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Home , Aglaophenia pluma, Aplysina, Asterozoa, Bryozoa, Cephalodiscus gilchristi, Crinozoa

APPENDICES

A. Biological fundamentals

EUKARYOTIC VS. PROKARYOTIC CELLS

Though is small, the cells of the smallest and flagellates can be easily seen under an ordinary microscope. However, in to observe planktonic free-living , which barely attain a diameter of one thousandth of a millimeter, special optical methods are needed. In all cases, to appreciate the fine details of the cells, one needs an electron microscope, which has a much higher resolving power than an optical microscope. The cells can be divided into two groups: the prokaryotic and the eukaryotic cells. Bacteria and are prokaryotes, whereas alI other organisms, with the exception of the archaebacteria to which we have alluded in chapter 4, are . In all cases biochemical studies have shown that cells are 90% water and that different functions are performed in the different organelles of the cell. In the following an idealized eukaryotic cell will serve to illustrate the main cellular features. The eukaryotic cell

174 mOLOOliCAlL lF1lJNDAMlENT AJL,§

cytoplasm is enclosed in a double-Iayered membrane, which is so thin that it appears as a single line in our drawing. In the central portion of the cell there is the nucleus surrounded by a membrane. The nucleoplasm contains a nucleolus and more than one linear chromosome, which is an association of DNA with a . The cytoplasm also contains various organelles, which are membrane-enclosed spaces, such as the lysosomes, where hydrolysis of occurs yielding monomeric sugars. These are taken up by the mitochondria, as centers of energy metabolism, and are oxidized to carbon dioxide. Another organelle is the endoplasmic reticulum, which contains the ribosomes where the are synthesized. The proteins are then packed and distributed by the Golgi apparatus. The cytoplasm of photosynthetic cells also contains plastids or chloroplasts where occurs. cells also have cavities, called vacuoles, for food storage. Finally, many unicellular organisms possess centrioles, small cavities near the nucleus which act as contractile or locomotory elements in the muscle function of higher . As with primary metabolites, though probably with less specificity, the synthesis of secondary metabolites of different classes occurs in different compartments of the cello For instance, certain hormonal regulators of plant growth, the gibbereJlins and abscisic acid, which are terpenes, are mainly produced in the plastids. Why has evolution led to this choice? The reason is probably that the plastids are particularly rieh in the reactants required for the biosynthesis of these hormones. Specialized ceUs are capable of accumulating secondary metabolites, such as brominated acetogenins in the red seaweed Bonnemaisonia nootkana and, as already noted in chapter 6, amino acid metabolites in the . All the ceJlular charaeteristics of eukaryotes are absent in prokaryotes, and the genetic organization is different. In prokaryotic ceJls the major part of the DNA forms a single circular chromosome, not restricted within a nuclear membrane, and genetic information is also eontained in extrachromosomal DNA. Some metabolie functions are also performed in a different way.

175 AlPlP']ENlJ)liClES

While there is general consensus that plastids and mitochondria of eukaryotic cells originate from prokaryotic cells along an endosymbiont line, the opinions differ in regard to the : some scientists advocate an endosymbiontic origin of the nucleus as the first step in the evolution of eukaryotes, whereas other scientists have proposed that the nucleus derives from cell compartmentation.

CELL TYPE AND EVOLUTIONARY MARKS

An important point is that while the eukaryotic cell seeks to maintain its characteristics, the prokaryotic cell lacks such a strict restraint; the prokaryotic cell is able to exchange genetic material, though this occurs less frequently than is generally thought. Genetic engineers have emphasized this property of eukaryotic cells to justify their efforts in mixing the characteristics of all organisms, including eukaryotes, which were devised not to do so; or at least not at the speed of genetic manipulation. In any event, an overall improvement on Nature through genetic manipulation is yet to be seen. This preamble serves to emphasize the fact that patterns of sequences of amino acids in proteins are related to the evolutionary his tory of species. As this is similar for evolutionarily-related species, such patterns can be used as evolutionary marks. An example in chapter 14 concerns the green turtles of Ascension Island. If, however, exchange of genetic material has occurred recently in prokaryotic cells, where it is allowed to happen, such patterns are altered and may not be used as evolutionary marks. Therefore, the prokaryotic cell, though more amenable to investigation than the eukaryotic cell, may be unsuited to unravel the evolutionary history of species.

176 mOlLOOrrCAlL lFUNDAMlEN1l'AlL§

PHOTOSYNTHESIS IN THE SEA

Photosynthesis occurs in the sea with or without the evolution of oxygen. When oxygen evolves, photosynthesis occurs the same way as in terrestrial , except for the attenuation and change in color of light with increasing depth, which influences both the distribution of marine organisms and the need for accessory pigments. Although all animals depend on photosynthesis for survival, as they feed on products of photosynthetic organisms, the way this occurs in certain marine animals is peculiar. A case in point is that of -building and other organisms which live in a with microscopic photosynthetic algae called zooxanthellae. The corals da not feed on zooxanthellae products in the usual sense; transfer of photosynthetic nutrients from zooxanthellae to corals occurs directly. As a consequence, reef corals need much light to support their zooxanthellae, so that shadowing seaweeds are not allowed to grow excessively. The photosynthetic process of green seaweeds and higher plants involves decomposition of water to give intermediate compounds which have reducing properties. These intermediates react with carbon dioxide to afford sugars in a dark process. Amino acids, fatty acids, and nucleotides, which are essential compounds for the growth of all organisms, are produced in subsequent steps which are difficult to distinguish from photochemical acts. This is the primary production; solar energy and a few simple inorganic compounds, in a process mediated by a complex system, yield the organic compounds which are needed in the construction of the complex molecules of . It is impressive that nearly half of the total world primary production occurs in the sea although the of photosynthetic organisms is far smaller in the sea than on the land. Even more striking is that net production of oxygen is higher in the sea than on the land; this is due to the fact that many marine organisms (such as reef-building corals and algae, , mollusks, , and

177 ascidians belonging to the family Didemnidae) have the ability to fix carbon dioxide yielding . This process counteracts the overproduction of carbon dioxide which results from massive fuel burning on the land. One should therefore pay more attention to the conservation of the sea resources and not be only concerned with the problems of the Amazonian forest which is no net porphin oxygen producer. All organisms capable of photosynthesis with oxygen evolution use chlorophyll-a to induce splitting of the water molecule, so that chlorophyll-a has been taken as an index of phytoplankton biomass. This has found practical application with the advent of satellites, which have replaced the slow-cruising research ships. Satellites furnish real-time maps of the distribution of chlorophyll-a which serve in the remote sensing of oceanic o primary production through appropriate COOH algorithms. and higher COOCH 3 plants also have chlorophyll-b, chlorophyll-c whereas brown seaweeds, diatoms, and (mixture of compounds with

R = CH=CIIz or ClIzCH3) have in its place chlorophyll-c, and red seaweeds have chlorophyll-d. All chlorophylls, in particular chlorophyll-c, are structurally related to heme, the prosthetic group of hemoglobin which is the most common biological carrier of

178 oxygen9l • While heme contains iron, all chlorophylls contain magnesium and chlorophyll-c (actually a mixture of two compounds) has the tetrapyrrole structure of

O~COOCH314' l' " H"" 2

(7S,8S,lOR,TR,11 'R)-chlorophyll-a (Rl = CH=~, R2 = CH3) (7S,8S,lOR,TR,11 'R)chlorophyll-b chlorophyll-d (Rl = CH=~, R2 = CHO)

heme, with different substituents, and the closure of ring e, at the hypothetical "porphin" nucleus. The magnesium ion is at the center of the tetrapyrrole unit, bound to the four nitrogen atoms; the same occurs in the other chlorophylls, where, however, reduction of the porphin nucleus has occurred. Derivatives of chlorophyll-c, where magnesium has been exchanged for nickel or vanadium, are widely distributed

')Non-heme oxygen-transporting conjugated proteins in which metal atoms are coordinatively bound to amino acids are also known. In hemerythrin, the oxygen carrier of echiurid and sipunculid worms, as weIl as of , there are two Fe(II) per place of coordination of O2, On binding oxygen by hemerythrin as peroxidianion (O/'), Fe(II) changes to Fe(III) with a corresponding change of color from pale yellow to red. In hemocyanin, the oxygen carrier of many and mollusks, there are two Cu(l) per place of coordination of O2, As a result of oxygen binding by hemocyanin, there is a change from Cu(I) to Cu(H) with a corresponding change from colorless to blue.

179 AlPlPlENlDliClES in oi! shales of the period. Quite recently another porphyrin-type chlorophyll, chlorophyll-c3, has been isolated from the brown alga Emiliania huxley (Prymnesiophyceae). Porphyrins are also represented by iron-coordinated prosthetic groups of respiratory pigments such as myoglobin and cytochromes, as weil as by the prosthetic groups of certain enzymes, such as catalases and peroxidases. Chlorophyll-a, -b, and -d have the structure of modified porphyrins, called chlorins, in which two hydrogen atoms are added to the extemal carbon atoms of ring d. As a further difference with respect to chlorophyll-c, the carboxylic group at ring d of chlorophyll-a, -b, and -d is esterified by the diterpenoidic alcohol phyto!. With the advent in the last decade of powerful chromatographic techniques for the separation of similar compounds, other chlorophylls have been found In photosynthetic organisms. A case in point is chlorophyll-RCI, a mixture of o-chloro-lO-hydroxy-chlorophyll-a isomers which has widespread occurrence in oxygenic photosynthetic organisms.

CARBON VS. SILICON AS A BASIS OF LIFE

The photosynthetic process, on which life depends, O=C=O beg ins with carbon dioxide, which is found both in carbon dioxide the atmosphere and dissolved in the waters and can be taken up by photosynthetic cells and added of active hydrogen to give sugars and other key compounds. Sugars bum with oxygen in living organisms to give back carbon dioxide and water, which can be used again in the photosynthetic process. Fictional science, in the search for the unusual, has imagined an extraterrestrial life based on silicon, on the grounds that silicon is the element chemically closest to carbon. However, the resemblance of silicon dioxide, SiOz, to carbon dioxide, COz, in terms of the same relative proportion of atoms, is purely

180 BllOlLOOllCAlL lFUNDAMlENTAUl

formal. Whereas single COz molecules do exist, SiOz molecules do not. The linear arrangement of the COz molecule allows the two oxygen atoms to stay as far away from each other as possible, in order to minimize repulsions. In contrast, in silicon dioxide there is a continuous network arrangement of oxygen atoms bridging two silicon atoms, which results from the joining of tetrahedra with silicon at the center. Silicon-oxygen double bonds are not formed as they are weaker than silicon-oxygen single bonds, which is just the contrary of what silicon dioxide occurs with carbon and oxygen. This deprives silicon dioxide of the facile reduction-oxidation capability of carbon. In conciusion, carbon is unique in that it is able to change from the inorganic state of carbon dioxide to the organic state of the molecules of life accompanied by the production of molecular oxygen, and then to return to the inorganic state when life molecules burn with oxygen in living organisms. In the case of silicon, such processes are unfavorable, and do not occur. This fact, as weil as its inability to form chains and rings, makes silicon an unsuitable backbone of life molecules.

THE ACCESSORY PIGMENTS OF PHOTOSYNTHESIS: A PHYLOGENETIC MARK FOR RED SEA WEEDS

In addition to light-harvesting chlorophyll-b, or in its stead, algae and cyanobacteria possess other pigments which have the same function and are therefore called accessory pigments. While the most general of these pigments are the carotenoids, cyanobacteria and red seaweeds also possess biliverdin-type pigments: phycoerythrobilin in red seaweeds and phycocyanobilin in cyanobacteria. These

181 pigments, wh ich are bound to a protein as phycobiliproteins in Nature, attest the

COOH COOH COOH [OOH

phycocyanobilin phycoerythrobilin ongm of the red seaweeds from cyanobacteria. Phycoerythrobilin and phycocyanobilin take, as free molecules, the helical form depicted here; when they are bound to a protein, the helical form is lost in favor of an elongated form.

BACTERIOCHLOROPHYLLS: THE NON-OXYGENIC PHOTOSYNTHESIS

In their detoxification processes, phototrophic bacteria use bacteriochlorophylls instead of the chlorophylls of photosynthetic eukaryotes and cyanobacteria. Purple non-sulfur bacteria, such as Rhodopseudomonas, carry out photosynthesis using bacteriochlorophyll-a and -b, whereas green and brown sulfur bacteria, such as Chlorobium and Chloropseudomonas, use bacteriochlorophyll-c, -d, and -e which are also called Chlorobium chlorophylls. In all cases the bacteriochlorophylls are coordinated to magnesium in the same way as the chlorophylls; bacteriochlorophylls b-e carry two extra hydrogen atoms at ring d and therefore are dihydroporphyrins while bacteriochlorophyll-a carries two more hydrogen atoms at ring band therefore is a tetrahydroporphyrin. An analog of bacteriochlorophyll-a with all-trans-geranylgeraniol instead of

182 (3R,4R,7S,8S,lOR)­ (3R,7S,8S)­ bacteriochlorophyll-a bacteriochlorophyll-b

phytol (i.e. with C(6')=C(T) and C(10')=C(II') trans double bonds) has been found in the purple non-sulfur bacterium Rhodospirillum rubrum, and other bacteriochlorophylls are also known or will be discovered with the aid of

modern, powerful chromatographie R1 R' R2 R3 techniques. Bu 1 Et Et Ca Bacteriochlorophyll-c is a mixture Bu' [l Me Cb R2 Pr 0 Et Et C( of compounds. It is also referred to as Pr' Et Me C( [ l Cb Chlorobium chlorophyll-660 since the El Me Ei Me r, e Cb absorption in the visible region occurs at the wavelength of about 660 x 10"9 meters. Actually, six absorption bands can be detected in such a region; four of these bands pertain to the compounds (7 S ,8S)-bacteriochlorophyll-c a) = (2'S) with R' = Bu i or = Et, whereas the other b) = (2'R) two bands are each for a mixture of two c) = (2'R) and (2'S)

183 MlP'lENDKClES diastereomers which differ from one another in the configuration at C(2'). One couple of these diastereomers has R' = Pr" and R2 = R3 = Et and the other couple has R' = Pr", R2 = Et, and R3 = Me. Thus, with respect to bacteriochlorophyll-a

R1 RC HO Bu' E l (a R Prn E l ( b El Cd Bu' Meta Prn ( a E l El Ce Prn Me (c Bu' (a E l Me Np E l Ca Np Me Ca

(7 S ,8S)-bacteriochlorophyll-d a) = (2'S) (7S,8S)-bacteriochlorophyll-e b) = (2'R) or (2'R) and (2'S) (a = (2'R) and (2'S) c) = (2'R) these molecules have an additional alkyl group at the 8 carbon atom'O), lack the methoxycarbonyl group at ring e, have an aIcohoIic function at the chain of ring a, and, in analogy with bacteriochlorophyll-d and -e, have the C'5 famesol instead of the Cw phytol at the estereal side chain of ring d. BacteriochlorophylI-d, or Chlorobium chlorophylI-650 (the absorption in the visible region occurs at a wavelength of about 650 x W- 9 meters), also represents a mixture of homologous compounds. Various absorptions bands can be detected, each corresponding to a bacteriochlorophyll with the R'!R2 substituents specified in our drawing; in a particular strain of Chlorobium, however, the case R' = Pr" and R2 = Et corresponds to two diastereomers differing from one another in the configuration at C(2').

IOlAbbreviations for the R alkyl substituents are as folIows: Me = -CH3, Et = i -CH2CH3, Pr" = -CHzCH2CH3, Bu = -CH2CH(CH3)z, and Np = -CHlCH3)3' 184 Bacteriochlorophyll-e is a mixture of six homologous compounds (in each of the three couples of diastereomers the difference lies in the configuration at C(2')). A more extensively hydrogenated porphyrin-like tetrapyrro1e compound (factor F430), where the four nitrogen atoms are coordinated to nickel, are used by methanogenic bacteria in carrying out the reduction of carbon dioxide to methane.

THE NATURE OF THE PHOTOSYNTHETIC PROCESSES

In purple photosynthetic bacteria e.g., which as prokaryotes are easier to study than eukaryotes, a membrane-bound sandwich-like pair of bacteriochlorophyll molecules receives a unitary amount of light whereby an electron is transferred to a nearby molecule of a pigment called bacteriopheophytin. Since the e1ectron bears a negative charge, the place from which it is taken remains positively charged whereas its place of relocation becomes negatively charged. At the membrane of the photosynthetic

apparatus such a charge separation is stabilized by an extremely rapid (2 x 10"10 seconds) transfer of an electron to a ubiquinone molecule. In other words, the primary act of photosynthesis is a conversion of absorbed photons into an electrical voltage difference at the membrane. A fine point is that the molecu1es involved in these electron transfers are separated from one another by 10 A, which is a large distance, considering the fact that bonding electrons reside between nuclei which are only about 1 A far apart in molecules. How can an electron transfer take place over such a large distance? It does so because of the bizarre nature of this particle: the better its energy is deterrnined, the worse can its position be described. In other words, the electron can go through the energy barrier for relocation, rather than having to go over it, as the thickness of the barrier is comparable to the uncertainty of the position of the electron in the space. Such a process is appropriately called tunneling. Perhaps the very reason for the extreme efficiency of the photosynthetic process, which is the fastest known photochemical reaction between two molecules,

185 has not yet been fully grasped, however. Recent studies with the isolated reaction centers of the purple photosynthetic bacteria Rhodopseudomonas viridis and Rhodobacter sphaeroides have in fact made the matter even more intriguing than heretofore thought. In such studies crystallographic tridimensional determinations of the structures of the reaction centers were carried out at the resolution of interatomic distances while studies of the reaction centers with ultrafast visible spectroscopy allowed the detection of the initial species, a charge-transfer complex of molecules.

H \ 2 R-H + o=c=o --- C=O + H2 0 + 2R / / H H generalized photosynthetic process

The primary chemical act which follows charge transfer is the splitting of a compound of type H2A whereby nicotinamide adenine dinucleotide phosphate (NADP) is reduced to NADPH; the latter is the actual reducing agent of carbon dioxide to formaldehyde (H2CO). At the same time adenosine diphosphate (ADP) is changed to adenosine triphosphate (ATP), which is the phosphorylating agent. Overall the process may be depicted as where A represents a generic atom (such as oxygen, in which case H2A = H20) or a group of atoms, or even nihil (in which case H2A = H2, as with certain bacteria). In other words, the electron flow in the photosynthetic process leads to the oxidation of H2A and reduction of CO2• While higher plants and algae obtain electrons from water, photosynthetic bacteria can get electrons from a variety of other molecules, such as hydrogen sulfide (H2S) or other oxidizable sulfur compounds, molecular hydrogen (HJ, or even small organic compounds made by other organisms. Being able to imitate the conditions of voltage difference in the photosynthetic process is rnan's dream in devising new solar batteries for energy conversion and setting up a photosynthetic reactor to produce sugars and other primary products.

