrrole derivatives 678Imidazole derivatives 678Pyridine and isoquinoline derivatives 679Indole derivatives 679

Heterocycles related to the oroidin family 681Atypical halogenated and sulfur-containingderivatives 682

Secondary metabolites of Haplosclerida 683Acetylenic derivatives 685Atypical fatty acids 691Terpenes and meroterpenes 693Triterpenic glycosides 699Hopanoids, steroids and sterosides 701Macrolides, depsipeptides and cyclic peptides 704Amino alcohols and glycosphingolipids(cerebrosides) 705Manzamines and related derivatives 707Quinolizidine and 1-oxaquinolizidine derivatives 707Pyridine derivatives and 3-alkylpyridinium salts 714Pyridoacridine alkaloids 716Pyrroloquinones and other examplesof nitrogen-containing heterocycles 717Quinones and sulfated hydroquinones 721Very long-chain linear sulfated derivatives 722Thiocyanatins: a,«-dithiocyanatesof Oceanapia sp. 722Some information on freshwater haplosderidsponges 723

Secondary metabolites of Poecilosderida 724Sterols, steroids and sterosides 725Terpenes and triterpenic glycosides 727Polybrominated acetogenins and oxylipins 732Long-chain acetynenic derivatives: raspailynes 732Glycolipids 733Brominated aromatic derivativesof Hamigera tarangaensis 733Macrolides 734Chondropsins: cyclic depsipeptidesof Chondropsis sp. 736Eurypamides (Microdona eurypa), microcionamides(Clathria abietina) and other cyclic peptides 737Linear amides 738Examples of some atypical sulfur-containingderivatives 739Pyrrole and indole derivatives 741Pyridines, quinolizines and pyridoacridines 742Guanidine derivatives 743Pyrroloiminoquinones and pyrroloquinones 747Azasugars 748Other examples of polycyclic alkaloids 748Phosphorus and arsenic-containing derivatives,betaines 750

General information on the metabolitesof sponges lacking mineral spicules 751

Secondary metabolites of Dendroceratida 753Terpenes and meroterpenes 754Sterols 760Polybromophenols and polybromodiphenyl ethersof Dysidea 761Nitrogen compounds 763

Secondary metabolites of Dictyoceratida 768Terpenes and meroterpenes 768Sterols 788Glycolipids 789Polybromodiphenyl ethers and other halogenatedaromatic derivatives 789Macrolides: laulimalide, altohyrtins, chondropsinsand haterumalides 790Linear and cyclic peptides, depsipeptides 791Alkaloids and other nitrogen-containingcompounds 793Phosphorus derivatives 795Atypical sulfur derivatives 796

Secondary metabolites of Verongida 7963,5-Dibromotyrosine derivatives 797Other nitrogen-containing compounds 805Glycerol ethers and glycosphingolipids 807Sulfated aromatic compounds 807Metabolites specific to the family Ianthellidae 808

X V I Contents

Selection of documentary resources 811References 811Some Proceedings of the International SpongeConferences 875Websites 875Synthesis 875

20

Cnidaria and Ctenophora 925


Simplified classification of Cnidaria 925

Hermatypic and ahermatypic corals:coral bleaching 928

General information on metabolites of Cnidaria 929

Membrane constituents and secondary metabolitesof Octocorallia (Anthozoa) 930Prostaglandins and prostanoids 930Phospholipid fatty acids, glycolipidsand other lipidic derivatives 935General remarks on the sterols of Octocorallia 939Gorgosterol and other cyclopropane-containingsterols 940Polyoxygenated steroids 944Sterones and chlorinated sterones 948Sulfur-containing steroids 951Cyclized side-chain sterols 951Secosterols 952Sterosides, pregnane and nor-pregnane derivatives 955Sesquiterpenic hydrocarbons 958Halogenated and nitrogen-containingsesquiterpenes 959Sesquiterpenes with original carbon skeletons 962Examples of sesquiterpeneswith a classical carbon skeleton 968General account of diterpenes 974Linear and monocyclic diterpenes 975General information on bicyclic diterpenes 991Chlorinated diterpenes 995Other examples of briarane derivatives 996Nitrogen-containing diterpenes of dadiellane/eunicellane: eleutherobin and analogues,labiatamides 999Other examples of cladiellane/eunicellanediterpenes 1004Diterpenes of serrulatane and other bicyclic carbonskeletons 1005Bicyclic C s /Cn diterpenes 1005Bicyclic diterpenes containing a cyclopropane 1006Some other examples of bicyclic diterpenes 1011

