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Chemical investigation of the South-Pacific marine sponge Suberea clavata led to the isolation of eight new bromotyrosine metabolites named subereins 1–8 (2–9) along with twelve known co-isolated congeners. The detailed configuration determination of the first representative major compound of this family 11-epi-fistularin-3 (11R,17S) (1) is described. Their chemical characterization was achieved by HRMS and integrated 1D and 2D NMR (nuclear magnetic resonance) spectroscopic studies and extensive comparison with literature data. For the first time, a complete assignment of the absolute configurations for stereogenic centers C-11/17 of the known members (11R,17S) 11-epi-fistularin-3 (1) and 17-deoxyfistularin-3 (10) was determined by a combination of chemical modifications, Mosher’s technology, and ECD spectroscopy. Consequently, the absolute configurations of all our new isolated compounds 2–9 were determined by the combination of NMR, Mosher’s method, ECD comparison, and chemical modifications. Interestingly, compounds 2–7 were obtained by chemical transformation of the major compound 11-epi-fistularin-3 (1). Evaluation for acetylcholinesterase inhibition (AChE), DNA methyltransferase 1 (DNMT1) modulating activity and antifouling activities using marine bacterial strains are also presented.

Four new brominated tyrosine metabolites, aplyzanzines C&ndash, F (1&ndash, 4), were isolated from the French Polynesian sponge Pseudoceratina n. sp., along with the two known 2-aminoimidazolic derivatives, purealidin A (5) and 6, previously isolated, respectively, from the sponges Psammaplysilla purpurea and Verongula sp. Their structures were assigned based on the interpretation of their NMR and HRMS data. The compounds exhibited quorum sensing inhibition (QSi) and antifouling activities against several strains of bacteria and microalgae. To our knowledge, the QSi activity of this type of bromotyrosine metabolite is described here for the first time.

International audience; Four new brominated tyrosine metabolites, aplyzanzines C-F (1-4), were isolated from the French Polynesian sponge Pseudoceratina n. sp., along with the two known 2-aminoimidazolic derivatives, purealidin A (5) and 6, previously isolated, respectively, from the sponges Psammaplysilla purpurea and Verongula sp. Their structures were assigned based on the interpretation of their NMR and HRMS data. The compounds exhibited quorum sensing inhibition (QSi) and antifouling activities against several strains of bacteria and microalgae. To our knowledge, the QSi activity of this type of bromotyrosine metabolite is described here for the first time.

WOS:000518678100003; Although the French Polynesian reefs are among the most well studied reefs of the world, sponges are still poorly known, with only 199 species or OTUs of sponges having been described from French Polynesia, 167 at an OTU level and 32 at a species level. From those 199 species, just five are calcareous sponges. As it is possible that this number is underestimated, the aim of the present work was to study the diversity of calcareous sponges from French Polynesia. Hence, different French Polynesian archipelagos were surveyed by SCUBA from 3 to 60 m of depth. Identifications were performed using morphological and molecular (ITS and C-LSU) tools. We found a total of nine species of Calcarea, comprising five different genera. Five species are new to science: Clathrina fakaravae sp. nov., Clathrina huahineae sp. nov., Ernstia variabilis sp. nov., Leucascus digitiformis sp. nov., and Leucandra tahuatae sp. nov. With the present work, the number of identified sponges from French Polynesia at a species level increased from 32 to 41. The only calcareous sponge previously known from French Polynesia that was recollected by our group was Leucetta chagosensis. Our results suggest that the Eastern Indo-Pacific Realm shows more affinity with the Central and the Western Indo-Pacific Realms Four species supported these affinities: Ascandra cf. crewsi, previously known only from Papua New Guinea, Leucascus simplex from South Australia, and Leucetta chagosensis and L. microraphis, both widespread species in the Indo-Pacific. These two Leucetta species, however, most likely represent species complexes. Once again the molecular markers ITS and C-LSU helped in the identification of calcareous sponges, showing how important is an integrative taxonomy. Although our work has increased in 250% (6 spp to 15 spp) the diversity of calcareous sponges in French Polynesia, it is most possible that this number is still underestimated.