186 Significant advances in this direction have recently been made, though photosynthesis remains one of the most difficult processes to imitate because of the fine-tuned, elose, cooperative action of so many partners.

SCREENING OF NATURAL PRODUCTS FOR BIOLOGICAL ACTION

Currently there are five main lines of interest in marine natural products. They concern the ecological role, the control of fouling and other noxious organisms, the pharmacological action, the exploitation of marine natural products as tools in physiology as weIl as developmental organic chemistry. In assessing the role exerted by marine natural products in controlling marine organisms, the choice is between actual life conditions (which are most difficult to set up, as I have mentioned in chapter 7) and laboratory conditions. What has not yet been taken seriously into account is the control of subtly noxious humans. I agree with Schopenauer that there are many humans who are far more dangerous than the white shark or the scolopendra of the tropics. Some of the problems involved with the screening of marine natural products for pharmacological action have already been discussed with the diatoms. In general, a drug, to exert useful pharmacological effects, has to fulfill many requirements that can not be tested in vitro. The first requirement is that translocation of the drug to the site of action occurs efficiently, i.e. that the pharmacokinetics is favorable. If this requirement is met, the drug has to be non-toxic at the dose required for pharmacological action. Other practical points concerning biological tests have already been dealt with, in particular the fact that preliminary indication of cytotoxicity can be obtained quickly from tests for the inhibition of the ceII division of fertilized or eggs (chapter 12).

187 BIOLOGICAL CLASSIFICATION

The first modem system of biological classifIcation appeared in the year 1735 with the first edition of the "Systema naturae", written by Carolus Linnaeus. The Swedish naturalist, ranked to nobility in 1761 as earl von Linne, and subsequently the anatomists George Cuvier in France and Richard Owen in Great Britain, established relationships among living species on the basis of similarities. Linnaeus' binomial system (whereby a living, or extinct, organism is indicated by two Latin names, the first one for the and the second one for the species) is still in use. Genera which bear similarities are grouped into farnilies, families into orders, orders into classes, and these into phyla or divisions. Currently, in describing a particular organism, the following descending hierarchical order is adopted superkingdom subkingdom (or division) subclass order suborder farnily genus species variety

This classifIcation system has many problems, first of all in the definition of a species as a group of interbreeding organisms; in captivity different species belonging to the same genus may breed with each other. Even the definition of a genus as a set of related species is problematic since establishing similarities is largely a subjective judgment. Many other criteria have recently been introduced, or resumed from the past, in ; they are based on embryological observations (as we have seen for the sponges), computer analysis of behavioral traits or all traits,

188 and observations that no two species can have exactly the same habitat in the same area. But perhaps the most unbiased criterion of biological classification has Darwin as its father. After the theory of evolution was introduced, taxonomic studies became part of the studies on the evolution of species in the sense that the closer two species are to a common ancestral organism, the closer the two species are placed in

the taxonomic scale. In OUf times such relationships are best based on similarities in proteins (as we have seen in chapter 14 for the green turtles of Ascension Island) or in genetic material (as we have seen in chapter 4 for bacteria). To what extent secondary metabolites may serve the same purpose is an intriguing matter which I have deferred to appendix C. In conclusion, taxonomy, being continuously faced with so many challenging problems, has many practical applications, and requires the scientist to have a profound knowledge in many areas. Changes in the way of classifying living organisms follow the progress in oUf 'knowledge and no complete agreement on any one system of classification has ever been reached. In this book I have adopted a compromise system of biological classification that should satisfy the needs of my readers; the list below is largely restricted to taxa of marine interest and is detailed down to class or subclass only.

superkingdom Prokaryotae (formerly Protokaryotes, from protos, first, and karyon, kerneI) kingdom Virus (from virus, poison) kingdom Monera division Bacteria division Cyanophyta (from kyanos, heavy blue, and phyton, plant) division Prochlorophyta (or Protochlorophyta, from protos, first, khloros, green, and phyton, plant) superkingdom Eukaryotae (from eu, true; karyon, kerne!) kingdom Plantae (plants) subkingdom Thallobionta (lower plants) division Rhodophyta (from rhodon, rose, and phyton, plant; )

189 division Chromophyta (from khroma, brown, and phyton, plant; brown aIgae) dass BaciIIariophyceae (diatoms) dass Chryptophyceae (cryptophytes) dass Dinophyceae (dinofiageIIates) dass Phaeophyceae (brown seaweeds) division Euglenophyta division (from khloros, green, and phyton, plant; green algae) dass Chlorophyceae (green seaweeds) division Eumycota (fungi) subkingdom Embryobionta (higher plants) division Magnoliophyta dass Monocotyledonae order NajadaIes (Seagrasses) kingdom Animalia (animals) subkingdom (from protos, first, and zoa, ) subkingdom Parazoa phylum Porifera (sponges) dass Calcarea (calcareous sponges) dass Demospongiae (spongin sponges) subdasses Homosderomorpha and Ceractinomorpha (viviparous spongin sponges) subdass Tetractinomorpha (oviparous spongin sponges) dass HexactineIlida (glass sponges) dass Sderospongiae (possibly a polyphyletic group, not a dass) subkingdom phylum (from cnida, neltIe) dass (from anthos, flower, and zoa, animal) subdass AIcyonaria (= OctocoraIlia) subdass Zoantharia (= HexacoraIIia) dass Cubozoa (true medusae) dass (from hydra, a multi-headed monster, and zoa, animal; hydroids) dass Scyphozoa (from scyphos, cup, and zoa, animal) phylum (from ctenos, comb, and phoros, to bear) phylum Platyhelminthes (from platy, flat, and helminthos, worm) dass (tapeworm) dass (flukes) dass TurbeIIaria (free-Iiving ) phylum (proboscis or ribbon worms) phylum Annelida dass Oligochaeta (from oligo, few, and chaeta, bristIe) dass Polychaeta (from poly, many, and chaeta, bristIe)

190 phylum Nematoda (roundwonns) phylum Echiuria (spoon wonns) phylum Sipunculida (peanut worms) phylum Arthropoda (from arthros, joint, and pod, leg) dass Crustacea (from crusta, shell) phylum (king crabs, sea spiders, ) phylum (mollusks, from molluscus, soft) dass (from gaster, belly, and podos, foot) subdass (from opistho, back, and branchia, gill) subdass Prosobranchia (from proso, in front, and branchia, gill) subdass Pulmonata (from pulmonis, lung) dass Cephalopoda (from kephale, head) dass (bivalves) dass Scaphopoda (from scaphe, boat, and podos, foot; elephant's tusk shells) phylum Phoronida (horseshoe worms) phylum ( animals, from bryon, moss and zoa, animal) phylum Brachiopoda (from brachium, ann, .and pod, foot; lamp shells) phylum Chaetognata (from chaetae, curved spikes, and gnata, jaws; arrow wonns) phylum Echinodennata (from echinos, spiny, and derma, skin) subphylum dass Stelleroidea subdass Asteroidea (from aster, star, and zoa, animal; sea stars) subdass Ophiuroidea (from ophis, snake; brittle stars and basket stars) subphylum (from krinon, lily, and zoa, animal; ) subphylum dass Echinoidea (sea urchins, from echinos, spiny) dass Holothuroidea (from holothurion, a water polyp; sea cucumbers) phylum Hemichordata (from hemi, half, and chorda, rod; acom wonns) phylum Chordata (from chorda, rod) subphylum Tunicata (, from their tunic) (= Urochordata, from oura, tail) dass (from asc; sea squirts) dass Thaliacea (from Thaleia, one of the three Graces) subphylum Cephalochordata (from cephalon, head, and chorda, cord) subphylum Vertebrata

191 B. Classification and structure of the natural products discussed abovell)

BIA. INORGANIC PROCESSES process occurrence/role

NH3 -+ NH20H -+ NO; -+ NO; nitrification carried out hydroxylamine nitrite nitrate by gram-negative bacteria (ammonia is the main base in the sea); it makes nitrogen available to plants.

8 S2- -+ SB -+ S032- -+ sot sulfur utilization by sulfide sulfur sulfite sulfate gram-negative bacteria as energy source.

BIß. INORGANIC COMPOUNDS structure isolated fromlbioactivity/role

seawater (0.0005 g/l) and seaweeds. It is incorporated in the thyroid (hormone tyroxin): an iodine deficiency leads to goiter in humans; incorporated also in the endostyle of of the genus Branchiostoma.

II)Classification of the metabolites here is generally based on likely biogenesis and not on biosynthetic evidence. Mixed biogenesis is not accounted for in the classification. No absolute configuration is implied by the following structural formulae. unless absolute-configuration notation or chiroptical data are reported. Trivial names coined by this author for natural products are enclosed within single quotation marks. 192 seaweeds; antibaeterial. seawater and seaweeds; biosynthetie pathways to bromocompounds are stimulated by peroxidases.

seawater; responsible, as sodium salt, for the high osmotic pressure of seawater. B2. CARBOHYDRATES

CH, I .

CH the brown seaweed JH Ecklonia radiata HO OH (Laminariales) and the 'eekloniarsenoribofuranoside' (R = S03)H bivalve molluse Tridacna 'tridaenarsenoribofuranoside' (R = OS03H) maxima; poison.

H N~

HO~O, 0 0 OH eultures of the aseomyeete Leptosphaeria (+ )-leptosphaerin oraemaris (Linder).

OR o Hfo2R the tropical prosobranch moHuse ; HtOR R~ related metabolites from the Mediterranean CH 2 0R OH prosobraneh Buccinulum kelletinin-I corneum; antibacterial.

193 B3. ACETOGENINS B3.1. FATTY ACIDS, THEIR DERIVATIVES, AND HYDROCARBONS B3.1A. FATTY ACIDS

COOH an undetennined sponge of the Caribbean (Homoscleromorpha, plakinic acid-A Plakinidae); antifungal. HO OH

~j\COOH the Balanus OH balanoides; hatching 'balanoacid ' factor.

B3.1B. FATTY ACID AMIDES, NITRILES, AND ARSENODERIVATIVES

the green seaweed ...... ~Ol ~ Caulerpa racemosa VVVVVVVY\N (CH 2 )n CH 3 (Forsskal) (Bryopsidiales, HO H Caulerpaceae); mild caulerpicin (n=16, 18, 20, 22, 24) poison.

an undetermined sponge of Benga Lagoon, Fiji (Astrophorida, Jaspidae); antibacterial and bengamide-B (R = CH3) anthelmintic.

194 NA1I1JIfWL lP!RODlUC1r §,][,!RlUCTIJlRlE§

N 'i> C the sponge Discodermia calyx (Spirophorida); calyculin-A antileukemic.

the shrimp Sergestes

(CH3),As+CH2COO­ lucens and various sharks arsenobetaine and fish j poison.

B3.1C. HYDROCARBONS AND HALOCARBONS

(+ )-ectocarpene ( -)-dictyo­ desmarestene (+ )-viridiene pterene-C'

(+ )-multifidene finavarrene

brown seaweeds; sexual ~ , ~\ attractants.

fucoserratene (-)-honnosirene (major isomer)

195 brown seaweeds of the genus Dictyopteris (Dictyotales); responsible (-)-dictyopterene-B hydrocarbon mixture for the " smeII".

CH3Br CH3CH2CH2Br various red and brown bromomethane I-bromopropane seaweeds; pollutants.

B3.1D. POLY ACETYLENES

OH OH ~CCH2)9-CH=CH-CCH2)9~ the sponge Cribrochalina dura (Haplosclerida); duryne antitumoral.

B3.2. GLYCERYL ETHERS

OCCH2)17CH3 shark liver oil, HO fH phytoplankton, sponges, and other ; OH chemically stable (+ )-batyl alcohol cell-wall components.

Methanococcus jannaschii (Archaebacteria); it has (3R, 7R, l1R, ISS ,22R ,26R,30R)-archaebacterial the same role as batyl diphytanyl diglyceryl cyclic ether alcohol.

196 B3.3. POLYETHERS

HO cultures of the CHO Gymnodinium breve [= Ptychodiscus brevisl (Davis) (Gymnodiniales); it affects the sodium channels at the membranes and causes repetitive fmng in neurons; inhibitor of the brevetoxin-B cell division of ferti!ized CD(MeOH) L1E = -3.93(225), +6.77(257) sea urchin eggs.

moray ee! (Gymnothorax javanicus); a congener toxin from Gambierdiscus OH toxicus (Dinoflagellates); broad spectrum of -XO~ symptoms in man, including skin irritation \ OH and respiratory failure.

ciguatoxin

197 cultures of the dinoflagellate Prorocentrum lima o OH, (Prorocentrales); the ~y O'~" 0 sponges Halichondria [= Reniera] okadai (Kadota) HO~~"::~H ~o and Halichondria melanodocia (+ )-okadaic acid (Halichondrida), and musseis; antitumoral.

OH

OH HO bacteria; the zoanthids OH OH OH O~ OH Palythoa toxica, Palythoa tuberculosa, and Palythoa H~~/'H OH OH HO OH ~H o OH OH caribeorum; the crab OH H OH OH Demania reynaudii; the ~ OH parrotfish Ypsiscarus HO OH OH HO , OH ovifrons; it induces , OH bradycardia, rapid breathing, cyanosis, and palytoxin block of renal functions.

B3.4. ICOSANOIDS the venom duct of the neogastropod mollusc Conus textile; precursor of bioactive metabolites ~OH (prostaglandins, punaglandins, thromboxanes, arachidonic acid leukotrienes ).

198 o the OH Phaeodactylum tricornutum; fish oil; EPA antithrombic and antiatherosclerotic. the semen of mammals; the gorgonian Plexaura homomalla (Esper) forma o kükenthaU Moser (as methyl ester) (Plexaura homomalla (Esper), forma homomalla, contains (15R)-PGAJ it induces a lowering of OH the blood pressure and muscular contraction; (l5S)-PGA2 inflammatory agent.

ORe CO'CH3

C1 ~ _ ORe ~f "- the telestacean octocoral OH Telesto riisei; (5S,6S,12R, 7E)-punaglandin-4 cytotoxic.

B3.5. POLYPHENOLS AND OTHER CYCLIZED POLYKETIDES

H~ the hydroid Garveja garveatin-A annulata; antimicrobial.

199 AlP'lP'lENlIJiKClES

B3.6. PYRONES

the sacoglossan opisthobranch '" 0 OCH, O~", I I Placobranchus ocel/alus /' (Van Hasselt); it acts as o a protective filter from tridachione solar radiation.

HO the onchidiacean mollusc o Peronia peronii; peroniatriol-I antileukemic,

B3.7. MACROLIDES

OCH]

an unidentified of Hawai; cytotoxic in KB cell sphinxolide lines.

'·0 the cyanobacterium ~,~O H3 CO R Lyngbya majuscula [= ~,~HO~ Microleus Iyngbyaceusl _ ~o I· (N ostocales) and the sea Y hare Stylocheilus OH OH longicauda; responsible aplysiatoxin (R = Br) for contact ; debromoaplysiatoxin (R = H) antifeedant.

200 the sponge Latrunculia magnifica (Keller) (Hadromerida) of the Red o Sea and the nudibranch Chromodoris elisabethina e""

the bryozoans neritina (L.) (Cheilostornata) and convoluta bryostatin-l (Anasca); antileukemic.

cultures of the bacterium Streptomyces griseus; inhibitor of Plasmodium (+ )-aplasmomycin and bacteria.

o

01 """"o i .••• HO ~o OH 0 scallops and musseis of " ' OH " Japanese waters, though o OH of dinoflagellate origin; diarrhetic shellfish pectenotoxin-l poison.

201 B4. SHIKIMA TES B4.1. QUINONES AND POLYPHENOLS ~ ~d the sponge Xestospongia o 0 sapra (Petrosiida); xestoquinone cardiotonic.

HO 0 HO~OH HO~OH HO 0 echinochrome-A sea urchins; antibacterial.

the chryptophyte Chrysophaeum taylori (Lewis and Bryan); antileukemic.

B4.2. OTHER SHIKIMATES

Sr the Thelepus setosus (Quatrefages, HO~O 1865) (Tereberellidae); structurally related Sr Sr substances occur in the mold Penicillium thelepin griseofulvum.

202 NATURAL'RODUCTST:RUC~

B5. TERPENES B5.1 HEMITERPENES

rl)0H_ . the seasquirt HO~ (Polyc1inidae ); antitumoral in vivo prenylquinone (leukemia in mice).

B5.2. MONOTERPENES

the tropical red seaweed Plocamium sp. (Gigartinales); plocamenone odoriferous.

the sponge Dysidea sp. of Venice adriadysiolide ().

B5.3. SESQUITERPENES B5.3A. Derived via 6-11 cyclization of a famesyl precursor: the monocyclofamesanes

~OCOCH'

green seaweeds of the genus Caulerpa CH 3 0CO (Caulerpaceae); 'caulerpatriene' ichtyotoxic.

203 AlPlPlENDKCIBS B5.3Al. Derived from monocyclofarnesanes

HO~

the sponge Dysidea avara ~OH (Dictyoceratida); inhibitor of the cell division of fertilized sea urchin eggs (+)-avarol and antiviral (AIDS).

the sponge Dysidea Jragilis (Dictyoceratida) nakafuran-8 of Hawaii; antifeedant.

B5.3B. Derived via 1-6 cyclization of a farnesyl precursor: cadinanes and pupukeananes

OH the roots of the H"ffi plant Heritiera littoralis; ichtyotoxic o~ (other cadinanes are found in tropical heritol alcyonaceans).

the nudibranch Phyllidia varicosa (Lamarck, 1801) 9-isocyanopupukeanane (Doridacea); antifeedant.

204 B5.3C. Derived via 5-10 cycIization of a famesyl precursor: penlanfuran

the sponge Dysidea fragilis (Montagu, 1818) (Dictyoceratida) of (-)-penlanfuran Brittany.

B5.3D. Derived via cycIization of a gennacrane precursor: eremophilanes and degraded eremophilanes

H'O .... ,,~O~CH20H 0 cultures of the ··hV deuteromycete (+ )-dendryphiellin-A Dendryphiella salina.