General account of tricydic diterpenes 1014Pseudopterosins, other amphilectane derivativesand analogues 1014Other examples of tricyclic and tetracydicditerpenes 1019Comments on the origin of terpenes 1023Non-terpenic nitrogenous derivativesof Octocorallia 1023

Membrane constituents and secondary metabolitesof Hexacorallia (Anthozoa) 1027Fatty acids, oxylipins and acetylenic derivatives 1027Sterols and ecdysteroids 1029Terpenes 1031Carotenoids of sea anemones 1033Aromatic derivatives 1033Ceramides 1033Examples of nitrogenous pigments:zoanthoxanthins and calliactin 1034Palytoxins 1034Mycosporines 1036Betaines, phosphobetaines, purinesand other nitrogen-containing derivatives 1037Zoanthamine alkaloids 1039Cytolysins, neuropeptides and other venomsof sea anemones 1042

Venoms and other metabolites of Medusozoa 1042Some data on the Cubozoa and other jellyfish 1043Bioluminescence of jellyfish and other Cnidaria 1044Some results on the secondary metabolitesof other Hydrozoa 1045

Ctenophora 1049


Volume 3

Part 6Protostomes

21Worm-like Organisms: 1 1097

Platyhelminthes 1097Macrolides and other compounds from symbiosiswith Amphidinium sp. 1097Staurosporine derivatives and other metabolitesfrom Platyhelminthes 1100

Contents X V I I

Nemertea 1101

Background on Annelida and Echiura 1102Lipids and sexual pheromones of polychaetes 1103Pigments of polychaetes and echiurans 1104Bromophenols of polychaetesand of the phoronid Phoronopsis viridis 1105Examples of nitrogen- and sulfur-containing derivativesfrom polychaetes 1105


22Bryozoa, Phoronida and Brachiopoda 1115

Bryozoans (Bryozoa, Ectoprocta) 1115Background and classification 1115Lipids and aromatic compounds 1116Bryostatins 1118Pyrrole and pyrrolidine alkaloids 1121Indole and physostigmine alkaloids 1123Quinoline, isoquinoline and /?-carbolinederivatives 1124Original heterocydic systems 1126Nitro compounds 1126Sulfoxonium salts and "Dogger Bank itch" 1126

Phoronida and Brachiopoda 1127


23Molluscs 1135

General characteristics and classification 1135

General information on lipids: hydrocarbons,fatty acids, oxylipins and sterols 1136

Metabolites of prosobranch gastropods 1140Some chemical data on Archaeogastropoda 1140Keyhole limpet haemocyanin 1143Chemical data on Mesogastropoda 1143Secondary metabolites of Neogastropoda 1145A brief history of Tyrian Purple 1146Indirubins 1147Conopeptides and conotoxins 1148

Toxic salivary secretions: tetrodotoxin, surugatoxinand neosurugatoxin 1151

Metabolites of opisthobranch gastropods 1152General characteristics of the order Anaspidea 1153Examples of food chains between sea haresand algae 1153Aplysioviolin and carotenoid pigments 1159Nitrogen-containing meroterpenes 1159Macrolactones: aplyolides, aplysiatoxins, aurisides,dolabelides, aplyronines and syphonoside 1160Peptides and depsipeptides: dolastatinsand aurilides 1162Other examples of nitrogenous derivativesof Anaspidea 1166Antimicrobial and anti-tumour glycoproteinsof the genera Aplysia and Dolabella 1168Polypropionates of Dolabella auriculariaand Dolabrifera dolabrifera 1168General information on the secondary metabolitesof Cephalaspidea 1169Alkylbenzenes and 2- and 3-alkylpyridinesof Cephalaspidea 1170Peptides and depsipeptides of Philinopsis speciosa 1171Polyketides of Clione antarctica 1172Secondary metabolites of Notaspidea 1173Background on the chemistry of nudibranchs 1175Terpenes, terpenoids and steroidsof nudibranchs 1175Prostaglandin lactones of Tethys fimbria 1187Cytotoxic macrolides of nudibranchs 1188Chlorinated polyacetylenic derivativesof Diaulula sandiegensis 1189Relations between nudibranchs and calcareoussponges: amino-2-imidazole derivatives 1190Relations between nudibranchsand bryozoans: pyrrole derivatives 1190Guanidine derivatives and other alkaloidsof nudibranchs 1191Nucleosides and peptides of nudibranchs 1192Simplified assessment of nudibranch chemistry 1193General remarks on metabolites of sacoglossans 1193Terpenes of sacoglossans 1194Polypropionate derivatives of sacoglossans 1194Kahalalides: cytotoxic depsipeptidesof the coupled Elysia/Bryopsis sp. 1196