We report herein a ring-distortion strategy applied to marine natural substances ilimaquinone and 5-epi-ilimaquinone. A chemically diverse library of molecules was synthesised that included rearrangements of the sesquiterpene moiety and original reorganisations of the quinone ring. Chemoinformatic analyses evaluated the rise of structural diversity and the exploration of chemical space. Some focussed biological activities of this library were also investigated; quorum sensing activity of Vibrio harveyi was envisaged and some of the new compounds were shown to be good quorum sensing inhibitor candidates, whereas others were activators. Toxicities were also evaluated and some products showed micromolar activities against human umbilical vein endothelium, human hepatocellular carcinoma and human lung carcinoma (A549) cells.

Treatment of acute myeloid leukemia (AML) patients is still hindered by resistance and relapse, resulting in an overall poor survival rate. Recently, combining specific B-cell lymphoma (Bcl)-2 inhibitors with compounds downregulating myeloid cell leukemia (Mcl)-1 has been proposed as a new effective strategy to eradicate resistant AML cells. We show here that 1(R), 6(S), 1&rsquo, (R), 6&rsquo, (S), 11(R), 17(S)-fistularin-3, a bromotyrosine compound of the fistularin family, isolated from the marine sponge Suberea clavata, synergizes with Bcl-2 inhibitor ABT-199 to efficiently kill Mcl-1/Bcl-2-positive AML cell lines, associated with Mcl-1 downregulation and endoplasmic reticulum stress induction. The absolute configuration of carbons 11 and 17 of the fistularin-3 stereoisomer was fully resolved in this study for the first time, showing that the fistularin we isolated from the marine sponge Subarea clavata is in fact the (+)-11(R), 17(S)-fistularin-3 stereoisomer keeping the known configuration 1(R), 6(S), 1&rsquo, (R), and 6&rsquo, (S) for the verongidoic acid part. Docking studies and in vitro assays confirm the potential of this family of molecules to inhibit DNA methyltransferase 1 activity.

Herein, we describe the isolation and spectroscopic identification of eight new tetrabrominated tyrosine alkaloids 2–9 from the Polynesian sponge Suberea ianthelliformis, along with known major compound psammaplysene D (1), N,N-dimethyldibromotyramine, 5-hydroxy xanthenuric acid, and xanthenuric acid. Cytotoxicity and acetylcholinesterase inhibition activities were evaluated for some of the isolated metabolites. They exhibited moderate antiproliferative activity against KB cancer cell lines, but psammaplysene D (1) displayed substantial cytotoxicity as well as acetylcholinesterase inhibition with IC50 values of 0.7 μM and 1.3 μM, respectively.

WOS:000430461000007; International audience; A new species of Raspailia (Raspaxilla) frondosa sp. nov. is described from the deep seamounts of the Norfolk and New Caledonia Ridges. The morphology of the species resembles that of a frond or a fern, and its unique highly compressed axial skeleton of interlaced spongin fibres without spicules in combination with a radial extra axial skeleton of a perpendicular palisade of spicules, differentiate it from all other species of the subgenus. This species is compared morphologically to all 18 other valid species described in Raspailia (Raspaxilla).

WOS:000449495400028; International audience; Marine sponges are prolific producers of physiologically active secondary metabolites [1, 2]. The chemical exploration of fatty acids derived from of marine organisms is a vital research area [3,4,5]. Fatty acids and lipids obtained from marine sources display unique molecular diversity, including saturated, mono-, di-, and polyunsaturated, branched, halogenated, hydroxylated, methoxylated, epoxide, and non-methylene-interrupted structure [6]. Marine fatty acids exhibit a variety of bioactivities, including antifungal, antibacterial, antimalarial [7], and anticancer [8]. Among the marketed eight marine-derived drugs, the ethyl esters of several omega-3 fatty acids from fish oils, in particular, ethyl esters of the major constituents eicosapentaenoic acid and docosahexaenoic acid, are approved as anti-hypertriglyceridemia and antibacterial drugs [9,10,11].