B5.3E. Other sesquiterpenes

the gorgonian COOH Subergorgia suberosa; cardiotoxic and inhibitor .m- of neuromuscular subergorgic acid transmission.

the gorgonian Pacifigorgia cf. adamsii; ichtyotoxic (a similar terpene, tamariscol, occurs in the liverwort pacifigorgiol Frullania tamarisci).

205 AlPl?lENlDlITCIES

(ORe " ORe OH MORe OH the gorgonian Euplexaura sp. of Morito Beach, Gulf of Sagami; inhibitor OH of the first cell division moritoside of fertilized starfish eggs.

B5.4. DITERPENES B5.4A. Linear diterpenes

the sea squirt Aplidium sp. (Polyclinidae) of the Gulf of California; aplidiasphingosine cytotoxic.

B5.4B. Derived via 2-6 and 7-9 cyclization of a geranyl geranyl (GG) precursor

tropical seaweeds of the genus Halimeda (Bryopsidales); iehtyotoxic; spermicidal in the sea ure hin Lytechinus pictus; antibaeterial and halimedatrial antifungal.

206 B5.4C. Derived via 2-10 cyclization of a GG precursor: degraded xenicanes

the gorgonian Acalycigorgia inermis; inhibitor of the cell division of fertilized eggs acalycixeniolide-A of sea urchins; cytotoxie.

B5.4D. Derived via 1-14 cyclization of a geranyl geranyl precursor: the cembranes

CHG

the gorgonians Lophogorgia alba, L. cuspidata, L. rigida, and L. chilensis; neuroactive, used as a neuropharmacological lophotoxin tool.

B5.4E. Derived via 5-14 cyclization of a cembrane precursor: the cladiellanes

the alcyonacean Cladiella sp. of the ; antiinflammatory, cladiellin though toxie.

207 AlP'lP'lENDIlClES

o N \.l //-/..~ the stoloniferous o/~ LN octocoral Sarcodictyon roseum [= Rolandia rosea]; the estereal nitrogenated chain originates from urocanic acid of marine bacteria (the level of urocanic acid is taken in USA as a measure of spoilage of sarcodictyin-A fish for market).

B5.4F. Derived via 8-13 cyc1ization of a cembrane precursor: the briaranes

the pennatulacean Renilla reniformis; it affects the central ; antifouling by inhibiting the settlement of larvae o of the barnac1e Balanus renillafoulin-A amphitrite.

B5.4G. Prenylated 9,4-friedodrimanes

Cl - CH 3 / N +~N

=. f~~N )..:::N) NH 2 the sponge Agelas sp. cpW ~ (Axinellida) of Okinawa; it inhibits age1asine-A Na+,K+-ATPase.

208 BS.4H. Other diterpenes

0,\0\ HO~OH OH OH the gorgonian Pseudopterogorgia elisabethae (sp. nov.); ( -)-pseudopterosin-A antiinflamrnatory .

from the dorid nudibraneh Doris verrueosin-A verrucosa; ichtyotoxic.

the brown seaweed Stypodium zonale (Lamoroux) (Dietyotales); H it inhibits the eell division of fertilized sea urchin eggs; eytotoxie; stypoldione iehtyotoxie.

BS.S. SESTERTERPENES BS.SA Linear sesterterpenes

the sponge idia o o o (de Laubenfels) [= /, Leiosella idial (Dietyoeeratida); toxie to starfish, shrimps, and idiadione bryozoans.

209 AJ?lP'lENDKClES

5.5B. Derived via Me(3)-7 eyelization of a geranyl farnesyl precursor

OH the sponge Spongionella sp. (Dietyoeeratida) of Okinoshima Island; antispasmodie; it inhibits o the eell division of okinonellin-A fertilized sea urehin eggs.

B5.5C. Derived via 1-7, 6-11, 10-15, and 14-19 eyclization of a geranyl farnesyl preeursor: the sealaranes

CHO

the sponge Cacospongia scalaris (Dictyoeeratida) of Wakayama; desaeetylsealaradial iehtyotoxic; antileukemic.

B5.5D. Derived via prenylation of a monoeyclogeranyl geranyl preeursor

the sponge Luffariella variabilis (Polejaeff) OH (Dictyoeeratida); antiinflammatory and ( 4R)-manoalide analgesie.

210 the sponge Fasciospongia cavernosa (Dictyoceratida); degraded terpene related to cavemosine manoalide; ichtyotoxic.

B5.5E. Other sesterterpenes

HoDe the spange Dysidea sp. (Dictyoceratida) of Palau; inhibitor of aldose reductase and therefore of interest in treating (+ )-dysideapalaunic acid diabetes.

B5.6. TRITERPENES B5.6A. Linear triterpenes

many marine animals, incIuding shark (Squalus); precursor of steroids and squalene triterpenes.

OH

" 0 OH Laurencia thyrsifera (Hook) and Laurencia obtusa (red seaweeds, thyrsiferol Cerarniales); cytotoxic.

211 B5.6B. Lanostane and cycloartane triterpenes

the holothurian Actinopyga echinites (Jaeger); toxic deterrent; hemolytic; aIarm substance; it inhibits echinoside-A Na+,K+-ATPase.

the green seaweed Tydemania expeditionitis (Weber-van Bosse) (Bryopsidiaceae ); 'tydemaniatriterpene' phylogenetic mark.

B5.6C. Friedelane triterpenes

"j/

:: :. the green seaweed ~ Monostroma nitidum o (UlvaIes) and the cork of the European oak; friedelin phylogenetic mark.

212 B5.6D Oleane triterpenes the scleractinian coral Echinopora lamellosa (probably: Esper, 1797) (Faviidae); other oleanes occur in terrestrial flowering plants and petroleum of flowering-plant origin (sediments of Cretaceous (20ß)-echinolactone-B or younger age).

B5.6E. Hopane triterpenes

OH OH "",,~OH

it acts as a stabilizer of membranes of bacteria; also found in fossil (32R,33R,34S)-bacteriohopanetetrol sediments.

B5.6F. Other triterpenes

o

the archeogastropod mollusc Collisella limatulone limatula; antifeedant.

213 B5.7. TETRATERPENES

main carotenoid of seaweeds and terrestrial plants as photosynthetic ß,ß-carotene accessory pigment.

" "" 0 ....,," ~.C'C.ij'~" 0 \ """ OH \ ~ 0 main carotenoid of 0/"-0 >'OH dinoflagellates as photosynthetic accessory peridinin pigment.

0-.c~ MORe main carotenoid of OH diatoms as photosynthetic fucoxanthin accessory pigment.

B6. STEROIDS B6.1. Cholestanes

24 main sterol of higher animals; common with marine animals, too; with certain sponges it is replaced by other H steroids; component of (-)-cholesterol cell walls.

214 the starfish Acanthaster planci (L.); toxie deterrent and alarrn aeanthaglyeoside-A substanee; hemolytie.

ORe

o ""O~OH U~OH Pardachirus pavoninus HO (peaeoek sole); shark (-)-pavoninin-l repelling; hemolytie.

B6,2. 4- Methylsteroids

H main sterol of the H dinoflagellates; found also found in gorgonians; dinosterol ehemieal mark.

215 B6.3. Ecdysteroids

HO OH

H the zoanthid Gerardia savaglia (Bertolini, 1819) H which also contains typical molting hormones of and gerardiasterone insects.

B6.4. Seco-steroids

the sponge Dysidea herbacea (Dictyoceratida); herbasterol ichtyotoxic.

B6.5. Dimeric steroids ""'.-"""OH OHH?l 0""",~ H 0 OH jIN'H-~ ~, N i H.""- H 0 0 0·'" "". ...15 "" ""OH the gilchristi; (+ )-cephalostatin-I antileukemic.

216 NA'fIlJlRAL lPIROD1lJCJr S1m.1lJC']['1lJ]R]ES

B7. NITROGEN COMPOUNDS B7.1. AMINO ACIDS B7.1A. Protein amino acids

COOH COOH H2N-tH H2 N-tH CH 3 CH 2 COOH L-aIanine L-aspartic acid COOH H2~H main amino acids in CH 2 CH 2COOH most seaweeds; protein L-glutamic acid components.

NH main amino acid in O seaweeds of the family IJ" COOH Rhodomelaceae; chemical L-proline mark.

B7.1B. Non-protein amino acids

NH Digenea simplex (red ~""[OOf seaweed, Ceramiales, Rhodomelaceae ); COOH insecticidal; anthelmintic; neurobiological tools as (-)-a-kainic acid (+ )-a-allokainic acid neuroexcitants.

COOH H COOH ' Chondria armata (red ~COOH y seaweed, Ceramiales, ~ ~ """H Rhodomelaceae ); bioactivity similar to ( -)-domoic acid a-kainic acid.

217 Heteroehordaria abietina [= Analipus japonieus] NH 2 and other brown seaweeds of the genus + ' Laminaria (Laminariales); (CH3)3N~COOH vascular and muscular laminine activities.

calcareous red seaweeds; H2N~COOH it induces the settlement GABA of mollusc larvae; neurotransmitter in man. many , in particular ~COO-+1 the gorgonians CH 3 and homarine L. setaeea; antifouling. the reef-forming coral Aeropora formosa OCH 3 (Scleractinia) and the zoanthid Palythoa H2N~NHCH2COO- tubereulosa as protective filter against solar radiations; similar compounds in the bivalve HXOH mollusc Mytilus palythine galloprovincialis. B7.2. PEPTIDES AND POLYPEPTIDES B7.2A. Peptides

the sea hare Dolabella aurieularia (Opisthobranchia, sea hares) antileukemic; (-)-dolastatin-l 0 anti-melanoma; antiviral.

218 OH

H~:lOH the ascidian Ascidia nigra H, (L.) (Phlebobranchia); H • OH reducing and complexing H ',OH H~ I agent for vanadium; H~N '" /. OH possibly is involved in HO~ 0 the immune system. OH tunichrome-B 1

B7.2B Depsipeptides

-l ~~O"

the ascidian rrididemnum "~,~~"~W. I solidum (Van Name) --' (Aplousobranchia, aCH, Didemnidae); antitumoral (-)-didemnin-B and anti viral.

B7.3. ALKALOIDS B7.3A. Alkaloids derived from arginine

the zoanthids and P. axinellae adriaticus; it intercalates zoanthoxanthin into DNA.

219 mollusks and fishes as dietary products of n):::::NH ' H2Nl~~' 2 dinoflagellate origin (of + J. N NH the genera Gonyaulax H2N./'- '" OH and Protogonyaulax j OH (Peridiniales)); it R obstructs the sodium sax.itox.in (R = R' = H) channels at the gonyautoxin-l (R = OS03'; R' = OH) memhranes of animals.

0-

~OHOOH ! NH marine bacteria, fish, ~ N~NH2 + starfish, xanthid crabs, HO OH H the blue-ringed octopus, OH and snails; also newts (-)- tetrodotoxin and frogs; toxin. ~ HN!(NH the sponge Ptilocaulis aft. P. spiculifer HN (Ax.inellida); antileukemic (+ )-ptilocaulin and antibacterial.

87.38. Alkaloids derived from tryptophan

the cyanobacterium Lyngbya majuscula [= Microleus lyngbyaceus]; similar alkaloids in terrestrial soil bacteria; tumor promoter and lyngbyatoxin-A inflammatory agent.

220 NAWIRAlL lP'lROJl)1lJCIr §1rlR1lJCWlRlES

the sponges Aplysinopsis retieulata and Smenospongia [= Polyfibrospongia 1 eehina (Dictyoceratida) and scleractinian corals (Dendrophylliidae); it affects neurotransmission; antidepressant; it alleviates noxious side effects of certain drugs; probably a protective filter against solar methylaplysinopsin radiation.

the ascidian Eudistoma HO olivaceum (Aplousobranchia); Br~--I\ -0 antiviral. Other N / ß-carbolines also from H S H N the ascidian RittereIla 2 sigillinoides (Brevin, eudistomin-C 1956) and the hydroid (O-a,ß equilibrium forms) pluma (L.).

the spange HaliclOlUl sp. (Haplosclerida) collected off Manzamo Island, manzarnine-A Okinawa; antileukemic.

221 o

prosobranch mollusks of o the genera M urex and 6,6' -dibromoindigotin (X = Br) Dicathais; dying pigment indigotin (X = H) stable to solar radiation.

B7 Je. Alkaloids derived from proline marine bacteria (prodigiosin: Beneckea gazogenes, Alteromonas rubra, and Serratia marcescens; cycloprodigiosin: B. gazogenes); inhibitors of the growth of green flagellates and prodigiosin cycloprodigiosin cyanobacteria.

o sea hares of the genus (Opisthobranchia, Anaspidea, Aplysiidae); apl ysioviolin deterrent.

B7.3D. Alkaloids derived from omithine

Br the sponge Hymeniacidon sp. (Halichondrida) of Okinawa; antagonist of serotonergic receptors in the rabbit aorta; it blocks hymenin a-adrenoceptor activity.

222 the sponge Agelas sp. of Kerama Retto (Axinellida); antagonist keramadine of serotonergic receptors.

B7.3E. Alkaloids derived from lysine

the spange Aaptos aaptos (Hadromerida); antagonist of serotonergic receptors in the rabbit aorta; it blocks a-adrenoceptor activity.

B7.3F. Alkaloids derived from phenyl alanine

o '" OH N:::-\ \ 4 N- CH3 ~: \ HN /- H:N-{ HO COOH COOH the starfish Dermasterias imbricatine imbricata; deterrent.

B7.3G. lmidazole alkaloids

the sponge Leucetta chagosensis (Dendy) (Calcarea); similar alkaloids in the Mediterranean calcareous CH,O spange Clathrina naamidine-A clathrus.

223 the sponge DysideaF .... '1' f the IJ1, frag! !S o. antifungal, antileukeIllic, . (-)-dysiazirine and antibactenal. OH HN~'i'/ n e Leucetta ~NJlN the spo g. (Calcarea); eH 3 s are insect microrap~!ds.other pten me leucettidine pigments.

the spong e Xestospongia"da)' ex!gu. a (PetroSll. , xestospongin-C vasodilatatlVe.

in coffee beans. and in the chamaeleon; Paramurl.ceagorg~man caffeine cardiotomc.

224 the sponges Prianos melanos (Haliehondrida, Hymeniaeidoniidae) and Latrunculia brevis (Ridley and Dendy) (Hadromerida); eytotoxie in vitro but not in vivo; prianosin-A (= discorhabdin-A) toxie to mammals.

o the ascidian Didemnum sp. (Aplousobranchia, Didemnidae); antileukemic; a Ca2+-releaser in sareoplasmie retieulum more potent than ascididemnin eaffeine.

the ascidian Cystodytes dellechiajei (Della Valle) (Aplousobranchia, Polyeitoridae; bioactive cystodytin-A as aseididemnin.

87.4. OTHER AMINO ACID META80LITES

~NH2 the alcyonaceans HO Sinularia heterospiculata P and Nephthea sp.; HO atriastimulant; mediator in the central nervous dopamine system of man.

225 AlP'lP'!ENDllC!ES

the sponge Aplysina [= Verongia 1 cavernicola Br~OH (Vacelet) (Verongida); ..V"'·NH antibacterial; cytotoxic . HO II",,·.~O

bromochloroverongiaquinol 7-bromocavemicolenone

the sponge Psammaplysilla purea (Verongida); inhibitor of Na+,K+-ATPase and myosin Ca++-ATPase; activator of myosin purealin K+,EDTA-ATPase.

NH HO OH 0 rI;) the fish pathogenic )-=\ gram-negative bacterium /N~N~N Vibrio anguillarum; ~~J OH siderophore strongly involved in the virulence. anguibactin

B7.5. NUCLEOSIDES

NH, CN N~ ~NJl..t! the sponge Mycale sp. (Poecilosc1erida) of the ~ Gulf of Sagami; inhibitor CH 3 0 OH of the cell division of mycalisine-A starfish eggs.

226 the colonial ascidian Trididemnum cereum (Giard, 1872), starfish, and acom worms; 2' -deoxyuridine phylogenetic mark.

B8. SULFUR COMPOUNDS

the annelid Lumbrinereis brevicirra [= L. nereistoxin heteropoda]; insecticidal.

B9. BIOPOLYMERS B9.1. POLYSACCHARIDES

red seaweeds; agarose is used in immunological studies; agar (made up of agarose, pyruvated agarose, and a sulfated polymer of galactose) is an emulsifying, binding, suspending, and thickening agent, used also as a degradable neutral agarose pyruvated agarose vehicle for oral drugs.

227 red seaweeds; gelling, OS 03- emulsifying and stabilizing agents used for food and non-food, ~H~~ O~ but especially for rnilky O~O,- /1~07'0~ and waterish media; also used to stimulate the "-( OH ~ growth of connective OR tissues and to lower the K-carrageenan (R = H) cholesterol level in the L-carrageenan (R = SOJ·) blood.

brown seaweed; alginic acids and alginates (made up of D-mannuronic and COOH COOH L-guluronic acid) have many of the uses of the HO~~ polysaccharides of red HO~HO seaweeds with an HO~ additional special OH OH OH capacity of binding water-soluble alkali-earth D-mannuronic acid L-guluronic acid salts.

fucoidan (made of L-fucose and D-galactose in about 10:1 brown seaweeds; base ratio) material for the production of L-fucose.

the cell walls of peptidoglycan gram-positive and R = -CH(CHJ)C(O)-peptide. A single chain of two gram-negative bacteria; parallel chains is represented structural polymers.

228 COCH 3 eH OH I f 20 NH CH 2 0H oHO4 0 0 HJ;74 the ceH walls of fungi o HO 0 NH CH OH 'I and, bound to a pro tein, COCH 2 ~H the cutic1e of crustaceans; J COCH 3 structural polymer.

B9.2. OTHER BIOPOLYMERS o 0 ~ 11 11 ?,O~O/~'O~O/~~~ XO HO XO HO? the ceH walls of gram-positive bacteria; NH 2 NH 2 structural polymers. teichoic acids

Rl~CH20H RJ R seagrasses, emergent building blocks of lignins plants, and terrestrial p-coumaric acid (Rt '" R3 '" H; R2 '" OH) plants; structural 2 3 ferulic acid (R' '" OCIl3; R = Oll; R = 1I) polymers. t 2 3 sinapic acid (R = OCH3; R '" R = Oll)

229 BIO. LUCIFERINS

OH I O-P-OH HO 11 marine bacteria; a HO 0 long-chain aldehyde, ~ molecular oxygen, HO vitamin-BJ2> phosphoric CH 2 acid, and the luciferase R= -L are also needed in the luminous process; dihydroflavin monophosphate luciferin.

most crustaceans; the luminous process is the simplest known, requiring only molecular oxygen and the luciferase; , cypridinaluciferin' luciferin.

coo­ the krill Euphausia pacifica (R=OH) and 'euphausialuciferin' (R = OH) dinoflagellates (R=H); 'dinoluciferin' (R = H) luciferins.