Metabolites of pulmonate gastropods 1197Sesquiterpenes and diterpenes of the generaOnchidella and Trimusculus 1197Polypropionate derivatives of pulmonates 1198Cytotoxic depsipeptides of Onchidium sp. 1199

XVI11 Contents

Metabolites of Bivalvia (Lamellibranchiata) 1200Degradation products of chlorophyll aof Ruditapes phillipiharum 1201Carotenoids 1203Some data on polar lipids (plasmalogensand cardiolipids) 1203Polar sterols of Patinopecten yessoensisand 20-isosterols of Macoma balthica 1204Fatty acids and other lipid derivatives 1206Azaspiracids and other toxins 1206Polyamines, alkaloidsand various nitrogen-containing derivatives 1211Arsenic-containing derivativesof Tridacna maxima 1213Examples of biopolymers 1213

Metabolites of cephalopods 1213


24

Arthropoda 1249

Chitin and chitosans 1249

Carotenoid pigments 1251

Lipid derivatives 1253

Hormones controlling crustacean moultingand other steroids 1253

Some examples of sulfur-, nitrogen- and arsenic-containing metabolites of crustaceans 1256

Some data on marine cheliceriforms 1257


25Introduction to chemical ecology 1263

Examples of intraspecific relations 1264Sexual pheromones: sperm-activating peptidesof urchins and molluscs 1264Examples of alarm pheromones 1265

Examples of interspecific relationships 1265Predator-prey relationships: defence allomonesof algae and invertebrates 1266

Defence allomones in associationsbetween microorganisms and invertebrates 1267Elicitors and defence allomones of algae 1271Substances inducing metamorphosis of larvae 1272Formation of epibiosis (biofouling)and antifouling substances 1273Food attractants and stimulants 1274


Part 7Deuterostomes

26Echinoderms 1283

General remarks and classification 1283

General comments on the chemistryof echinoderms 1284

Metabolites of crinoids(feather stars and sea lilies) 1287Quinonic pigments 1287Sterols, glycolipids and phosphoceramides 12883,5-Dibromotyrosine derivatives 1289

Metabolites of echinids (sea urchins) 1290Echinochrome A, spinochromes and carotenoids 1290Fatty acids, prostaglandins, glycosphingolipidsand other lipids 1292Nitrogen- and sulfur-containing metabolites 1296Sulfated fucans and galactans 1297

Metabolites of ophiuroids(brittle stars and basket stars) 1297Lipids 1298Sulfated carotenoids 1299Sterols and sulfated sterols 1300Alkaloids 1301

Metabolites of asteroids (sea stars and starfish)Sterols and sulfated sterols 1304Free and sulfated polyhydroxysterols 1309Nitrogen- and phosphorus-containingpolyhydroxysterols 1313Steroidal glycosides and asterosaponins 1313Carotenoids 1328Fatty acids and oxylipins 1328Glycolipids, ceramides, cerebrosidesand gangliosides 1329Nitrogen-containing derivatives 1329

1304

Contents X I X

Metabolites of holothuroids (sea cucumbers) 1335Fatty acids 1336Sterols, 4<z-methylsterols and triterpenes 1336Holothurins 1336Carotenoids 1347Trepang 1348Cerebrosides and gangliosides 1348Atypical nitrogen-containing derivativesof Cucumaria frondosa 1351Oligosaccharides and sulfated polysaccharides 1352


27Worm-like Organisms: 2. Chaetognathaand Hemichordata (Enteropneustaand Pterobranchia) 1369