WOS:000413167100012; International audience; Guided by a "chemistry first" approach using molecular networking, eight new bright-blue colored natural compounds, namely dactylocyanines A-H (3-10), were isolated from the Polynesian marine sponge Dactylospongia metachromia. Starting from ilimaquinone (1), an hemisynthetic phishing probe (2) was prepared for annotating and matching structurally related natural substances in D. metachromia crude extract network. This strategy allowed characterizing for the first time in Nature the blue zwitterionic quinonoid chromophore. The solvatochromic properties of the latter are reported.

Two new acyclic bis-guanidine alkaloids, unguiculins B-C (2–3), were isolated from a French Polynesian sponge Monanchora n. sp. together with the known compound unguiculin A (1). Their structures were established by spectroscopic data interpretation and comparison with the literature. Unguiculins A-C displayed antiproliferative and cytotoxic efficacy against several human cancer cells with IC50 values in the micromolar range.

WOS:000416240300004; International audience; The Indo-Pacific is the world's largest marine biogeographic region, covering the tropical and subtropical waters from the Red Sea in the Western Indian Ocean to the Easter Islands in the Pacific. It is characterized by a vast degree of biogeographic connectivity in particular in its marine realm. So far, usage of molecular tools rejected the presence of cosmopolitan or very widespread sponge species in several cases, supporting hypotheses on a higher level of endemism among marine invertebrates than previously thought. We analysed the genetic diversity of Hyrtios erectus and Stylissa massa, two alleged widespread sponge species of the Indo-Pacific, from the Red Sea and Mayotte in the West Indian Ocean to Polynesia in the Central Pacific. In the region of its type locality, the Red Sea, Hyrtios erectus is genetically distinct, and the populations from the remaining Indo-Pacific are a potentially different species and paraphyletic in respect to H. altus. Stylissa massa falls into different, but widespread genetic clades, one of them (Stylissa cf. massa), with distinct potentially hairpin-forming elements in mitochondrial intergenic regions. The results also indicate that morphologically established demosponge species in the Indo-Pacific can be widespread, but simultaneously harbour cryptic, genetically distinct lineages.

00000; International audience; Dactylospongia metachromia and Dactylospongia elegans collected from French Polynesia were studied with a particular focus on the variation of the diastereomeric ratio between ilimaquinone (4) and 5-epi-ilimaquinone (5). More than 100 samples, covering an area of 4100km(2), were studied to try to clarify this intriguing issue. Nuclear magnetic resonance appeared as the non-destructive, straightforward technique of choice for a relative quantitative study. A random distribution, unique at that point in nature, is observed and leads to biosynthetic considerations. Biological evaluation of both compounds was also performed and showed moderate discrepancies in cytotoxicity and apoptosis induction.

WOS:000414234400035; International audience; Two sporothriolide-related compounds were obtained from an extract of the fungus Hypoxylon monticulosum CLL-205, isolated from a Sphaerocladina sponge collected from the Tahiti coast. Compound 2 is a deoxy analogue of sporothric acid (4). Compound 3 is a newly reported unusual scaffold combining sporothriolide (1) and trienylfuranol A (5) moieties, through a Diels-Alderase-type reaction. Various experimental and analytical arguments supported the biocatalytic origin of compound 3. The structures of the isolated compounds were elucidated using 1D and 2D NMR, HRMS, and IR data. The structure and the absolute configuration of 3 were unambiguously confirmed by a single-crystal X-ray diffraction analysis.