230 NArulRAlL IP'IRODUcr STIRUCruillliS

Aequorea forskalea (hydroid); calcium and luciferase are also involved; unusually for cnidarians another pro tein is implicated in the luminous process while molecular oxygen is not; prosthetic group of this coelenterazine luciferin (aequorin).

231 C. Phylogenetic relationships among living organisms and natural products of phylogenetic significance

The biological classification of living organisms is generally controversial, and phylogenetic relationships is what specialists disagree on most. Dntil recently this was especially true for soft-bodied organisms, such as the ascidians, which have left no fossil records. N ow opinions are changing: fossil records, which were held in great respect in establishing phylogenetic relationships, are no longer deemed informative enough to alter a phylogeny based on data for living species. This alleviates the problems with soft-bodied organisms while calling for revisions in phylogenetic assignments for the other organisms. What I am presenting here is an attempt to establish phylogenetic relationships among li ving organisms on the basis of their natural products. Phy logenetic relationships based on proteins or genetic material are the best examples, and have been already dealt with in previous sections of this book, while secondary metabolites confront us with a most ambitious task. This is apparent from the frequent isolation of the same secondary metabolites from taxonomically unrelated species. In some cases this phenomenon is clearly the result of retention from the diet or production by symbionts and therefore there is no danger of deducing false phylogenetic relationships. Examples of dietary metabolites from previous chapters in this book concern antifeedant or toxic compounds found in opisthobranch mollusks, and toxins found in filter feeding mollusks. Exampies of natural products which have symbiontic origin are okadaic acid (which is produced by the dinoflagellate Prorocentrum lima and accumulated in the sponges Halichondria okadai and Halichondria melanodocia) and dinosterol (which is produced by the dinoflagellate Zooxanthella microadriatica and transferred to gorgonians). In other cases a dietary or symbiontic origin of the natural products are likely but not proven. This is exemplified by acanthifolicin (which is found in the sponge Pandaros acanthifolium and has a molecular structure very similar to that of okadaic

232 lP'HYlLOOlENlETIC llrnLATIONSJH[][JP'S

acid), (20ß)-echinolactone-B (found in the scleractinian coral Echinopora lamellosa), domoic acid (found in both the red seaweed Chondria armata and musseis cultured in Cardigan Bay, Prince Edward Island, Canada), latrunculin-A (present in the sponge Latrunculia magnifica of the Red Sea and the nudibranch Chromodoris elisabethina of Guam and Eniwetok), and methylaplysinopsin (fIrst found in and lately in scleractinian corals). In certain cases neither a dietary nor a symbiontic origin can be advocated to rationalize the presence of the same secondary metabolite in taxonomically umelated

organisms; e.g. prostagiandin (l5S)-PGA2 (which is found as such in the semen of mammals and as methyl ester in the gorgonian Plexaura homomalla forma kükentali), ecdysterone (which is found in large amounts in the zoanthid Gerardia savaglia and as a hormone in crustaceans and insects), ajugasterone-C (a phytoecdysteroid first found in the terrestrial oriental plant Ajuga sp. and lately in the Mediterranean zoanthid Gerardia savaglia), caffeine (long known to be present in coffee seeds and recently found in the gorgonian Paramuricea chamaelon), and GABA (a primary metabolite in man and a settlement inducer in calcareous red seaweeds). The danger of building up false phylogenetic conclusions through natural products, which is implicit in some of the above examples, can be minimized through a proper analysis. Let me first of all remark that primitive animals, such as the sponges, are not limited to dietary products but are also capable of de novo synthesis of secondary metabolites12l• Such metabolites may safely be used in establishing phylogenetic relationships. In the subtle cases of sponge products of symbiontic origin there is a growing awareness that when obligate symbiosis is involved, as is frequently the case, the macroorganism-symbiont couple behaves, in what regards the synthesis of natural products, as if it were a single organism, irrespective of location and season, or a reproducible trend with changing seasons is

12)De novo synthesis of conventional and unusual sterols occurs, for example, in the marine sponges Microciona prolifera and Tethya aurantia californiana. 233 observed. This applies to sponge sterols whieh have the C(24)-alkyl(alkenyl) ehain typieal of plant sterols and are in fact synthesized by the sponge algal symbionts. Such metabolites may therefore be used for taxonomic purposes. In the following ehart organisms which are regarded as equal in rank appear on the same horizontalline even if they belong to different phyla. Phylogenetic relationships are indicated by either an upward arrow or by a horizontal double arrow. Phylogenetieally signifieant natural produets appear endosed in a box either at the right side or below the group of organisms of pertinence. The chart (whieh does not take into account rRNA sequenees beeause they are too short so far) illustrates that everything began with the primeval broth (moleeular hydrogen, water vapor, carbon dioxide, nitrogen, anunonia, and methane) whieh formed the early atrnosphere of the Earth. Under the action of the sun and of lightning, the primeval broth formed the arnino acids which dissolved into the and formed the proteins. Although it is not yet dear how, supramoleeular organization of the proteins and of genetic material gave origin to the cells of the simplest bacteria from whieh life evolved into either the autotrophie bacteria13), capable of non-oxygenie photosynthesis, or the more complex cyanobacteria which are eapable of oxygenic photosynthesis; the latter made molecular oxygen available for further evolution of living organisms. The cyanobacteria gave origin to the red algae along an endosymbiont line. The green algae originated from photosynthetic bacteria via the prokaryotic green alga Prochloron didemni and gavc origin to the higher plants which inherited the ability of their phylogenetie precursors to synthesize cydoartane or, as in the ease of the European oak, friedelane triterpenes. The ancestral animals, the protozoans, originated from the algae, tao. In fact certain groups of algae, like the dinoflagellates, that have the typical feeding modes

13)It has been lang debated whether life originated from hydrothermal vents at the oeeanic ridge (which are presented in chapter 4). Now this possibility has been dismissed; the temperatures there are too high.

234 of animals, are traditionally in the of both the zoologist and the botanist. The protozoans gave origin to the sponges, and probably also to the cnidarians

Origin of, and phylogenetic relationships among living organisms, and natural products of phylogenetic significance

""lIlIlI .. 15 repti I es hisher i.lllph ib i .ns chord.hs jawf!d Fishe.s ji.\.Iless Fishes Rsnah (h.Sfishl!s and f 141.111preys) lO\H!1'" (asddLlns) eh CI'" d a hs 12 ,- de 0": XI'" i bonuc I. os i cle 51

er h i"o derDIs 12 '-de'lxyr ibonuc 1 eos i des I

!2 '-deo)(yribonu( lusidul

.. rthropods [heIllQey.ninsl L- mollusc.s IhUlocyardn.s! ill"lne 1 i ds

tr"Uliotodu c'lst~df!s 1urbelliu"'iilns ~ ? (+.,tni dar i ans

.1,9'U !phycobi I1ns]

----~ cYilnobilCil!ria 'U!'!"Phi'~lphY"bilin'l

hlidel"'otroph it b., hri.a t prohins L sen.He •• hri.l f amino acids L nud.jc bUtI.s f priuYil\ broth (Hz, HzO, CO ZI Nz • NH ll CH f )

235 AlP'lP'lEl'IDllClES

which may have descended from the sponges as weil. Within the cnidarians, gorgonians of the family Briareidae and sea pens are interrelated by the production of briarane diterpenes. Worms originated from cnidarians following two different lines of evolution. One line led, via an undefined interrnediate organism, to the trematodes, cestodes, and turbellarians. The other line led to the from which the large phyla of

the mollusks and the arthropoc!~ originated14l• The arthropods are the branching point before the more evolved invertebrates (echinoderrns, , and lower ). The latter, which have a dorsal hollow nerve cord at the embryonal stage, evolved into the chordates, fIrst into the and the lampreys and then into the jawless fishes, the jawed fishes, the amphibians, the reptiles, and finally the mammals. The elose phylogenetic relationship between the echinoderrns, hemichordates, and lower chordates, proposed on elassical biological grounds, is supported by the production of unusual 2' -deoxyribonucleosides in animals belonging to these groups.

14lAlthough many crustaceans and mollusks contain hemoglobin, in general these are blue-blooded animals; as I have indicated in appendix A, their oxygen carrier, hemocyanin, when bound to oxygen takes a blue color due to the Cu(II) oxygen-binding centers. Arthropodal and molluscan hemocyanins differ in size (Iarge in arthropods and extremely large in mollusks) and in quatemary structure. From the analysis of the sequence of amino acids and X-ray structure it is believed that both arthropodal and molluscan hemocyanins arose from a common primordial oxygen-carrier protein where oxygen was bound to only one copper atom. Although we do not know if this primordial protein was contained in an annelid, the binding site of copper is the same as the one found in certain enzymes, called tyrosinases, which are present in lower fungi and bacteria. In the Pre- era the uptake of the second copper atom followed different strategies: in arthropods there was perhaps a doubling of the above-mentioned primordial copper center (and the scission of arthropods into aquatic and terrestrial species did not affect the hemocyanins) whereas in both mollusks and tyrosinase-bearing organisms the second copper center was built ex novo. Why mollusks have developed, and saved, such large proteins as oxygen carriers is a mystery. 236 lRlElFJEIRlENClES REFERENCES AND SUGGESTIONS FOR FURTHER READING

biologicaI aspects

Algae and plants den Hartog, C. "The seagrasses of the world" North-HoIland, Amsterdam, 1970.

Taylor, F.J.R, Ed. "The biology of dinoflagellates" Blackwell Scientific, London, 1987. van den Ende, H. "Sexual interactions in plants" Academic Press, London, 1976.

Bacteria and fungi

Clayton, R.K.; Sistron, W.R., Ed. "The photosynthetic bacteria" Plenum Press, New York, N. Y., 1978.

Johnson, T.W.; Sparrow, F.K. "Fungi in oceans and estuaries" Cramer, 1961; reprinted by Wheldon & Wesley, Codicote, Herts, 1970.

Kohlmeyer, J.; Kohlmeyer, E. "Marine mycology" Academic Press, New York, N.Y., 1979.

Sieburth, J.McN. "Sea microbes" Oxford University Press, New York, N.Y., 1979.

Cnidarians

Joubin, L. "Le fond de la mer" Librairie Hachette, Paris, 1920.

Lacaze-Duthiers, H. "Histoire de la Laura gerardiae, type nouveau de crustac(~ parasite" Firmin-Didot, Paris, 1882.

Evolution

Schubert, 1. "Eukaryotic nuclei of endosymbiontic origin" Naturwissenshaften, 75, 89, 1988.

237

Moran, P.J. in "Oceanography and " Aberdeen University Press, vol. 24, 1986.

General treatises

George, J.D.; George, 1.1. ". An illustrated encyclopedia of invertebrates in the sea" Lionel Loventhal Ltd., London, 1979; published in USA by 1. Wiley & Sons, New York, N.Y. Taxonomy and general biological aspects of marine invertebrates.

Parker, S.P. ed., "Synopsis and classification of living organisms" McGraw-Hill, New York, N.Y., 1982. Encyclopedic treatise on the taxonomy and general biological aspects of all living organisms.

History of coral reefs and theories about Iife

Daly, R.A. "The changing world of the ice age" Yale University Press, New Haven, 1934.

Darwin, C.R. "The structure and distribution of coral reefs", Smith, Eider & Co., London, 1842.

Roffmeister, J.E.; Ladd, H.S. "The antecedent-platform theory" 1. Geol., 52, 388, 1944.

Lovelock, L. "Gaia: a new look at life on Earth" Oxford University Press, Oxford, 1979.

Wiens, H.J. "Atoll environment and ecology" Yale University Press, New Haven and London, 1971.

238 Pharmacology

Baslow, M.H. "Marine pharmacology" Krieger, Huntington, New York, N.Y., 1977.

Hoppe, H.A.; Levring, T.; Tanaka, Y., eds., "Marine algae in pharmaceutical sciences" de Gruyter, Berlin, 1979.

Lewis, D.A. "Anti-inflammatory drugs from plants and marine sources" Birkhäuser, Basel, 1989.

Ragelis, E.P. "Seafood toxins" ACS Symposium Series 262, American Chemical Society, Washington D.C., 1984.

Wong, K. c.; Wu, L.T. "History of Chinese medicine" 2nd ed., National Quarantine Service, Shangai, 1936.

Scientific cruises

Challenger, H.M.S. "Reports of the scientific results of the exploring voyage H.M.S. Challenger", 1872-76.

Sponges

Bergquist, P.R. "Sponges" University of California Press, Berkeley and Los Angeles, 1978.

Levi, C. "Systematique de la classe des Demospongiaria" in Grasse P.P., ed., "Traite de Zoologie" Tome III, Fascicule I, pp. 577-631, Masson et Cle., Paris, 1973.

Simpson, Y.L. "The cell biology of sponges" Springer-Verlag, New York, N.Y., 1984.

Tuzet, O. "E'ponges caJcaires" in Grasse P.P., ed., "Traite de Zoologie" Tome III, Fascicule I, pp. 27-132, Masson et Cle., Paris, 1973.

Tuzet, O. "HcxactinclIides ou hyalosponges" in Grasse P.P., cd., "Traite de Zoologie" Tome III, Fascicule I, pp. 633-690, Masson ct CIe., Paris, 1973B.

239 chemistry

Christophersen, C. "Marine alkaloids" in "The alkaloids" Vol. XXIV, Academic Press, New York, N.Y., 1985

Dedekind, A. "Ein Beitrag zur Purpurkunde. Nebst Anhang: Neue Ausgaben seltener älterer Schriften über Purpur" Meyer und Müller, Berlin, 1898.

Faulkner, DJ. "Marine natural products: metabolites of marine algae and herbivorous marine mollusks" Nat. Prod. Rep., 1, 251, 1984; "Marine natural products: metabolites of marine invertebrates" ibid., 1, 551, 1984; "Marine natural products" ibid., 3, 1, 1986; ibid., 4, 539, 1987; ibid., 5, 613, 1988.

Garson, MJ. "Biosynthetic studies on marine natural products" Nat. Prod. Rep., 6, 143, 1989.

Hashimoyo, Y. "Marine toxins and other bioactive marine metabolites" Japan Scientific Societies Press, Tokyo, 1979.

Hegnauer, R. "Chemotaxonomie der Pflanzen" Band 1-7, Birkhäuser Verlag, Basel, 1962-1986.

Krebs, H.Chr. "Recent developments in the field of marine natural products with emphasis on biologically active compounds" Fortshritte ehern. org. Naturst., 49, 151, 1986.

Lee, WL, Ed. "Carotenoproteins in animal coloration" Dowden, Hutchinson & Ross, Inc., Stroudsburg, Pennsylvania, 1977.

Moore, R.E. "Volatile compounds from marine algae" Ace. ehern. Res., 10, 40, 1977.

Moore, T.C. " and physiology of plant hormones" Springer-Verlag, New York, N.Y., 1979.

Peter, M.G. "Chemical modifications of biopolymers by quinones and quinone methides" Angew. ehern. Int. Ed. Engl., 28, 555, 1989. A review on the structure and biogenesis of plant lignins, chitin, and sc1erotized proteins of insects.

240 Pietra, F. "Total synthesis of marine natural products: a powerful contribution to the understanding and development of marine organic chernistry" Gazz. Chim. Ital., 115, 443, 1985.

Scheuer, P.J., ed., "Marine natural products. Chernical and biological perspectives" Acadernic Press, New York Vol I-V, 1978-1983. General, multiauthor treatise.

Scheuer, P.J. ed., "Bioorganic Marine Chernistry" Springer-Verlag, New York, N.Y. Vol. I, 1987; Vol. II, 1988. General, multiauthor treatise.

Scheuer, P.J. "Marine toxins" Acc. Chem. Res., 10, 33, 1977.

241 GWSSARY

GLOSSARY

absolute contiguration-configuration that defines the chirality of the moleeule, i.e. whether the molecule is like the left or the right hand. Old notations of absolute configuration are L- or D-, as related to L-glyceraldehyde or D-glyceraldehyde, to

L-glyceraldehyde D-glyceraldehyde which the compound under examination has to be correlated by chemical transformations in order to assign the absolute configuration. This is shown above in Fisher projections, where the substituents at the vertical lines must be viewed below the plane and those at the horizontal lines above the plane of the paper. It is implied that the absolute configuration of glyceraldehyde is independently known via an absolute method. Recent notations of absolute configuration, Rand S (from "rectus", right and "sinister", left) are based on arbitrarily assigned priorities to the substituents at the asymmetrie carbon. accessory pigments-pigments that harvest light and transfer the corresponding energy to the photochemical center in photosynthetic cells. acetogenins-compounds that originate biogenetically from acetic acid

(CH3COOH) or from higher carboxylic acids derived from acetic acid. acetylcholine activity-interference with the chemical transmission, due to acetylcholine, of impulses along nerve fibers of higher animals. active hydrogen-hydrogen in astate more reactive than free molecular hydrogen (HJ, such as it occurs in photosynthesis and catalytic hydrogenations.

242 GWSSAlRY

adrenalin (epinephrine)-honnone of the adrenal medulla and sympathetic nerves. u·adrenoceptor blocking activity-inhibition of neurotransmitters by a drug. The synthetic drug chlorpromazine is quite active in this respect and is usually taken as a reference standard. alcohols-an alcohol (R-OH) may be fonnally imagined to derive from a hydrocarbon (R-H) by substitution of a hydrogen atom with a hydroxyl (OH) residue. alkaloids-nitrogen-containing metabolites that usually display basic reaction and originate biogenetically from amino acids. They inc1ude physiologically active compounds such as strychnine, morphine, nicotine, and caffeine. alkyl group-residue (R) from a hydrocarbon (RH), resulting from the fonnal abstraction of a hydrogen atom. amines-an amine (R-NR'R") may be fonnally imagined to derive from a hydrocarbon (R·H) by replacement of a hydrogen atom with the NR'R" residue, where R' and R' may be hydrogen atoms or alkyl or aryl groups. amino acids-organic compounds in which the amino group (NR'R") and the carboxyl group (COOH) are in the same mo1ecule. With u-amino acids the two functions are at the same carbon atom. Twenty u-amino acids in the L-configuration constitute the building blocks of the proteins. Natural products comprise many more types of amino acids, not necessarily of the u-type, or in the inverse absolute configuration with respect to protein amino acids. anabolism-constructive metabolism. anaerobie processes-biochemical processes that occur in the absence of molecular oxygen. Anaerobes are organisms that live without oxygen; certain organisms are facultative anaerobes. analgesie drug-a drug that alleviates pain without blocking nerve impulses. anion-an ion which bears a negative charge.