Short description of Chaetognatha 1369

Short description of Hemichordata 1369

Aromatic and heteroaromatic derivativesof enteropneusts 1370

Cephalostatins of Cephahdiscus gikhristi(Pterobranchia) 1372


28Ascidians (Tunicates) 1377

Reminder about the concept of the chordate 1377

Description of tunicates and classificationof the Ascidiacea 1377

General information on the chemistryof ascidians 1379

Lipids: fatty acids, acyltunichlorins, polyketidesand oxylipins 1380

Amino alcohols, sphinganines, serinolipids,ceramides and cerebrosides 1382

Sterols and steroids 1384

Carotenoids 1386

Sulfated polysaccharides of ascidian tunics 1386

Nitrogenous biopolymers and lectins 1387

Metabolites of Didemnidae 1388Didemnaketals and chlorinated diterpenesof Lissoclinum species 1388Aromatic polysulfanes and other atypicalsulfur derivatives 1390Lamellarins and other pyrrole alkaloids 1392Derivatives of quinoline, pyridoacridineand pyrroloacridine 1394Derivatives of tyramine, tryptophan, indoleand yS-carboline 1396Cytotoxic linear amides: bistratene Aand bistramides 1400Linear peptides and 1,4-diketopiperazines 1401Cyclic peptides 1402Macrolides: patellazoles 1408Cyclic depsipeptides: didemnins, Aplidin® (plitidepsin)and other derivatives 1409Purines, nucleosides and analogues 1413

Metabolites of Polycitoridae 1414Terpenes of Cystodytes sp.and Polycitor adriaticus 1414Aromatic polysulfanes of Polydtor adriaticus 1414Nitrogenous macrolides: iejimalides 1415Simple pyrrole and indole alkaloids 1415/?-Carboline alkaloids: eudistominsand related derivatives 1416Decahydroquinoline alkaloids: lepadins 1418Quinolizidine and indolizine alkaloids 1420Perhydropyrrolo[2,l-j] and perhydropyrido[2,l-j]quinoline alkaloids: cylindricines 1420Pyridoacridine alkaloids and related derivatives 1421Other types of alkaloids 1424Cyclic peptides 1426

Metabolites of Polydinidae 1426Long-chain sulfated alkanes and terpenesof Sidnyum turbinatutn 1427Terpenes and meroterpenes 1427Para- and metacyclophanes: longithoronesand related derivatives 1427Simple aromatic derivatives 1430Nitrogenous and non-nitrogenous macrolides 1430Long-chain amines and amino alcohols,sphingosines 1432Piperidine alkaloids: pseudodistomins 1433Indole and yS-carboline alkaloids 1434Quinoline and pyridoacridine alkaloids 1436Bis-steroidal alkaloids of Ritterella tokioka:ritterazines 1436Purines and nucleosides 1437

XX Contents

Miscellaneous nitrogenous derivatives 1439

Metabolites of Ascidiidae 1441Vanadium, intracellular acidity of blood cellsand peptide ligands 1441

Metabolites of Cionidae 1445

Metabolites of Diazonidae 1446

Metabolites of Perophoridae 1447Metabolites isolated from speciesof the genus Perophora 1447Tetrahydroisoquinoline alkaloids: ecteinascidins

Metabolites of Molgulidae and Pyuridae 1449Lipids and non-nitrogenous derivatives 1449Nitrogenous derivatives, antimicrobial peptidesand proteins 1450

Metabolites of Styelidae 1453Non-nitrogenous derivatives 1453Phenylethylamine derivatives, various alkaloidsAntibacterial purines and peptides 1456


1447

1453

29Vertebrates: Fish, Reptilesand Mammals 1489

Fish 1489Squalene and other lipid derivativesof Chondrichthyes and Agnatha 1489Bile steroids of sharks and hagfish:scymnol, myxinol and derivatives 1490Squalamine and other aminosterols of sharksMigratory pheromones and sex hormonesof lampreys 1493Inhibition of angiogenesis by shark cartilage:Neovastat® 1494General account of lipid derivatives ofOsteichthyes 1494Venoms and toxins: defence substances offishAntifreeze proteins of polar fish 1501Sulfated glycosaminoglycans of the extracellularmatrix 1502

Reptiles 1502

Mammals 1503Lipid composition and residues of chlorinatedpesticides 1503Ambergris, ambrein and ambrox 1504

1491

1497

Selection of documentary resourcesReferences 1504Websites 1511Synthesis 1511

1504

Index 1515

Documents

WILEY-BLACKWELL - GBV · Archaea (Archaebacteria) 73 General introduction 73 Membrane lipids 74 Pranylquinones 79 Cyclic polysulfides 80 ... Frustules: fundamental characteristics