WOS: 000412959500037, PubMed: 28185932, Since the discovery of chitin in skeletal structures of sponges (Porifera) in 2007, studies on search of novel species which possess this structural aminopolysaccharide continue up today. The most potential source of chitin is suggested to be localized in the four families of sponges related to the order Verongida (Demospongiae) which nevertheless require further clarification. Here, we report for the first time the isolation and identification of alpha-chitin from the Suberea clavata demosponge (Aplysinidae: Verongida). Raman spectroscopy, Calcofluor White staining, chitinase test and ESI-MS techniques were used to identify chitin. We suggest that the presence of chitin within fibrous skeletons of diverse species of Verongida order, and, especially in all species of the Aplysinidae family, may be useful for the identification of novel, previously unidentified marine demosponges. (C) 2017 Elsevier B.V. All rights reserved., DFG (Germany) [EH 394-3]; PUT research grant (Poland) [03/32/DSPB/0706/2017], This work was supported by DFG Grant EH 394-3 (Germany) and PUT research grant 03/32/DSPB/0706/2017 (Poland). The authors thank Prof. Dr. Yixin Zhang for the use of the ESI-MS instrument and Rob van Soest for his support and comments.

International audience; Highly biologically active marine sesquiterpene ilimaquinone was selected for chemical modifications. Its biotransformation was investigated using a combinatorial approach as an original way to screen different strains of microorganisms. Mucor circinelloides ATCC 8541 was able to structurally modify ilimaquinone into three different compounds. A stereospecific epoxidation was observed and compared to chemical epoxidation. A hydroxylation of the decalin ring was also observed as well as an unexpected substitution on the quinone ring by ethanolamine. Compounds were evaluated against several cell lines.

Four bicyclic and three pentacyclic guanidine alkaloids (1-7) were isolated from a French Polynesian Monanchora n. sp. sponge, along with the known alkaloids monalidine A (8), enantiomers 9-11 of known natural product crambescins, and the known crambescidins 12-15. Structures were assigned by spectroscopic data interpretation. The relative and absolute configurations of the alkaloids were established by analysis of (1)H NMR and NOESY spectra and by circular dichroism analysis. The new norcrambescidic acid (7) corresponds to interesting biosynthetic variation within the pentacyclic core. All compounds exhibited antiproliferative and cytotoxic efficacy against KB, HCT116, HL60, MRC5, and B16F10 cancer cells, with IC50 values ranging from 4 nM to 10 μM.

The debromokeramadine ( 2a ), which was isolated from the Pacific sponge Agelas cf. mauritiana , is described in this manuscript. We also report the synthesis of the debromokeramadine ( 2a ) and its known brominated analog, keramadine ( 1 ), based on the regioselective oxidative addition of a guanidine derivative on N -acylpyrrole dihydropyridines. This flexible approach was applied to the preparation of three debromo-analogs 2b – d by varying the substitution of the guanidine bis-nucleophile. The reaction is a great progress for the regio- and stereoselective synthesis of debromokeramadine ( 2a ) analogs and interesting library of pyrrole-2-aminoimidazole allowing biological activity studies.

The debromokeramadine ( 2a ), which was isolated from the Pacific sponge Agelas cf. mauritiana , is described in this manuscript. We also report the synthesis of the debromokeramadine ( 2a ) and its known brominated analog, keramadine ( 1 ), based on the regioselective oxidative addition of a guanidine derivative on N -acylpyrrole dihydropyridines. This flexible approach was applied to the preparation of three debromo-analogs 2b – d by varying the substitution of the guanidine bis-nucleophile. The reaction is a great progress for the regio- and stereoselective synthesis of debromokeramadine ( 2a ) analogs and interesting library of pyrrole-2-aminoimidazole allowing biological activity studies.