243 GLOSSAlRY

antiatherosclerotic drug-a drug that prevents the deposit of fats along the arteries. aquaculture-exploitation of water media for the growth of seaweeds, invertebrates, and fish.

aragonite-a form of calcium carbonate (CaC03) which is harder, more dense, and thermodynarnicaIly less stable than the form of cornrnon calcareous rocks. Aragonite is produced by some invertebrates (shells, pearls) and by certain calcareous algae. It is also formed as low-temperature surface deposits. asystolic drug-a drug that induces a decreased contraction of the . ataxia-an inability to coordinate voluntary muscular movements that is symptomatic of some nervous disorder. atomic number-for the atom of a given element it represents the number of protons in the nucleus. atomic weight-the weight in grams of an element relative to that of carbon taken as 12. atoms-as far as chemistry and biology are concemed, the atoms are the ultimate building blocks of matter. atriastimulant drug-a drug that affects the contraction of the upper part of the heart. autotroph-a nutritionally self-sufficient organisms. barophiIic organisms-organisms growing at high pressures; generally they do not survive when brought to atmospheric pressure. barotolerant organisms-organisms which grow best at atmospheric pressure, but survive under conditions of high pressure. In the case of unicellular organisms functions such as cellular division are inhibited at high pressure, however. beam trawh:atching marine organisms on the sea bed by a tool made of a beam equipped with a bag-like net. bile pigments- pigments, originating from heme, which are eliminated from the liver and accumulated in the gall-bladder.

244 GlLOSSARY

bioluminescence-emission of light of biological origin; in macroorganisms it is often due to luminescent bacteria. biomass-total weight of living things in a given volume. bioassay-determination of the relative strength of a substance (as a drug) by comparing its effect on a test organism (or organ) with that of a standard preparation. biosynthesis-the synthesis of a natural product by a living organism or by a cellular culture, or by an enzymatic extract. biotechnology-exploitation of living organisms, or their products, for technological purposes. calcite-the softer form of calcium carbonate (see aragonite).

carbohydrates-compounds, also called sugars, of generally C.(H20). proportion

of atoms which are produced in the photosynthetic process from CO2 and Hp. Comprised are mono-, oligo-, and polysaccharides, which are made up of one, a few, or many sugar molecules, respectively, carotenoids-pigments, comprising eight isoprene-like units, and thus belonging to the tetraterpene class, which often occur in Nature as carotenoproteins, i.e. bound to a protein. central nervous system-the brain and the spinal cord. chemical bond-the bond that holds the nuclei together in a compound. The ionic bond results from the mutual attraction of ions of opposite electrical charges. The covalent bond resuIts from electron sharing between the nuclei. The hydrogen bond results from a mixture of these two bonding modes. The Van der Waals bonding, which is the weakest bonding, results from the mutual attraction of instantaneous dipoles formed by instantaneous displacements of the electrons with respect to the nuclei. chemical equilibrium-dynamic condition of a chemical system in which the rate of transformation of the reagents into the products equals that of the reverse reaction.

245 GW§§AlRY

chemical mark-a compound characteristic of a specific homogeneous group of living or fossil organisms and which can be used for taxonomie purposes. chemotaxonomy-a branch of biology that deals with the classification of living organisms on the basis of their specific chemical compounds. chirality (keir, hand)-the property of a molecule of not having a superimposable mirror image. chloroplast-a structure about 2.5 microns thick and 5 microns long, bound in a double-Iayered membrane, and composed of photosynthetic ceIls; it is the site of photosynthesis. chromosome-thread-like part of the ceIl nucleus, made of DNA bound to a protein, which carries genetic information. colonial organisms-organisms formed by aggregates of ceIls where neither organs nor tissue organization are discernible. Colonial should not be confused with multiceIlular; multiceIlular organisms have different ceIls for different functions. color and structllre-the carbon compounds that have a long series of alternate single and multiple chemical bonds absorb visible light and are thus colored. In contrast, when a moleeule does not possess multiple bonds, or the multiple bonds are separated by more than one single bond, such as the polyunsaturated fatty acid EPA of diatoms, only high-energy, non-visible light is absorbed so that the visible spectrum emerges unaltered and the compound is colorless. comparative biochemistry-a branch of biochemistry where similarities and differences in the biochemistry of the various taxa are emphasized. concentration-the amount of a dissolved chemie al compound per unitary volume. In order to make the measure independent of the nature of the compound, the concentration can be expressed in mole per liter. configuration-for a molecule it specifies an arrangement of the atoms with respect to one another that can not be changed without breaking and reforming bonds.

246 conformation-for a moleeule it specifies an arrangement of the atoms with respeet to one another that ean be ehanged by rotations around single chemie al bonds. coordination compounds--compounds made up of a eentral metallic atom linked to heteroatoms of molecules which are ealled ligands. -a ridge formed by ealeareous of living scleraetinian eorals and ealcareous algae, and of their remains. cross-linked polymers-in cross-linked polymers the polymerie chains are bridged to one another by chemical bonds; this reinforces the whole system. de novo synthesis-synthesis of a natural product by a living organism starting from simple precursors. diastereomers-stereoisomers which are not related to one another as mirror images. dopamine-alkaloid involved in the transmission of nerve impulses in the brain; it is the biogenetie precursor of other neuroactive hormones (epinephrine and norepinephrine ). dredging-or dredge sampling- eollecting sampies of living organisms or sediments from the sea bottom by means of a dredge. Earth's gases-methane and other simple natural gases. electronegativity-it is a measure of the ability of an atom, or of a group of atoms, to attract electrons. electron microscope-a microscope that uses a beam of electrons instead of a light beam to detect small objects. As the light assoeiated with the electron has much shorter wavelength than visible light, the electron mieroscope has a higher resolution than the light microscope. The light associated with the electron, by impinging on a fluorescent screen, is made visible to the eye. electrons-subatomic, negatively charged, small particles which travel around the nucleus at large distances (in terms of the dimensions of the electron and the nucleus) in such a number as to balance the positive charge of the nucleus.

247 GWSSAlRY

-branch of developmental biology that deals with the development of the . emulsion-mixture of two or more liquids where one of them occurs as non-miscible droplets of microscopic to submicroscopic size. enantiomers-isomers related to one another as mirror images. endoplasmic reticulum-system of membranes in the interior of the cytoplasm. enzyme-a protein, or protein complex, that speeds up chemical reactions. Chiral products of enzymatic reactions generally are pure enantiomers. epiphyte-a plant growing on another plant or on inanimate objects. evolution-the process by which living things originate from earlier forms. fatty acids-Iong-chain carboxylic acids of acetogeninic origin. They may be bound to glycerol to constitute the fats. follicle cell-a small sac, chiefly a lymphatic gland. fouling organisms-organisms that invade and obtrude other organisms or objects. functional group-small, reactive portion of a molecule, the chemical behavior of which is largely independent of the type of molecule. gel-liquid in which ultramicroscopic particles are dispersed or ordered. It may be elastic as gelatin or solid as silica gel. genetic engineering-misleading term to indicate a branch of biochemistry that is concemed with the manipulation of genetic material. ActuaIly, engineering is the application of scientific knowledge to problems of non-living systems. gill nets-series of superimposed nets of different sizes that is suspended vertically in the water with meshes that allow the head of a fish to pass but entangle it as it tries to withdraw. glycerol-the aJcoholic portion of ordinary fats. glycosides-acetals formed by the condensation (reaction with elimination of a water molecule) of the anomeric hydroxyl group (OR) of a sugar and the hydroxyl group of an alcohol.

248 GlLOSSA]R.Y

hatching factor-a compound that affects the emergence of young from eggs or other structures.

hepatopancreas-glandular organ of invertebrates which is called liver In . heteroatoms-in coordination chemistry heteroatoms are atoms rich in electrons, e.g. oxygen or nitrogen. heterotrophie bacteria-non-photosynthetic bacteria that can grow in specialized niches on various, even inorganic, compounds. histamine eITect-histamine is an alkaloid released under stress from tissues; it induces a dilatation of blood vessels, and thus a lowering of the blood pressure and inflammation of tissues. hormones-compounds produced in tiny amounts in living bodies where they serve to regulate physiological functions. hydrocarbons-compounds composed of carbon and hydrogen only. They are abundant in petroleum but are also biosynthesized by living organisms. hydrolysis-the splitting of a compound, such as a , by reaction with water to give smaller units (in this case the component mono- or oligosaccharides). indomethacin-synthetic indole alkaloid; it is taken as a reference standard for the analgesie and antiinflammatory action of other compounds. invertebrates-animals that lack a vertebral column. ion-an atom which has lost or gained one or more electrons and which therefore carrles positive or negative charges. ionophoric antibiotics-macrolides that have the ability to sequester an ion, or a complex ion, by placing it at the center of their macrocycle, coordinated to heteroatoms, generally oxygen atoms. irregular terpenes terpenes that can not be formally dissected into isoprene-likt units; they do not follow the isoprene rule.

249 isoprene (2-methyl-l,4-butadiene)-for simplicity it may be considered as the fonnal precursor of the terpenes; the true precursor is mevalonic acid, however. isoprene rule-the regular joining together of intact isoprene-like units to give compounds made up of two to eight of such blocks. isotopes-atoms having the same atomic number and thus constituting the same element while differing in the mass (Le. in the number of neutrons in the nucleus). K.,Na+-ATPase-enzyme active in the transport of potassium and sodium ions across cellular membranes. Le Chatelier principle-a system reacts to an extemal stimulus by moving in the direction in which the effect of the applied stimulus decreases. Iipids-a class of diverse compounds, of animal and non-animal origin, which include fats. macrolides-compounds having a large lactone (cyclic ester) ring. magnesium-one of the alkaline-earth metals; it is the central meta! in chlorophylls and bacteriochlorophylls. metabolism-it is the dynamic condition of the compounds contained in organisms. It includes all enzymatic processes that occur in the cell to allow growth and reproduction. micIoscIere-minute sclerite, i.e. sclerotized plate, in sponges. mixed biogenesis metabolites-natural products deriving from two, or more, different biogenetic routes. mole-it is the amount of a compound numerically equal to its molecular weight. molecular label-an isotope that can be distinguished from the other isotopes of the same element, usually through its radioactive or magnetic properties. Via synthetic or biosynthetic technologies, atoms of a molecu\e may be replaced by such a molecular label. molecule-two or more atoms bound together by chemical bonds to constitute the smallest units into which a pure compound can be separated.

250 GlLOSSARY

morphine-opium alkaloid with potent analgesic activity but with deleterious side effects. It can be chemically transfonned into heroin, which has a much higher euphorie effect. net production-the part of the primary production that is left after losses from respiration. neurotransmitter-a compound that diffuses across the synaptic cleft through nerve cells. nitrogen cycle-other than through nitrogen fixation, biological transfonnations of nitrogen compounds involve oxidation of soil ammonia by nitrifying bacteria, first into nitrites (NO;) and then into nitrates (N03"). Soil ammonia is released in the decomposition of organic material. nitrogen fixation-process in which nitrogen-fixing bacteria and certain cyanobacteria transfonn molecular nitrogen (N2) into nitrates (N03) nucleosides-compounds resulting from the joining of a sugar moleeule with a molecule of a nitrogen-containing aromatic base. By phosphorylation they yield nucleotides. Various types of free nucleosides are found as secondary metabolites. nucleotides-nucleoside phosphates, four types of which are found in the nucleic acids. nucleus (of the atom)-central small part of the atom with a positive electrical charge and practically the whole of the mass of the atom. nucleus (of the ceIl)-in eukaryotic cells it is a specialized structure enclosed in a double-layered membrane; it contains genetic material. one-carbon biomethylation-methylation of electron-rich atoms in molecules of living organisms by S-adenosyl-L-methionine. optical activity-plane-polarized light is rotated by the solution of a chiral compound present either as a single enantiomer or in enantiomeric excess. The instrument which measures the extent of rotation is called polarimeter. Looking toward the light source, through the solution, clockwise or counterclockwise rotations are indicated with the plus or minus sign, respectively. The extent of the rotation is

251 proportional to the amount of enantiomer in the sampIe tube and depends on the wavelength of the light. No prediction of absolute configuration can generally be made from the sign of the optical rotation. A more complex instrument, the dichrograph, uses circularly polarized light which, as a chiral light, recognizes opposite enantiomers. This technique is called circular dichroism. organelles-specialized substructures of ceHs. oxidation-oxidation of a chemical compound involves removing electrons from it. With organic compounds, oxidation often results in removing hydrogen atoms, such as it occurs in oxidizing an alcohol (R2CHOH) to a ketone (RzCO). Reduction is the reverse process.

oxygenic photosynthesis-conversion of water (H20) and carbon dioxide (C02) into carbohydrates (Cn(H20)n) and other essential metabolites under the action of light with production of molecular oxygen (02). parasite-a living organism that is associated with another living organism and benefits from it, generally not attempting to kill it. penicillins-antibacterial alkaloids produced by molds of the genus Penicillium. peptides-compounds formed by the condensation of a few amino acids (see peptidic bond). peptidic bond-bond formed by the condensation (reaction with elimination of a water molecule) of the amino group (NHR) of an amino acid with the carboxylic group (COOH) of a second amino acid. periodic table of the elements-arrangement of the elements in horizontal periods and vertical groups according to increasing atomic number. The elements of a group have similar chemical properties whereas from the left to the right along a period there is a change from metallic to non-metallic properties. Petri dish-round, flat, glass container used for the culture of microorganisms.

phenols-derivatives of benzene (C6~) with a hydroxyl group (OH) replacing a hydrogen atom.

252 GWSSA]RY

photochernical reactions-chemical transformations that begin with absorption of light by a rnolecule, which is thus raised to an electronically excited state. This rnay be followed by deactivation to the initial state with light emission, or by a chemical transformation in a dark process, or even by transfer of energy in a collision with a second molecule wh ich is thus raised to an electronically excited state. In the latter case, the first excited molecule acts as asensitizer. phylogenetic rnark--chemical compound characteristie of organisms whieh belong to phylogenetically related groups. phylogeny-evolutionary history, or evolution, of a homogeneous group of organisms. phytoalexins-compounds produced by plants under physieal or biologieal stress and which act as antimicrobials. -the floating or weakly swimming bacterial and minute animal and plant life of a body of water. plasmids-extrachromosomal genetic material of bacteria. plastids-membrane-enclosed organelles of photosynthetic cells; those containing chlorophyll are called chloroplasts. platelet-aggregation inhibitory action-ability of certain natural products to hinder the coagulation of blood by preventing platelet aggregation. polar cornpounds-compounds whieh have polar functional groups (i.e. groups formed with atoms of largely different electronegativity). Polar compounds are soluble in polar solvents. Non-polar compounds, typieally the hydrocarbons, lack polar groups and are soluble in non-polar solvents, typieally other hydrocarbons. A polar compound is strongly retained by polar chromatographie substrates, such as siliea gel or alumina, and requires solvents with hydroxyl functions, or other polar functions, to be eluted. polyrners-compounds of high molecular weight, consisting of repeating structural units that result from the union of simpler monomers.

253 GlLOSSA]RY

polypeptides-compounds of the type of the peptides, but formed from a higher number of amino acids.

polyphenols-highly oxidizable phenyl (C6Rs-) or polyphenyl compounds with two or more hydroxyl groups (OR) replacing hydrogen atoms at the phenyl rings. polysaccharides-see carbohydrates. pressure-force per unitary area. primary metabolism-biochemical reactions that start from carbon dioxide and light to afford primary metabolites (sugars, amino acids, and nucleotides). primary production-the production of compounds through photosynthesis. principle of maximum separation of electron couples-owing to electron repulsion, the electron couples of chemical bonds and lone pairs on atoms tend to lie as far apart as possible from one another in molecules. This determines the geometry of the molecule. prosthetic group-the non-protein group in a conjugated protein. proteins-compounds of the type of the polypeptides but consisting of a higher number of amino acids, which are chosen from only twenty types of a-amino acids. Conjugated pro teins are made up of a protein and a loosely bound prosthetic group; on mild treatment, the free protein and prosthetic group can be obtained. pyrrolic pigments-a-linked polypyrrole pigments typical of bacteria. racemate-a fifty to fifty mixture of the two enantiomers of a chiral compound. receptors-specialized cells wh ich have the ability to convert a stimulus into a nerve impulse. Receptors and their accessory structures constitute sense organs. Sense organs may react to various extemal stimuli, such as sound, light, or ehemical eompounds, usually with high speeificity resulting from the combination of various hand-glove systems or a more elaborated strategy. reduction-it is the reverse process of oxidation; see oxidation. saponins-compounds eomposed of asteroid or triterpene bound to a sugar by a glyeosidie bond.

254 GW§§AlRY

secondary metabolism-biochemieal reaetions that start from primary metabolites to give natural produets (= secondary metabolites) which are specifie of eertain groups of organisms or even of a single species. siderophore-a compound, generally of microbial origin, which has the ability to transport iron. sodium channels-to import nutrients, the cell has to export some substances in order to maintain a material balance. The cell membranes act as selective filters and in normal animal cells the imported substances are potassium ion, glucose, and amino acids, and the exported substance is sodium ion. When dinoflagellate toxins, such as saxitoxin and gonyautoxins, are ingested, they dissolve into body fluids as cations, thus being electrostatically attracted by negatively charged groups located around the orifiee of the sodium ion channe!. The channel is thus blocked, which prevents the cell from importing nutrients and causes its rapid death. stereoisomers-compounds differing in the spatial positions of the constituent atoms, which are bonded to one another in the same order. steroids-irregular triterpenoids which generally have lost some carbon units; certain sponge sterols have also acquired some carbon units. structural isomers-two or more compounds that are made up of the same number of atoms of the same elements but differ in the sequence the atoms are connected to one another. surfactants (= detergents)-compounds that affect the surface tension of a liquid. symbiont-a living organism that is associated for mutual cooperation with another living organism. -unit in biological classification. Taxa are arranged in ascending order from species to superkingdom. terpenoids-compounds that can be forrnally imagined to derive by the joining together of five-carbon isoprene-like units. The number of such units indicates the class of the terpene; thus, hemiterpenes, monoterpenes, sesquiterpenes, diterpenes,

255 GWSSAlIff sesterterpenes, ttiterpenes, and tetraterpenes are formed from two, three, four, five, six, and eight isoprene-like units, respectively. tetrahedral, trigonal, and digonal carbon-bonding modes of carbon to either four, three, or two partner atoms which lie at the vertices of a tetrahedron, the vertices of a ttiangle, or along a line, with carbon at the center. total synthesis-Iaboratory synthesis of a natural product starting from simple precursors. truncated (or degraded) terpenes-terpenes that have lost at least one carbon atom during biogenesis. X.ray ditTraction-light being reflected from a ruled surface, such as a grating, may produce fringes of parallel light of high luminosity and low luminosity, while decomposing into its component colors. This is the phenomenon of diffraction of light. With light of very short wavelength, such as the X-rays, diffraction can only occur with such tightly mIed surfaces as those created by the network in crystalline matter. In this case, diffraction bands allow us to measure the interatomic distances and to reconstruct the relative positions of all atoms in the crystal. yeasts-unicellular phase of many lower fungi where reproduction occurs by fission or .

256 INDEX

The location of illustrations is indicated by page numbers in boldface. The location of structural forrnulae is indicated by page numbers in italics.

Acantharians peroniatriol-I 145, 200 Acantholithium dicopum 9, 9 plakinic acid-A 96, 194 Acetogenins prostanoids acrylic acid 18, 31 from Clavularia sp. 121 aplasmomycin 71, 201 {l5R)-PGAz 199 aplysiatoxin, debromoaplysiatoxin 32, (15S)-PGAz 127,199,233 46, 101, 139,200 (15S)-PGAz methyl ester 127 arachidonic acid 43, 104, 144,198 punaglandin-4 120,199 arsenobetaine 50, 195 sphinxolide 143, 200 'balanoacid' 151, 194 swinholide-A 102 bengarnides 104, 194 thyrsiferol 9, 45, 211 brevetoxin-B 26, 197 tridachione 140,200 bryostatin-l 167,201 ulapualide-A 143 calyculin-A 100, 195 Algae caulerpicin 54, 194 green boring diemenensins 145 Ostreobium 58 dinophysistoxins 136 green flagellates 2,3-diphosphoglycerate 75 Chlorella vulgaris 13 duryne 101,196 green prokaryotic duryne-like 102 Prochloron didemni 54, 234 EPA 18, 160,199 red endolithic from brown seaweeds 52,195 Conchocelis 11 from hexactinellids 106 see also under "", from Leiopathes sp. 121 "Diatoms", "Dinofiagellates", from Siphonochalina truncata 102 "Non-marine species", halogenated from seaweeds 39, 196 "Phytoplankton" , kabiramide-C 143 "Prymnesiophyceae", "Seaweeds" latrunculin-A 98, 143, 201, 233 Alkaloids misakinolide-A 100 aaptamine 103,223 mycalarnide-A 102 aplysinopsins 115, 221 odoriferous hydrocarbons of brown aplysioviolin 140, 222 seaweeds 52, 196 ascididemnin 166, 225 okadaic acid 93, 198, 232 caffeine 123, 224, 233 palytoxin 130, 198 coelenterazine 119,231 pectenotoxin-I 136,201 cyc1oprodigiosin 71,222

257 lINJDilEX (Al\Al][NO ACID MJE1['AlBOUflES-ASCIDlfANS)

cystodytin-A 166, 225 a-allokainic acid 217 6,6' -dibrornoindigotin 139, 222 dornoie acid 44, 217, 233 dopamine 122,225 GABA 47, 218, 233 dragmacidin 100 hornarine 125,218 dysiazirine 97, 224 a-kainic acid 44, 217 eudistomidins 167 laminine 49, 218 eudistomin-C 167,221 non-protein 49 frorn Glossobalanus sp. 149 palythine 115,218 gonyautoxin-l 21,220 proline 45, 217 hymenin 103,222 Archaebacteria imbricatine 161,223 lipids of 75,196 indigotin 222 Methanococcus jannaschii 75, 196 keramadine 103,223 Methanopyrus 74 leucettidine 106, 224 factor F430 in reducing enzymes 185 lyngbyatoxin-A 33, 220 Pyrodictium 74 rnanzamine-A 101, 221 Ascidians (Aplousobranchia) rnethylaplysinopsin 122, 221, 233 Aplidium californicum 81, 166, 166 naamidine-A 106, 223 Aplidium californicum frorn Bahia nereistoxin 148,227 Kino 167 prianosin-A (= discorhabdin-A) 100, Aplidium californicum of Golden Gate 225 Bridge 166, 203 prodigiosin 71, 222 Aplidium sp. of the Gulf of California ptilocaulin 94, 99, 220 166,206 saxitoxin 24, 220 Cystodytes dellechiajei (Della Valle) surugatoxins 72, 136 166,225 tambjamines 142 Didemnum sp. 166, 225 tetrodotoxin 72, 169,220 Didemnum voeltzkowi 166 xestospongin-C 103,224 Eudistoma glaucus 167 zoanthoxanthin 121,219 Eudistoma olivaceum 167,221 Amino acid rnetabolites Leptoclinides sp. 166 aerothionin, hornoaerothionin 95 Lissoclinum patella 166 anguibactin 71, 226 Ritterella sigillinoides (Brevin, 1956) aplysinopsins 115 221 7-brornocavernicolenone 95, 226 Trididemnum cereum (Giard, 1872) 167, brornochloroverongiaquinol 95, 226 227 cavernicolins 95 Trididemnum cf. cyanophorum 166 dopamine 122, 225 Trididemnum solidum (Van Name) 94, purealin 103, 226 165,219 Amino acids Ascidians (Phlebobranchia) alanine, aspartic acid, glutamic acid Ascidia nigra (1...) 165, 219 45,217 Ciona intestinalis 164

258 lINDlEX (ASCIDnAN lP'IRODUcrS-lBllOACflIVlH lP'IRODUCll'S)

Ascidian natural products dihydroflavin monophosphate 230 aplidiasphingosine 166,206 2,3-diphosphoglycerate 75 ascididernnin 166,225 diphytanyl diglyceryl cyclic ether 196 aplysianin 140 macrolide of a deep-sea bacterium 72 cystodytin-A 166, 225 methane 74, 185 2'-deoxyuridine 167,227 palytoxin 72, 198 didernnin-B 166,219 peptidoglycans 68, 74, 228 eudistomidins 167 prodigiosin 71, 222 eudistornin-C 167,221 prosthetic group (factor F430) in prenylquinone 166,203 reducing enzymes 185 sulfuric acid 141 surugatoxins 72, l36 tunichrome-Bl 165,219 teichoic acids 68, 229 ulicyclamide 166 tetrodotoxin 72, 220 Bacteria Bioactive marine natural products Actinomycetes 72 alarm substances Alteromonas rubra 70, 222 acanthaglycoside-A 160,215 Beggiatoa 69 aplysioviolin 140,222 Beneckea gazogenes 70, 222 echinoside-A 161,212 ceil walls of 69,228,229 allergenic substances Chainia sp. 71-72 of gelatinosum 155 chemolithotrophic 69 anthelrninthic substances in deep sea 65, 72, 77 a-allokainic acid 217 luminous 72 bengamides, bengazoles 104, 194 photosynthetic 69, 182, 185-186 domoic acid 44, 217, 233 Pseudomonas bromoutilis 71 a-kainic acid 44, 217 Pseudomonas sp. 71 antiatherosclerotic substances Rhodobacter sphaeroides 186 carrageenans 43, 44, 228 Rhodopseudomonas viridis 186 EPA 160,199 Serratia marcescens 71, 222 antibacterial substances Streptomyces 33, 68, 71 acrylic acid 18, 31 Streptomyces griseus 71, 201 aerothionin and homoaerothionin 95 Vibrio anguillarum 71, 226 aplasmomycin 71, 201 Bacterial natural products aplysianin-A 140 antibiotic SS-228Y 72 7-bromocavernicolenone 95,226 aplasmomycin 71, 201 bromochloroverongiaquinol 95, 226 bacteriochlorophyil-a, b, c 182-184, cavernicolins 95 183 diemenensins 145 bacteriochlorophyil-d, e 184, 184-185 dysiazirine 97, 224 bacteriohopanetetrol 75, 213 echinochrome-A 159,202 bacteriopheophytin 185 EPA phytol ester 18 cycloprodigiosin 71, 222 from diatoms 18

259 ][N][Jl]EX (lB][OAClrlIVlE lPlRODUCfS)

garveatin-A 124, 199 halimedatrial 58, 206 halimedatrial 58, 206 kabiramide-C 143 kelletinin-I 144, 193 jasparnide 94 melinacidins 81 plakinic acid-A 96, 194 phenolic compounds from seaweeds antiinflammatory substances 70 cladiellin 123, 207 proteins from Aplysia kurodai 140 foliaspongin 104 ptilocaulin 94, 99,220 luffariellin-A and -B 104 siccayne 81 manoalide 104,210 anticoagulant substances pseudopterosin-A 123,209 fucoidan 49, 228 antileukernic substances antidepressant substances ascididemnin 166, 225 methylaplysinopsin 122, 221, 233 bryostatin-l 155, 201 antifeedant substances calyculin-A 100, 195 aplysiatoxin, debromoaplysiatoxin cephalostatin-l 149,216 32,46,200 cystodytin-A 166, 225 from A/disa sanguinea cooperi 142 desacetylscalaradiall0l,210 9-isocyanopupukeanane 142,204 discorhabdins 100 nakafuran-8 97, 142,204 dolastatin-1O 140,218 polygodial142 dragmacidin 100 tambjamines 142 duryne 101,196 antifouling substances hormotharnnione 27, 202 briareins 122 dysiazirine 97, 224 cycloprodigiosin 71, 222 manzamine-A 101,221 fatty acid from Cladosiphon rnisakinolide-A 100 okamuranus 50 peroniatriol-I 145, 200 homarine 125,218 prianosin-A (= discorhabdin-A) 100, idiadione 98, 209 225 low molecular weight polymers from ptilocaulin 94, 99,220 Renilla reniformis and ulapualide-A 143 Lophogorgia virgulata 125 anti-protozoan substances mucous substance from Pterogorgia aplasmomycin 71, 201 citrina 126 melines 104 muricins 126 antispasmodic substances palustrol 126 agelasidines 133 prodigiosin 71, 222 okinonellin-A 103, 210 renillafoulin-A 122, 125, 208 antiviral substances stylatulide 126 avarol 102, 204 antifungal substances didemnin-B 166, 219 dysiazirine 97, 224 dolastatin-1O 140, 218 goniodomin-A 27 eudistomin-C 167,221

260 KNDlEX (lEIlOACTIVlE lPlRODUClI'S)

macrolide of a deep-sea bacterium hatching factors 72 'balanoacid' 151, 194 mycalamide-A 102 hemolytic substances proteins from abalone 144 acanthaglycoside-A 160,215 calmodulin antagonists echinoside-A 161,212 eudistomidins 167 pavoninin-l 170,215 cytotoxic substances proteins 117 acanthifolicin 26 herbicidal substances aplidiasphingosine 166,206 from hexactinellide sponges 106 aplysianin-A 140 from Neomeris annulata 58 didemnin-B 166,219 hormones dolastatin-lO 140,218 and circadian rhythms 20 duryne 101,196 molting 129, 151-152,216,233 dysiazirine 97, 224 molt -inhibiting laulimalide 10 1 3-hydroxy-L-kynurenine 151 from 101,226 plant growth regulators 175 from Aplysia kurodai 140 ichtyotoxic substances okadaic acid 26, 101,198,232 'caulerpatriene' 58,203 prenylquinone 166,203 cavemosine 98, 211 punaglandin-4 120, 199 denticulatolide 127 sphinxolide 143,200 desacetylscalaradial 98, 101, 210 SS-228Y 72 halimedatrial 58, 206 stypoldione 50, 209 herbasterol 97, 216 swinholide-A 102 heritol 63, 204 thyrsiferol 45, 211 in Uthophyton viridis 127 deterrent substances latrunculins 98, 201 acanthaglycoside-A 160, 215 limatulone 144, 213 aplysioviolin 140,222 mosesins 170 echinoside-A 161,212 pacifigorgiol 127, 205 imbricatine 161, 223 pardaxins 170 enzyme inhibitors pavoninin-l 170, 215 agelasine-A 103, 208 PG~ methyl ester 127 dysideapalaunic acid 103, 211 stypoldione 50, 209 peptide of Tetrosia sp. 102 verrucosin-A 142, 209 purealin 103,226 inflarnmatory substances terpene of Epipolasis 102 aplysiatoxin, debromoaplysiatoxin enzyme activators 32,46, 101, 139,200 purealin 103, 226 lyngbyatoxin-A 33, 220 growth regulators inhibitors of crustaceans litophynins 123 palustrol 126 stylatulide 126

261 llNDID{ (lBllOACll'lIVlH lPlRODUCfS)

inhibitors of the cell division of cystodytin-A 166, 225 fertilized sea-urchin eggs doparnine 122,225 acalycixeniolides 121, 207 GABA 47,218,233 and cytotoxicity 159 hymenin 103,222 avarol 102, 204 keramadine 103,223 diemenensins 145 lophotoxin 123, 131,207 imbricatine 161, 223 renillafoulin-A 125,208 okinonellin-A 103, 210 methylaplysinopsin 144,221, 233 stypoldione 50, 209 spongosine 103 terpenes from Cacospongia scalaris terpenes from Armina maculata and from Izu Peninsula 99 Veretillum cynomorium 122 inhibitors of the cell division of tetrodotoxin 72, 169, 220 fertilized starfish eggs phytoalexins acalycixeniolide-A 121,207 in green seaweeds 55 moritoside 128, 206 removers of noxious salts mycalisine-A 103, 226 alginic acids (Sr salts) 48-49 saponins from Anthoplexaura fucoidan (Pb salts) 49 dimorpha 128 settlement inducers inhibitors of platelet aggregation GABA 47, 218, 233 from Halichondria sp. 104 high-molecular-weight from Renilla insect-growth inhibitors reniformis 125 litophynins 123, 151 sodium-channe1-affecting substances insecticidal substances brevetoxin-B 26,197 a-allokainic acid 217 from Anemonia sulcata 120 a-kainic acid 44, 217 tetrodotoxin 72, 169,220 nereistoxin 148, 227 solar filters laxative substances aplysinopsins 115, 221 carrageenans 42, 228 melanins 115 inducers palythine 115, 218 jacaranone 47 tridachione 140,200 musc1e-affecting substances spawning inhibitors aaptarnine 103, 223 asterosaponins 160 agelasidines 103 spermicidal substances hymenin 103, 222 halimedatrial 58, 206 laminine 49, 218 tissue-growth stimulators peptides from Chironex fleckeri 117 carrageenans 42, 228 neuroactive substances toxins aaptarnine 103, 223 acanthaglycoside-A 160,215 ascididemnin 166, 225 aplysiatoxin, debromoaplysiatoxin briareins 122 32,46,101,139,200 caffeine 144,224, 233 arsenobetaine 51, 195

262 lINDlEX (lBKOACJmllE lPlRODUcrS-CAlRlBOHlIDlRA1'lES)

avoidance by Chaetodon ocellinatus xestospongin-C 103, 224 127 Bioactivity tests 7, 19, 150, 187 brevetoxin-B 26, 197 Bioluminescence caulerpicin 54, 194 extracellular 118, 153 ciguatoxin 25, 197 of bacteria 72, 230 conotoxin 144 of cnidarians echinoside-A 161, 212 Aequorea forskalea 118, 118,231 diarrhetic 136 Pelagia noctiluca 118, 118 dinophysistoxins 136 Pennatula phosphorea 119, 119 'eckloniaarsenoribofuranoside' 50, Renilla reniformis 119 193 of crustaceans geographus toxin 144 Cypridina hilgendorfii 153, 230 gonyautoxin-l 21,220 Euphausia pacifica 153,230 heritol 63, 204 of fish idiadione 98, 209 Argyropelecus 73, 73 irnbricatine 161, 223 Paralepsis 73 latrunculin-A 98, 143,201,233 Photoblepharon 74, 74 lophotoxin 123, 131,207 of dinoflagellates 16, 20, 153, 230 lyngbyatoxin-A 33, 220 Brachiopods palytoxin 130, 198 Gryphus vitreus 157, 157 paralytic shellfish poisons 21, 136 Bryozoans (Anasca) pectenotoxin-I 136, 201 155, 155, 201 polypeptidie from cyanobacteria 33 foliacea 155 saxitoxin 21, 220 Flustra papyracea 155 sumgatoxins 136 Sessibugula translucens 142 tetrodotoxin 72, 169,220 Bryozoans (Cheilostomata) 'tridacnaarsenoribofuranoside' 50, Alcyonidium gelatinosum 154-155 193 Amathia convoluta 155, 201 yessotoxin 136 Myriapora truncata 154 tumor promoters Sertella beaniana 154 lyngbyatoxin-A 33, 220 Bryozoan natural products vascular-system-affecting substances bryostatin-l 167, 201 caffeine 123,224, 233 from Alcyonidium gelatinosum 155 1aminine 49, 218 from Flustra 155 from Halichondria sp. 104 Carbohydrates okinonellin-A 103,210 acanthag1ycoside-A 160,215 palytoxin 130, 198 batyl alcohol196 polypeptides from sea anemones 120 dihydroflavin monophosphate 74, 230 spongosine 103 echinoside-A 161,212 subergorgie acid 131,205 'eckloniaarsenoribofuranoside' 50, 193 xestoquinone 103, 202 fucose 228