International audience; Symbioses with the dinoflagellate Symbiodinium are widespread among marine invertebrates and protists, especially in nutritionally demanding habitats, such as tropical coral reefs, where they play a major role in ecosystem survival. Moreover, apart from corals and sea anemones, many of the Symbiodinium species and clades involved in these partnerships remain to be characterized. This study provides new insights into nudibranch and sponge associations with Symbiodinium by sequencing regions of the Symbiodinium 28S rDNA and the host mitochondrial COI oxidase. Specimens were sampled between 2011 and 2013 from locations around the islands of Moorea and Tahiti, French Polynesia. Our results revealed that some of the sponges and nudibranchs harbored typical Symbiodinium from clade B or C while others harbored new, undescribed Symbiodinium-like dinoflagellates. A detailed analysis of the different life stages of the nudibranch Phestilla lugubris and of its specific coral prey, Porites rus, suggests a prey-predator horizontal transfer of the symbiont and its vertical inheritance from the parent to the eggs.; Les symbioses à zooxanthelles, dinoflagellés du genre Symbiodinium, sont largement répandues chez les invertébrés marins et les protozoaires, notamment dans les eaux oligotrophes, où ils jouent un rôle important dans la survie des récifs coralliens. De plus, excepté chez les coraux et les anémones, les différentes espèces et clades de Symbiodinium impliqués dans ces associations restent à être caractérisés. Notre étude, grâce à l’utilisation des marqueurs génétiques 28S ADNr des Symbiodinium et la sous-unité 1 de la cytochrome oxydase mitochondriale (COI) de l’hôte, procure de nouvelles données quant aux associations des éponges et des nudibranches avec les Symbiodinium. L’échantillonnage a eu lieu autour de Moorea et de Tahiti (Polynésie française), entre 2011 et 2013. Nos résultats révèlent que certaines espèces d’éponges et de nudibranches possèdent les clades B et C communément retrouvés, chez les coraux notamment, alors que d’autres présentent de nouveaux dinoflagellés « Symbiodinium-like ». Une analyses détaillée des Symbiodinium à différents stades du cycle de vie du nudibranche corallivore Phestilla lugubris et de son corail hôte Porites rus suggèrent l’existence d’un transfert horizontal de Symbiodinium proie–prédateur et un transfert vertical du parent P. lugubris à ses œufs.

Seven 2,5-diketopiperazines (DKPs) were isolated from the Fijian marine sponge Acanthella cavernosa. NMR and circular dichroism (CD) comparison with synthetic L-L DKPs allowed us to determine unambiguously the L-L absolute configuration of the natural DKPs. This work initiated the setting up of an optical properties database of natural DKPs, including specific rotation and CD. 2,5-Diketopiperazines (DKPs) are cyclic secondary metabolites directly resulted from the primary peptidic metabolites. They have been detected in beverages, foods and microorganisms. As the smallest cyclic peptides, DKPs provide interesting biological properties such as organoleptical, antitumoral, antifungal, antibacterial, antifouling and antiviral activities. 2 Many natural metabolites including alkaloids are biosynthetically derived from diketopiperazines by oxidation and rearrangement reactions. They represent an interesting tool for medicinal chemistry since their heterocyclic cores provide a good template for further chemical and stereochemical modification. Proline (Pro) and arginine (Arg) units are usually found in biologically active DKPs. Despite the increasing interest of DKPs, their stereochemical information was not well documented. DKP derivatives have attracted significant attention because of their potential rule as important class of multifunctional biomolecules. Their putative roles as signaling molecules in the chemical ecology context is more and more considered. Thus, determination of absolute configuration of cyclic dipeptides is of significant importance. As a part of our on-going research on bioactive natural compounds from Pacific Axinellidae marine sponges, a scrutinized study of secondary metabolites of a Fijian sample of the marine sponge Acanthella HETEROCYCLES, Vol. 90, No. 2, 2015 1351

Among the Pyuridae family the genus Herdmania Lahille, 1888 differs from the diagnose of Pyura Molina, 1782 by the presence of needle-shape echinated spicules in all tissues. These striking elements formerly led to identify many specimens collected in tropical or temperate waters as Herdmania momus (Savigny, 1916). Later the genus was split into several species with a special attention to the different structure of the gonoducts. Newly collected specimens and a revision of previously described animals in Polynesia lead to the redescription of Herdmania papietensis Herdman 1882 from Polynesia and to compare it to the other Herdmania species known in the Pacific Ocean.