263 ][N]DlEX (CAlltO'flENOIDS-CNIDAlUANS)

galactose 228 Xenia 121 guluronic acid 228 antipatharians kelletinin-I 144, 193 Leiopathes sp. 121 leptoshaerin 81, 193 gorgonians mannuronic acid 228 Acalycigorgia inermis 121, 207 moritoside 128, 206 Anthoplexaura dimorpha 128 pavoninin-l 170,215 Briareum asbestinum 28, 28, 122 pseudopterosin-A 123, 209 Corallium rubrum 108, 108 verrucosin-A 142, 209 Corallium sp. 128 see also under "Phycocolloids" and Eunicella 132 "Polysaccharides" Euplexaura sp. 128, 128, 206 Carotenoids Leptogorgia setacea 125, 218 B,B-carotene 14, 18, 214 Leptogorgia virgulata 125, 125, 218 fucoxanthin 14, 214 Lophogorgia 123,207 peridinin 14, 214 Lophogorgia alba 207 Carotenoproteins 14-15 Lophogorgia chilensis 131, 207 Cephalochordates Lophogorgia cuspidata 131, 207 Branchiostoma 192 Lophogorgia panamensis 131 Chelicerates Lophogorgia rigida 131,207 Carcinoscorpius rotundicauda 152, 153 Muricea calijornica 126 Chemical marks Muriceafructicosa 125 dinosterol for the dinoflagellates 29, Pacijigorgia cf. adamsii 127, 205 215 Paragorgia arborea 128, 128 proline for the Rhodomelaceae 45, 217 Paramuricea 132 Circadian rhytms 20 Paramuricea chamaeleon 123, 224, Cnidarians 233 alcyonaceans Plexaura homomalla (Esper), forma Alcyonium [= Parerythropodium] homomalla 127,199 coralloides 132, 132 Plexaura homomalla (Esper), forma Cespitularia aff. subviridis 126 kükenthali Moser 127,199, Cladiella sp. 123,207 233 Heliopora coerulea 112, 112 Pseudopterogorgia elisabethae (sp. Litophyton sp. 123 nov.) 123, 209 Litophyton viridis 126 Pterogorgia citrina 126 Lobophytum denticulatum Subergorgia suberosa 131,205 (Tixie-Durivault, 1956) 127, hydroids 127 Aglaophenia pluma (L.) 221 Nephthea sp. 122, 225 Corymorpha nutans 109,117,117 Sarcophyton trocheliophorum 109 Garveja annulata 124, 124, 199 Sarcophyton sp. 109 Millepora 112, 116 Sinularia heterospiculata 122, 225

264 jellyflsh zoanthids Aequoreaforskalea 118, 118-119, Gerardia savaglia (Bertolini, 1819) 231 128-130, 129, 152, 216, 233 Chironex fleckeri 117, 117 Palythoa 72, 130 Chiropsalmus 117 Palythoa caribeorum 130, 198 Pelagia noctiluca 109, 118, 118 Palythoa toxica 130-131, 198 Physalia 117 Palythoa tuberculosa 115, 130-131, pennatulaceans 130, 198, 218 Pennatula phosphorea 119, 119 Parazoanthus axinellae 121, 121, Renilla reniformis 119, 122, 208 219 Scytalium tentaculatum 122 Parazoanthus axinellae adriaticus Stylatula sp. 126 219 Veretillum cynomorium 122, 122, Cnidarian natural products 125 acalycixeniolide-A 121, 207 sc1eractinians aequorin 118 Acropora 115, 116 ajugasterone-C 233 Acropora formosa 115, 218 aplysinopsins 115, 221 Dendrophylliidae 115, 122, 221 arboxeniolide-l 128 Echinopora lamellosa 116, 213, 233 briareins 122 Fungia compressa 112, 112 caffeine 123, 224, 233 Goniopora 111 c1adiellin 123, 207 Montipora verrucosa 112 coelenterazine 119,231 Pavona 111 coralloidins 132 Pocillopora 111 denticulatolide 127 Pocillopora damicormis 112 dinosterol28-29, 116,215,232 Porites compressa 112 doparnine 122, 225 Tubastraea 115, 122 ecdysterone 129, 151, 233 sea anemones (20p)-echinolactone-B 116,213, 233 Anemonia sulcata 120, 120 fatty acids from Leiopathes sp. 121 Anthopleura elegantissima 121 from Anthoplexaura dimorpha 128 Anthopleura xanthogrammica 121 from Lithophyton viridis 126 Calliactis parasitica 120, 120 from Scytalium tentaculatum 122 stoloniferans from Veretillum cynomorium 122, 125 Clavularia sp. 121 garveatin-A 124, 199 Sarcodictyon roseum [= Rolandia gerardiasterone 129,216 rosea] 123, 124, 132, 208 high-molecular-weight polymers from Tubipora musica 112, 112 Renilla reniformis 126 telestaceans homarine 125,218 Telesto riisei 120, 120, 199 litophynins 123 lophotoxin 123, 131,207 methylaplysinopsin 122,221, 233

265 llNDlEX (COWlR-CY ANOlBACfJElIUAlL lPlRODUCfS)

moritoside 128, 206 Crustaceans mucous substance from Pterogorgia amphipods 56, 77 citrina 126 Balanus amphitrite 125, 125 mucous polymers from scleractinians Balanus balanoides 151, 194 115 Cypridina hilgendorfii 153 muricins 126 Daphnia magna 150 pacifigorgiol 127,205 Demania reynaudii 131, 198 palustrol 126 Euphausia pacijica 153, 230 palythine 115,218 Laura gerardiae 129-130 palytoxin 130,198 Pseudosquilla ciUata 152 (15R)-PG~ 199 Sergestes lucens 50, 195 (15S)-PG~ 127, 199, 233 Tisbe furcata 126 (15S)-PG~ methyl ester 127 Crustacean natural products polypeptides 120-121 arsenobetaine 50, 195 prostanoids 41, 120-121, 127 'balanoacid' 151, 194 proteins 117-119 'cypridinaluciferin' 153,230 pseudopterosin-A 123,209 ecdysterone 129, 151, 233 punaglandin-4 120, 199 'euphausialuciferin' 153,230 renillafoulin-A 122, 125, 208 homarine 125,218 sarcodictyin-A 123, 208 palytoxin 130, 198 scleroproteins 128 Cryptophyceae 27 stylatulide 126 Chrysophaeum taylori 27, 202 subergorgic acid 131,205 Chryptophyceae natural products zoanthoxanthin 121,219 honnothanmione 27, 202 Color Cyanobacteria of marine invertebrates 14 aerial nitrogen fixation, by 29 of mollusks 137-138 Anabaena jlos-aquae 33 of phytoplankton (red tides) 14 Hormothamnion enteromorphoides of seaweeds 35 (alleged) 27 of sea urchins 159 Lyngbya majuscula [= Microleus photoreceptors 152 lyngbyaceus] 32, 32, 46, 200, 220 Coral reefs Microcystis aeruginosa 33 atoll 111, 111 Nostoc 32, 32 barrier reef 110, 110 pesticide-resistant 30 faros 111 Cyanobacterial natural products fringing reef 110, 110 aplysiatoxin, debromoaplysiatoxin 32, lagoon 110-111 200 rnicroatoll 111 lyngbyatoxin-A 33, 220 patch reef 111 phycocyanobilin 181,182 table reef 111

266 Depsipeptides luciferin 16, 20, 230 didenmin-B 166, 219 luminescence 16 jaspamide 94 Noctiluca scintillans 21 Diatoms Prorocentrum lima 24, 26, 198,232 Chaetoceros 17,17 Prorocentrum sp. 26 Chaetoceros lauderi 19 Protogonyaulax 22, 220 Navicula 17 Zooxanthella microadriatica [= Navicula delognei var. elliptica 18 Symbiodinium microadriaticum] 28, 28, Navicula salinicola 125 29,114,232 Nitzschia 17, 17 Dinoflagellate natural products Nitzschia frustulum 13 amphidinolide-C 27 Phaeocystis costatum 18 brevetoxin-B 26, 197 Phaeodactylum tricornutum 18, 199 carotenoids 18 Skeletonema costatum 18 ciguatoxin 25, 197 Diatom natural products 'dinoluciferin' 16, 20,230 acrylic acid 18 dinophysistoxins 136 carotenoids 14-15, 18 dinosterol 28-29, 215, 232 ß-dimethylpropiotethin 18, 31 goniodomin-A 27 dimethyl sulfide 18,31 gonyautoxin-l 21,220 EPA 18,199 okadaic acid 26, 93, 198, 232 EPA phytol ester 18 pectenotoxin-I 136, 201 polymerie sugar of Chaetoceros lauderi peridinin 14, 214 18-19 saxitoxin and gonyautoxins 21,220 Dinoflagellates yessotoxin 136 Alexandrium hiranoi [= Goniodoma Echinoderms (crinoids) pseudogonyaulax] 27 Comantheria 158 Amphidinium sp. 24, 27 Comanthus bennetti 158, 158 Dinophysis 136 Cromatula 158 Dinophysis acuminata 136 Lamprometra 158 Dinophysis acuta 136 Echinoderms (olothurians) Dinophysis fortii 136 Actinopyga echinites (Jaeger) 161, 212 Gambierdiscus 11 Actinopyga sp. 161 Gambierdiscus toxicus 24, 24, 25, 197 Echinoderms (sea urchins) Gonyaulax 22, 220 Diadema antillarum 57, 57 Gonyaulax catenella 22 Lytechinus pictus 58, 206 Gonyaulax 22 Paracentrotus lividus 159 Gonyaulax polyhedra 20, 20 Strongylocentrotus intermedius 160 Gonyaulax tamarensis 21-22 Strongylocentrotus purpuratus 160 Gymnodinium breve Davis [= Echinoderms (starfish) Ptychodiscus brevis] 22-23, 136, 197 Acanthaster planci (L.) 60, 160-161, Gymnodinium sp. 22 161,215

267 llNlDlEX (lOClHDlNODlElRM lP'llWDUcrs-lFlL§JH[ lP'lRODUcrs)

Asterina pectinifera 99, 128 Fattyacids Dermasterias imbricata 161, 223 arachidonic acid 43, 104, 144,198 Pisaster giganteus 98 EPA 18, 160,199 Echinodenn natural products from Leiopathes sp. 121 acanthaglycoside-A 160,215 Fish echinochrome-A 159,202 Alutera scripta 131 echinoside-A 161, 212 Anoplopoma jimbria 77 EPA 160, 199 Aphanopus carbo 77 growth factors 160 Aracana omata 169 imbricatine 161,223 Argyropelecus 73, 73 pigments 159 Chaetodon 97 tetrodotoxin 72, 169,220 Chaetodon ocellinatus 127 Emergent plants damselfish Heritiera littoralis 10, 63, 204 Abudefduf annulatus 126 mangrove swamps 62 Abudefduf leucogaster 126 salt marshes 62 Duscyllus aruanus 58 Emergent-plant natural products Eupomacentrus leucostictus 127 heritol 63, 204 Eupomacentrus planifrons 58 Enzymes Pomacentrus coeruleus 47 aldose reductase 103, 211 Hoplostethus atlanticus 77 bacterial luciferase 230 Macrourus 77 bromoperoxidases 9, 193 moray eel (Gymnothorax javanicus) 25, Ca++-ATPase 103, 226 197 catalases 180 menhaden 23 cnidarian luciferases 119, 231 Oryzias latipes 127 Cypridina luciferase 153, 230 Ostracion cubicus 169 dinoflagellate luciferase 16, 20 Paralepsis 73 Na+,K+-ATPase 45, 102-103,208,226 Pardachirus marmoratus 170 K+-EDTA-ATPase 103, 226 Pardachirus pavoninus 170, 170,215 nitrogenase of cyanobacteria 30 parrotfish of Archaebacteria 185 Scarus scaber 56, 56 peroxidases 180 Ypsiscarus ovifrons 169, 198 prostaglandin synthase 123 Photoblepharon 74, 74 tyrosinases 236 puffer fish 169 Eukaryotic cell174 Rhinesomas reipublicae 169 Evolutionary marks Squalus 211 phycocyanobilin 181-182 surgeonfish 56 phycoerythrobilin 181-182 Fish natural products type and sequence of amino acids in choline esters 169 proteins 176 ciguatoxin 25, 197 EPA 199,199

268 lINDEX (lFUNGli-MOUUSKS)

mosesins 170 MammaIs palythoxin 130,198 bottle-nose dolphin 23 pardaxins 170 Mollusks pavoninin-1 170,215 accumulation of toxins by 136 shampoo 168 feeding on Earth's oils 134 squalene 211 shipworms 135 tetrodotoxin 72, 169 220 Mollusks (Archaeogastropoda) Fungi Turbo pica 24 Asteromyces cruciatus 81 Mollusks (bivalve) Corollospora pulchella 81 musseIs of Japanese waters 201 Dendryphiella saUna 81-82, 81, 205 Mytilus californianus 22 Halocyphina villosa 80, 80 Mytilus galloprovincialis 115,218 Helicascus kanaloanus 81 Pecten maximus 47, 47 Leptosphaeria oraemaris 81, 81, 193 Pinctada margaritifera 139 pathogenic 80 Pinctada mertensi 139 Zopftella marina 81-82 Pinna nobilis 134 Fungal natural products scallops of Japanese waters 201 dendryphiellic acid 82 Tridacna gigas 133 dendryphiellin-A 82, 205 Tridacna maxima 50, 133, 133, 193 from Helicascus kanaloanus 81 Mollusks (Cephalopoda) gliovictin 81 Octopus vulgaris 134 leptosphaerin 81, 193 Mollusks (Mesogastropoda) melinacidins 81 Cyphoma gibbosum 127 ochracin 81 Mollusks (nudibranchs) siccayne 81 Aldisa sanguinea cooperi 142 zopfinol82 Archidoris montereyensis 142 Hydrocarbons Armina maculata 125 flavors from brown seaweeds 52 Chromodori elisabethina 143, 143, "ocean smell" 52,196 201, 233 terpenoidal of algae 13 Chromodoris maridadilus 142 Lignins Dendrodoris limbata 142 building blocks of 229 Discodoris planata 141 in seagrasses 61, 229 Doris verrucosa 142-143,209 lack in seaweeds 10 Hexabranchus sanguineus 143 Lucüerins Hypselodoris godeffroyana 142 aequorin 118 Phyllidia varicosa 142,204 coelenterazine 119,231 Roboastra tigris 142 'cypridinalucüerin' 153,230 Tambje 142 'dinolucüerin' 16, 20,230 Tylodina perversa 95, 95 'euphausialucüerin' 153,230 unidentified from Hawaii 143, 200 of bacteria 74, 230 unidentüied from Kabyra Bay 143

269 llNDlEX (MOU.USKS-NATIJJRAL JFlRODUCll'S)

Mollusks (prosobranchs) diemenensins 145 abalone (Haliotis) 47 6,6'-dibromoindigotin 139,222 Babylonia japonica 72, 136 dinophysistoxins 136 Buccinulum corneum 193 dolastatin-lO 140,218 Charonia tritonis (giant triton) 162 from Aldisa sanguinea cooperi 142 Collisella limatula 144,213 from Armina maculata 125 Conus geographus 144 geographus toxin 144 Conus textile 144, 144, 198 indigotin 222 Cyphoma gibbosum 127 9-isocyanopupukeanane 142,204 Dicathais 222 kabiramide-C 143 Kelletia kelletii 144, 193 kelletinin-I 144, 193 Murex 138, 222 latrunculin-A 143, 201, 233 Murex brandaris 138, 138 limatulone 144, 213 Purpura 137 nakafuran-8 142,204 Mollusks (pulmonates) pectenotoxin-I 136, 201 Onchidella binneyi 145 peroniatriol-I 145, 200 Onchidellafloridanum 145 polygodia1142 Peronia peronii 145,200 sphinxolide 143,200 Siphonaria diemensis 145 surugatoxins 136 Siphonaria sp. 145 tambjamines 142 Mollusks (sacoglossan) tridachione 140,200 Placobranchus ocellatus 140,200 'tridacnarsenoribofuranoside' 50,193 Mollusks (sea hares) ulapualide-A 143 Aplysia 139-140, 222 verrucosin-A 142, 209 Aplysia californica 46, 46 Natural products Aplysia kurodai 140 accumulation in specialized cells 46, Dolabella auricularia 140, 218 95, 175 Stylocheilus longicauda 32, 46, 139, actual form in living organisms 15 200 as models for the synthesis of drugs Mollusc natural products 148 adenochrome 134 biodegradation 75 aplysianin-A 140 biosynthesis in cell compartments 175 aplysiatoxin, debromoaplysiatoxin 101, chemical marks 139,200 dinosterol 29, 215 aplysioviolin 140,222 proline 45, 217 arachidonic acid 144, 198 evolutionary marks 7-bromocavemicolenone 95, 226 phycocyanobilin 181,182 bromochloroverongiaquinol 95, 226 phycoerythrobilin 181,182 byssus 134-135 proteins 176 cavernicolins 95 inorganics and organometallic 192-193 conotoxin 144 aragonite 57, 139

270 arsenosugars 50 Chloropseudomonas 182 calcite 57 Mycobacteriun avium 19 carbon dioxide 180 Mycobacterium leprae 19 magnesium compounds 178-179, Mycobacterium tuberculosis 19 183-185 Rhodobacter sphaeroides 186 magnetic iron compounds 70 Rhodopseudomonas 182 mercury compounds 12 Rhodopseudomonas viridis 186 silicon dioxide 89, 181,181 Rhodospirillum rubrum 183 strontium in place of calcium 9 Staphylococcus aureus 145 sulfate 31 Streptococcus 94 sulfuric acid 141 Streptococcus pyrogenes 94 vanadium compounds 165, 179, 219 Streptomyces sp. 33,68, 71 limits in the detection 23, 157 cyanobacteria of dietary origin 4, 12, 21, 23, 24-26, Anabaena jlos-aquae 33 28-29,94,95, 114, 139, 141, 149, Microcystis aeruginosa 33 169, 232 Nostoc 32, 32 of symbiotic origin 4, 106, 136-137, fish 171, 232-233 Lebistes reticulatus 98 photodegradation 14 Tilapia ni/otica 63 phylogenetic map 235 fungi plylogenetic marks Aspergillus ochraceus 81 de novo synthesized sponge Aspergillus sp. 79 metabolites 233 Candida albicans 27 2'-deoxyuridine 167,227 Cephalosporium 149 metabolites from obligate symbiosis Helminthosporium siccans 81 233 Helminthosporium victoriae 81 phycobiliproteins 181, 182 Penicillium atrovenetum 96 triterpenes 234 Penicillium griseofulvum 148, 202 physiological tools 22, 120, 130, 187 Saccharomyces 79 production by culture 18,68, 71-72, Saccharomyces cerevisiae 96 81-82 plants production by total synthesis 44, 71, Ajuga sp. 233 139 Chrysanthemum cinerarifolium 45 Non-marine species Frullania tamarisci 205 algae Jacaranda caucana 47 Botryococcus brownii 13 johnsongrass 58 arthropods Senecio isatideus 52 Apis mellifera 170 that produce ecdysteroids 129 Opilio canestrinii 15, IS that produce polygodial 142 bacteria protozoans Chlorobium 182 Giardia 104