Our team is one of the partners of the international project PoMaRe ("Benthic Invertebrates of Polynesia, Martinique and Reunion"). We worked directly with Dr. Cécile Debitus from the IRD in French Polynesia, her team was in charge of collecting samples of marine sponges in different atolls of the Pacific.In the laboratory, we focused particularly on two abundant species in Polynesia: Dactylospongia metachromia and Dactylospongia elegans. Our job was to isolate their major metabolites: the ilimaquinones and perform various studies around these two epimeric sesquiterpene quinones.The work was organized as follows:- Extraction of ilimaquinones: ilimaquinones were isolated from the sponge Dactylospongia metachromia with a yield > 3%. A study of the variation of their respective percentage in relation with the geography of collection was undertaken, involving more than one hundred samples. This is the first study of this scale to be achieved. The sponge D. elegans was also studied, our results revealed the presence of ilimaquinone but also a nearby structure: isospongiaquinone.- Structural modifications of ilimaquinones:* Chemical modifications: structural changes were studied on ilimaquinones to delimit their reactivity: various analogues have been obtained. Among others, natural substances isospongiaquinone, 5-epi-isospongiaquinone and neomamanuthaquinone have been obtained. In these studies, a new reaction was discovered modifying the quinone surprisingly under oxidizing conditions.* Enzymatic modifications: micro-organisms were used to carry out biotransformations on the skeleton of ilimaquinone, three compounds were obtained. These changes have affected both the decalin and the quinone of our substrate. An original reaction has also been observed for the first time.-Molecular modeling and electrochemistry: a molecular modeling study has allowed us to calculate the energy of formation of ilimaquinones based on biosynthesis assumptions that we can now better understand. Finally an electrochemistry study evaluated the redox properties of these natural molecules with high potential in terms of biological activity.; Notre équipe est l’un des partenaires du projet international PoMaRé (« Invertébrésbenthiques de Polynésie, Martinique et de la Réunion »). Nous travaillons encollaboration directe avec le Dr Cécile Debitus de l’IRD en Polynésie française, sonéquipe étant notamment en charge de collecter des échantillons d’éponges marinesdans différents atolls du Pacifique.Au laboratoire, nous nous sommes intéressés particulièrement à deux espècesabondantes en Polynésie : Dactylospongia metachromia et Dactylospongia elegans.Notre travail a consisté à isoler leurs métabolites spécialisés majoritaires : lesilimaquinones, puis à réaliser diverses études autour de ces deux sesquiterpènesquinoniques épimériques. Le travail s’est organisé de la façon suivante :- Extraction des ilimaquinones : les ilimaquinones ont été isolées de l’éponge Dactylospongia metachromia avec un rendement > 3 %. Une étude de la variation de leur pourcentage respectif par rapport à la géographie de collecte de l’éponge a été entreprise. Impliquant plus d’une centaine d’échantillons, c’est la première fois qu’une étude d’une telle ampleur est réalisée. L’éponge D. elegans a également été étudiée, nos études ont révélé la présence de l’ilimaquinone mais aussi d’une structure proche : l’isospongiaquinone.- Modifications structurales autour des ilimaquinones : Par voie chimique : des modifications ont été étudiées sur les ilimaquinones afin de cerner leur réactivité, divers analogues ont ainsi été obtenus. Entre autres, les substances naturelles isospongiaquinone, 5-epi-isospongiaquinone et néomamanuthaquinone ont pu être hémisynthétisées. Lors de ces études, une nouvelle réaction a été découverte modifiant la quinone de façon surprenante dans des conditions oxydantes. Par voie enzymatique : des micro-organismes ont été utilisés pour réaliser des biotransformations sur le squelette de l’ilimaquinone, trois composés ont été obtenus. Ces modifications ont touché à la fois la décaline et la quinone de notre substrat. Une réaction de fonctionnalisation originale a d’ailleurs pu être observée pour la première fois.- Modélisation moléculaire et électrochimie : une étude de modélisation moléculaire nous a permis de calculer l’énergie de formation des ilimaquinones en nous basant sur les hypothèses de biosynthèse que nous pouvons maintenant mieux appréhender. Finalement une étude d’électrochimie nous a permis d’évaluer les propriétés oxydo-réductrices de ces molécules naturelles à fortes potentialités en termes d’activités biologiques.