271 Plasmodium 71, 201 garveatin-A 124, 199 virus heritol 63, 204 equine thinovirus 140 hormothamnione 27, 202 Herpes simplex 140, 167 imbricatine 161,223 worms kelletinin-I 144, 193 Ascaris lumbricoides 43 moritoside 128, 206 Bombyx mori 123, 151 naamidine-A 106,223 Dioctophyma renale 146 ochracin 81 Oxyuris 43 prenylquinone 166, 203 Taenia 43 pseudopterosin-A 123, 209 Taenia solium 146 tunichrome-B1 165,219 Trichuris 43 Phycocolloids Nucleosides agar 38, 42-43, 227 2'-deoxyuridine 167,227 agarose 42, 227 from Ptychoderaflava laysanica 149 alginic acids and alginates 48, 228 mycalisine-A 103, 226 carrageenans 42, 44, 228 spongosine 103 cellulose 38 Osmotic pressure 7-8, 68 Ceylon moss 43 Peptides Chinese moss 43 conotoxin 144 Funoran 43 dolastatin-lO 140,218 Fucoidan 49, 228 from fish 170 Furcellaran 43 from Tetrosia sp. 102 Ginnanso 43 geographus toxin 144 Gracilaria Gum 43 in crustaceans 151 Gulaman 43 jaspamide 94 Iridophycan 43 pardaxin-l 170 laminaran 38 peptidoglycans 68, 74, 228 Phyllophoran 43 tunichrome-Bl 165,219 starch 38 ulicyclamide 166 Phytoplankton Phenolic products growth limitation by nitrogen, anguibactin 71, 226 phosphorus, and iron 12 aplysiatoxin, debromoaplysiatoxin 32, in detoxification of waters 12 46, 101, 139,200 morphological adaptations 12 avarol 102, 204 parasitic or endolithic 11 coelenterazine 119, 231 photosynthetic or not 11 DOPA 165 planktonic or benthic 11 dopamine 122, 225 red tide 13-14,22, 50 echinochrome-A 159,202 see also under "Algae, green eudistomin-C 167,221 flagellates" , "Cyanobacteria", from seagrasses 62 "Diatoms", "Dinoflagellates"

272 Pigments in bryozoans 154 carotenoids 14, 18,214 lipopolysaccharides 68 carotenoproteins 15 peptidoglycans 68, 74, 228 of ascidians 165 tuniein 164 of bacteria 70-71 see also under "Phycocolloids" of calcareous sponges 223, 224 Prokaryotic cell 175-176 of crinoids 158 Proteins of crustaceans 151 aequorin 118 of insects 224 aplysianin-A 140 of mollusks 134, 137-140,222 bovine serum albumin 23 of scleractinians 115,218,221 collagen 89 of sea hares 140, 222 byssus 134-135 of sea urchins 159, 202 carotenoproteins 14-15 of zoanthids 121,219 depression of the freezing point of photosynthetic 177 solutions, by 8 bacteriopheophytin 185 from abalone 144 carotenoids 14, 181,214 from cubomedusae 117 chlorophyll-a, b, d 179, 180 from Geodia mesotriena 100 chlorophyll-c 178, 178-179 geodiastatins 100 chlorophyll-c3 180 glycoproteins of Aplysia kurodai 140 chlorophyll-RCI 180 imrnunoglobulins 112 in prokaryotic green algae 54 in gram-negative bacterial cell walls 68 in seaweeds 35, 40 in the glue of bryozoans 154 phycobiliproteins 182,182 in seaweeds 37,40 respiratory 5,178-179,236 in the stinging cells of cnidarians 118 solar fIlters 14, 115-116, 140, 165,200, lectins 90 214,218,221 of Chironex jleckeri 118 visual pigments 152 scleroproteins 128 see also under "Bacterial natural spongin 87, 89 products, bacteriochlorophylls" structural or enzymatic 14 Polypeptides under the deep-sea conditions 77-78 in Anemonia sulcata 120 see also under "Enzymes" in Anthopleura elegantissima, and A. Protozoa xanthogrammica 121 as decomposers 64 in Chironex jleckeri 117-118 Codosiga 64 in cyanobacteria 33 in the control of algal blooms 64 in sea snakes 172 Prymnesiophyceae in Strongylocentrotus purpuratus 160 Emiliania huxley 13, 180 Polysaccharides Prymnesiophyceae natural products byssus 134-135 chlorophyll-c3 180 chitin 56, 79, 117, 133, 151,229 long-chain oxidized hydrocarbons 13

273 lINIDlEX (lRlECOONIT][ON-S]EAWJElEDS)

Recognition phenomena Dictyopteris 52, 196 and immune response 93 Dictyota dichotoma 52 lectins 90 Durvillea 52 Red tides 13-14, 22, 50 Durvillea antarctica 43 Reptiles Ecklonia radiata 50, 193 Enhydrina schistosa 172 Ectocarpus silicosus 51 Eretmochelys imbricata (hawksbill Emiliania huxley 13, 180 turtle) 60, 92, 96, 96, 171 Fucus 39, 50 Liopleurodon macromerus 171 Fucus serratus 51 Reptile natural products Heterochordaria abietina [= Analipus polypeptidie neurotoxins 172 japonicus] 49, 218 Saponins Hizikia 48 acanthag1ycoside-A 160,215 Hormosira 52 echinoside-A 161,212 Laminaria 48, 218 mosesins 170 Macrocystis pyrifera 37, 37, 48 muricins 126 Sargassum Jilipendulum 35, 3S pavoninin-l 170,215 Sargassum fluitans 70 Seagrasses Sargassum natans 70 Amphibolis antartica 61 Sargassum vulgare 35, 43, 43 Cymodocea 61 Scytosiphon 52 ee1 grass (Zostera) 61 Spermatochnus paradoxus 52 Enhalus 61 Stypodium zonale 50, 209 Halodule 61 Syringoderma 52 Halophila 61 toxic 39, 50 Posidonia 10,61 Undaria 48 Posidonia oceanica 61, 61 Xilophora 52 Syringodium 61 Seaweeds (green) turtle grass (Thalassia) 61 Caulerpa 41, 54, 58, 203 Seagrass natural products Caulerpa bikiniensis 58 lignins 61, 229 Caulerpa racemosa 54, 54, 194 phenols 62 Codium 54 terpenes 61 Enteromorpha 39, 54 Seaweeds (brown) Halimeda 37,58,206 Ascophyllum 39 Halimeda tuna 37 Ascophyllum nodosum 48, 52 Monostroma 54 Chorda tormentosa 51 Monostroma nitidum 55, 212 Cladosiphon okamuranus 50 Neomeris annulata 58 Colpomenia 52 phy10geny of 54, 234 Cutleria multiftda 51 Prasiola japonica 54 Desmarestia aculeata 51 toxic 39,41,54 Desmarestia viridis 51

274 lINlDlEX (SJEAWlEJEDS-SJEA WlEJED lP'IROlOiUcrn)

Tydemania expeditionitis (Weber-van Lithophyllum 37 Bosse) 55, 212 Lithothamnion 37 Udotea flabellum 58 Lithothamnion calcareum 43 Ulva 39 Lithothamnion corallioides 43 Ulva lactuca 43, 43, 54 Ochtodes 46 Seaweeds (red) Ochtodes crockeri 47 Acanthopeltis 42 Plocamium 46, 46, 203 Ahnfeltia 42 Porphyra 37, 40 Alsidium helminthocorton 44 Porphyra nereocystis 40 Asparagopsis 39 Pterocladia 42 Asparagopsis armata 39 Ptilota filicina 45 Bonnemaisonia nootkana 175 Rhodymenia palmata 44 Chondria armata 44, 137, 217, 233 Sarconema filijormis 42 Chondrococcus 46 toxic 39, 41 Chondrus crispus 42 Seaweed natural products Corallina officinalis 44 alanine, aspartic acid, and glutamic Delesseria sanguinea 47 acid 45, 217 Digenea simplex 44,44,217 a-allokainic acid 217 Eucheuma 42 arsenosugars 50 Gelidium 42 bromomethane 196 Gigartina sp. 39, 39 I-bromopropane 196 Gigartina stellata 42 ß,ß,-carotene 214 Gracilaria 41-42 'caulerpatriene' 58 Gracilaria chorda 41 caulerpicin 54, 194 Gracilaria compressa 41 desmarestene 195 Gracilaria confervoides 41 dictyopterene-B 196 Gracilaria cornea 41 dictyopterene-C' 195 Gracilaria coropijolia 41 domoie acid 44, 217, 233 Gracilaria edulis 41 'eckloniaarsenoribofuranoside' 50, 193 Gracilaria eucheumoides 41 ectocarpene 52, 195 Gracilaria lichenoides 41 fatty acid from Cladosiphon Gracilaria taenioides 41 okamuranus 50 Gracilaria verrucosa 41 finavarrene 195 Halymenia venusta 42 flavors 52 Hypnea 42 friedelin 55,212 Hypnea muscijormis 44 fucoserratene 195 Jania rubens 44, 44 GABA 47,233,218 Laurencia 94 halimedatrial 58, 206 Laurencia obtusa 9, 45, 45, 211 haloderivatives of earth gases 39 Laurencia papillosa 42 hormosirene 195 Laurencia thyrsijera (Hook) 9, 45, 211

275 ][N][)lEX (SJEAWlElED lPIRODUCJ['§-SlPUNOlES)

hydrocarbons responsible for the Aplysinafistularis 95,95,175 "ocean smell" 52, 196 Aplysinopsis reticulata 123, 221 hydrocarbon sexual attractants 51-52, Batzella sp. 100 195 Cacospongia scalaris from Cap de in Neomeris annulata 58 Nice 101 iodine 48, 50, 193 Cacospongia scalaris from Izu jacaranone 47 Peninsula 99 u-kainic acid 44, 217 Cacospongia scalaris from Wakayama larninine 49, 218 101,210 lipids of calcareous seaweeds 43, 58 Carteriospongia foliaseens 98 multifidene 195 Cribrochalina dura 101, 104, 196 odoriferous terpenes 46, 203 Cribrochalina sp. 101 PGEz 41 Dasychalina cyathina 103 phycobiliproteins 181 Dysidea avara 102, 204 phycocyanobilin 40, 181,182 Dysideafragilis (Montagu, 1818) 97, plocamenone 203 97 stypoldione 50, 209 Dysidea fragilis from Fiji 97, 224 thyrsiferol 45, 211 Dysidea fragilis from Brittany 97, 205 'tydemaniatriterpene' 55,212 Dysidea fragilis from Hawaii 97, 204 udoteal 58 Dysidea herbacea 97, 216 viridiene 195 Dysidea sp. from Palau 103, 211 see also under "Phycocolloids", Dysidea sp. from Venice 105, 203 "Polysaccharides" Fasciospongia cavernosa 98, 211 Seaweed nutritional products Fasciospongia sp. 98 aonori 54 Halichondria [= Reniera] okadai awo-nori 54 (Kadota) 26, 101-102, 198,232 hijiki 48 Halichondria melanodocia 26, kombu 48 101-102,232 nori 40 Halichondria panicea 142 wakame 48 Halichondria sp. 101 Sponges Halichondria sp. of Palau 104 economic activities with 86 Haliclona sp. 101,221 Pandaros acanthifolium 26, 232 Hippospongia communis 92 Sponges (Calcarea) Hippospongia equina 87 Clathrina clathrus 223 Hippospongia sp. 103 Leucetta chagosensis (Dendy) 106, 223 Hyattella sp. 101 Leucetta microraphis 106, 224 Hymeniacidon sp. 103, 142,222 Sponges (Ceractinomorpha) Luffariella variabilis (Polejaeff) 104, Amphimedon sp. 166 210 Aplysina [= Verongial cavernicola Microciona prolifera 233 (Vacelet) 95, 95, 101, 103,226

276 lINlDlEX (SlPOWGlES-SlPOWGlE lP'lRODUCJrS)

Mycale sp. from the Gulf of Sagruni Geodia mesotriena 100 99, 226 Jaspis sp. 94 Mycale sp. from New Zealand 102 Latrunculia brevis (Ridley and Dendy) Petrosia sp. 166 100,225 Phyllospongia joliascens 104 Latrunculia magnifica 98, 143,201, Prianos melanos 100, 225 233 Psammaplysilla purea 102,226 Ptilocaulis aff. P. spiculifer 94, 99, Siphonochalina truncata 102 220 Siphonodictyon coralliphagum 99 Raspailia ramosa 84 Smenospongia [= Polyfibrospongia] Spheciospongia vesparia 86 echina 123, 221 Tethya aurantia californiana 233 Spongia adriatica 87 Theonella sp. from Hachijio-jima 100 Spongia arabica 87 Theonella sp. from Maeda-misaki 100, Spongia idia (de Laubenfels) [= 100 Leiosella idia] 98, 209 Theonella swinhoei 102 87 undetermined finger-like Astrophorida Spongia officinalis var. mollissima 87 94, 194 Spongia zimocca 87, 93 Sponge natural products Spongionella sp. 102, 210 aaptamine 103, 223 Tetrosia sp. from Hachijio-jima 102 . acanthifolicin 26 Xestospongia exigua 104,224 acetogenins from Siphonochalina Xestospongia sapra 72, 103, 202 truncata 102 Xestospongia sp. 104 adriadysiolide 105, 203 Zygomycale parishi (Bowerbank, 1875) aerothionin, homoaerothionin 95 [de Laubenfels, 1950, and Bergquist, agelasidines 103 1967] 97 agelasine-A 102, 208 Sponges (Hexactinellida) avarol 102, 204 from the Crozet Islands 106 batzellines 100 from New Zealand 106 bengarnides Y4, 104, 194 Sponges (Homoscleromorpha) bengazoles 104 undetermined Plakinidae 95, 194 bistheonellide-A (= Sponges (Tetractinomorpha) misakinolide-A) 100 Aaptos aaptos 103, 223 7-bromocavemicolenone 95,226 Agelas sp. from Kcrama Retto 103, bromochloroverongiaquinol 95, 226 223 calyculin-A 100, 195 Agelas sp. from Okinawa 102, 103, cavemicolins 95 208 cavemosine 98, 211 Axinella sp. 83, 83 collagen 89-90 Cliona 92 desacety lscalaradial 98, 210 Cryptotethya crypta 103 discorhabdin-A (= prianosin-A) 100, Discodermia calyx 100, 195 225 Dragmacidon sp. 99 dragmacidin 100 Epipolasis sp. 102 duryne 101,196 Geodia cydonium 106 dysiazirine 97, 224

277 dysideapalaunic acid 103, 211 Steroids and steroidal glycosides fatty acids from hexactinellides 106 acanthaglycoside 160,215 foliaspongin 104 cholesterol 28, 42, 161,214 geodiastatins 100 dinosterol 28, 116,215 hymenin 103,222 ecdysterone 129, 151,216,233 idiadione 98, 209 gerardiasterone 129,216 in Halichondria sp. 104 in hexactinellids 106 in Epipolasis sp. 102 pavoninin-l 106, 170,215 9-isocyanopupukeanane 142,204 Steroid derivatives jaspamide 94 cephalostatin-l 149,216 keramadine 103,223 herbasterol 97, 216 latrunculin-A and -B 98, 201 Sulfur products laulimalide 101 dimethyl sulfide 18, 31 lectins 90 nereistoxin 148,227 leucettidine 106, 224 of Alcyonidium gelatinosum 155 luffariellin-A and -B 104 Terpenes and terpenoidaI glycosides manoalide 104,210 acalycixeniolide-A 121,207 manzamine-A 101,221 adriadysiolide lOS, 203 methylaplysinopsin 122, 221, 233 ageJasidines 103 misakinolide-A (= bistheonellide-A) agelasine-A 102, 208 100 aplidiasphingosine 166,206 mycalamide-A 102 arboxeniolide-l 128 mycalisine-A 103, 226 avarol 102, 204 naamidine-A 106, 223 bacteriohopanetetrol 75, 213 nakafuran-8 97, 142,204 briareins 122 okadaic acid 101,198,232 ß,ß-carotene 14, 18,214 okinonellin-A 102-103, 210 'caulerpatriene' 58,203 penlanfuran 97, 205 cavemosine 98, 211 peptide from Tetrosia sp. 102 cIadiellin 123, 207 plakinic acid-A 96, 194 coralloidins 132 prianosin-A (= discorhabdin-A) 100, dendryphiellin-A 82, 205 225 denticulatolide 127 ptilocaulin 94, 99, 220 desacetylscalaradial 98, 101,210 purealin 103, 226 dysideapaIaunic acid 103, 211 spongin 87, 89 (20ß)-echinolactone-B 116,213,233 spongosine 103 echinoside-A 161,212 sterone from Geodia cydonium and foliaspongin 104 hexactinelIids 106 friedeJin 55, 212 swinholide-A 102 fucoxanthin 14,214 terpenes from Cacospongia scalaris halimedatriaI 58, 206 from Izu Peninsula 99 heritol 63, 204 xestoquinone 103, 202 hydrocarbons from algae 13 xestospongin-C 103, 224 idiadione 98, 209 in Armina maculata 122

278 in Cacospongia scalaris from Izu Thelepus setosus 148,202 Peninsula 99 Worms (hernichordates) in calcareous green seaweeds 58 Cephalodiscus gi/christi 149, 216 in Epipolasis sp. 102 Glossobalanus sp. 149 in Halichondria sp. 104 Ptychoderaflava laysanica 149, 149 in Lithophyton viridis 126 Ptychodera sp. 149 in seagrasses 61 Worms (Platyhelminthes) in Veretillum cynomorium 122, 125 Amphiscolops sp. 27 9-isocyanopupukeanane 142,204 Worm natural products limatulone 144,213 cephalostatin-l 149,216 litophynins 123 nereistoxin 148,227 lophotoxin 123, 131,207 thelepin 148, 202 luffariellin-A and -B 104 Zooxanthellae (see under manoalide 104,210 "Dinoflagellates ") moritoside 128,206 nakafuran-8 97, 142,204 odoriferous from red seaweeds 46 okinonellin-A 103, 210 pacifigorgio1127,205 palustrol 126 penlanfuran 97, 205 peridinin 14, 214 plocamenone 203 polygodial 142 prenylquinone 166, 203 pseudopterosin-A 123,209 renillafoulin-A 123, 208 sarcodictyin-A 122, 125,208 siccayne 81 squalene 9, 211 stylatulide 126 stypoldione 50, 209 subergorgic acid 131,205 thyrsiferol 45, 211 'tydemaniatriterpene' 55,212 verrucosin-A 142,209 Worms (annelids) Amphitrite edwarsi 147, 147 Aphrodite 147 Lepidasthenia argus 147 Lumbrinereis brevicirra [= L. heteropoda] 148, 227 Sabella pavonina 147 Spirographis spallanzani 147, 147, 149 279