Our team is one of the partners of the international project PoMaRe ("Benthic Invertebrates of Polynesia, Martinique and Reunion"). We worked directly with Dr. Cécile Debitus from the IRD in French Polynesia, her team was in charge of collecting samples of marine sponges in different atolls of the Pacific.In the laboratory, we focused particularly on two abundant species in Polynesia: Dactylospongia metachromia and Dactylospongia elegans. Our job was to isolate their major metabolites: the ilimaquinones and perform various studies around these two epimeric sesquiterpene quinones.The work was organized as follows:- Extraction of ilimaquinones: ilimaquinones were isolated from the sponge Dactylospongia metachromia with a yield > 3%. A study of the variation of their respective percentage in relation with the geography of collection was undertaken, involving more than one hundred samples. This is the first study of this scale to be achieved. The sponge D. elegans was also studied, our results revealed the presence of ilimaquinone but also a nearby structure: isospongiaquinone.- Structural modifications of ilimaquinones:* Chemical modifications: structural changes were studied on ilimaquinones to delimit their reactivity: various analogues have been obtained. Among others, natural substances isospongiaquinone, 5-epi-isospongiaquinone and neomamanuthaquinone have been obtained. In these studies, a new reaction was discovered modifying the quinone surprisingly under oxidizing conditions.* Enzymatic modifications: micro-organisms were used to carry out biotransformations on the skeleton of ilimaquinone, three compounds were obtained. These changes have affected both the decalin and the quinone of our substrate. An original reaction has also been observed for the first time.-Molecular modeling and electrochemistry: a molecular modeling study has allowed us to calculate the energy of formation of ilimaquinones based on biosynthesis assumptions that we can now better understand. Finally an electrochemistry study evaluated the redox properties of these natural molecules with high potential in terms of biological activity.; Notre équipe est l’un des partenaires du projet international PoMaRé (« Invertébrésbenthiques de Polynésie, Martinique et de la Réunion »). Nous travaillons encollaboration directe avec le Dr Cécile Debitus de l’IRD en Polynésie française, sonéquipe étant notamment en charge de collecter des échantillons d’éponges marinesdans différents atolls du Pacifique.Au laboratoire, nous nous sommes intéressés particulièrement à deux espècesabondantes en Polynésie : Dactylospongia metachromia et Dactylospongia elegans.Notre travail a consisté à isoler leurs métabolites spécialisés majoritaires : lesilimaquinones, puis à réaliser diverses études autour de ces deux sesquiterpènesquinoniques épimériques. Le travail s’est organisé de la façon suivante :- Extraction des ilimaquinones : les ilimaquinones ont été isolées de l’éponge Dactylospongia metachromia avec un rendement > 3 %. Une étude de la variation de leur pourcentage respectif par rapport à la géographie de collecte de l’éponge a été entreprise. Impliquant plus d’une centaine d’échantillons, c’est la première fois qu’une étude d’une telle ampleur est réalisée. L’éponge D. elegans a également été étudiée, nos études ont révélé la présence de l’ilimaquinone mais aussi d’une structure proche : l’isospongiaquinone.- Modifications structurales autour des ilimaquinones : Par voie chimique : des modifications ont été étudiées sur les ilimaquinones afin de cerner leur réactivité, divers analogues ont ainsi été obtenus. Entre autres, les substances naturelles isospongiaquinone, 5-epi-isospongiaquinone et néomamanuthaquinone ont pu être hémisynthétisées. Lors de ces études, une nouvelle réaction a été découverte modifiant la quinone de façon surprenante dans des conditions oxydantes. Par voie enzymatique : des micro-organismes ont été utilisés pour réaliser des biotransformations sur le squelette de l’ilimaquinone, trois composés ont été obtenus. Ces modifications ont touché à la fois la décaline et la quinone de notre substrat. Une réaction de fonctionnalisation originale a d’ailleurs pu être observée pour la première fois.- Modélisation moléculaire et électrochimie : une étude de modélisation moléculaire nous a permis de calculer l’énergie de formation des ilimaquinones en nous basant sur les hypothèses de biosynthèse que nous pouvons maintenant mieux appréhender. Finalement une étude d’électrochimie nous a permis d’évaluer les propriétés oxydo-réductrices de ces molécules naturelles à fortes potentialités en termes d’activités biologiques.

Raspailia (Raspaxilla) frondosa sp. nov. (Figs 1–4, Table 1) Etymology. Latin for leafy, reflecting the gross morphology of the sponge resembling the frond of a fern. Material examined. Holotype: MNHN-IP-2015-1402 (fragment of the holotype QM G335124) Station DW3110, New Caledonia Ridge 23o1.35’ S 168o16.99’ E to 23o1.71’S 168o15.86E, 270–310 m, Coll. Cécile Debitus, 28.x.2008 (Samadi 2008). Paratypes: QM G335144 (same data as holotype). QM G318701 NORFOLK 1 Station DW 1724, Norfolk Ridge Seamount Banc.no.1. 23o17.05’S 168o14.28’E, Dredge 200–291 m, Coll. Bertrand Richer de Forges, 27.vi.2001 (Richer de Forges 2001). Description. Growth form: A stalked foliaceous, flabellate to reniform sponge growing mainly in one plane but showing some undulations. The blades are between 55 and 65 mm high and 55 to 85 mm wide, with a maximum thickness of 3 mm at the base sloping to less than 1 mm at the apex. It has a circular stalked base with a diameter of 10 mm and small basal holdfast. Colour: Pale cream to orange on deck and beige to brown in ethanol. Texture: Firm and barely compressible, but easy to tear. Surface: Oscules are not visible, however on the surface the absence of parchment-like ectosome over the aquiferous channels resembles leaf veins (this is could also be due to friction or predation). Otherwise the surface is highly hispid and velvety from protruding long styles. Ectosomal skeleton: Membranous, parchment-like, without a specialised ‘raspailiid’ skeleton of spiculebouquets, but with a thick palisade of subectosomal styles protruding through the ectosome up to 0.5–2 mm. Choanosomal skeleton: With well-differentiated axial and extra-axial skeletons. The axial skeleton is compressed, lacking spicules, but with heavy interlaced spongin fibres forming a wide core up to 50% of the diameter of the skeleton. Long subectosomal styles and shorter choanosomal rhabdostyles have their bases embedded in the axial spongin skeleton, standing perpendicular to the axis forming a radial extra-axial skeleton, with the subectosomal styles protruding through the ectosome and the choanosomal rhabdostyles supporting the parchment-like ectosome on both dorsal and ventral surfaces of the sponge. Megascleres (Table 1). There are only two categories of megascleres. Choanosomal rhabdostyles are very smooth, moderately thick, with a smooth non-tylote base, varying from slight to well-developed rhabds (97–469 x 6.2–31.6 µm). Subectosomal styles are rare ( Microscleres: Absent. Molecular data. DNA barcodes for 28S and CO1 could not be retrieved for the holotype or for the paratypes. All samples underwent two different DNA extractions (see Methods section) and multiple amplification attempts with different deviations from the PCR protocol, but amplification success could not be achieved under the described methods.