Treasures from the Deep: Characellides as Anti-Inflammatory Lipoglycotripeptides from the Sponge Characella pachastrelloides Sam Afoullouss, †,‡,∇ Kevin Calabro, †,∇ Gre ́ gory Genta-Jouve, § Sandra Gegunde, ⊥ Amparo Alfonso, ⊥ Robert Nesbitt, † Christine Morrow, ‡,∥ Eva Alonso, ⊥ Luis M. Botana,* ,⊥ A. Louise Allcock,* ,‡ and Olivier P. Thomas* ,† † Marine Biodiscovery, School of Chemistry and Ryan Institute, National University of Ireland Galway (NUI Galway), University Road, H91TK33 Galway, Ireland ‡ Zoology, School of Natural Sciences and Ryan Institute, National University of Ireland Galway (NUI Galway), University Road, H91TK33 Galway, Ireland § C-TAC, COMETE UMR 8638 CNRS, Université Paris Descartes, 4 avenue de l’observatoire, 75006 Paris, France ⊥ Departamento de Farmacología, Facultad de Veterinaria, Universidade de Santiago de Compostela, 27002 Lugo, Spain ∥ Department of Natural Sciences, National Museums Northern Ireland, 153 Bangor Road, Cultra BT18 0EU, Northern Ireland * S Supporting Information ABSTRACT: The chemical investigation of marine invertebrates from the deep Northeastern Atlantic revealed new lipoglycotripeptides named characellides isolated from the tetractinellid sponge Characella pachastrelloides. This new family of natural products features a central tripeptide linked to a rare sugar unit and a long alkyl chain ending with a 2,3- dimethyltetrahydropyran. The configurations of all 13 chiral centers were determined by extensive use of NMR data and circular dichroism spectra combined with calculations. A mong the new horizons for marine biodiscovery, the deep ocean has recently attracted much attention. Technological advances exemplified by the development of underwater remote operated vehicles (ROVs) have enabled in situ photography and careful collection of specimens from depths that were previously inaccessible, except by dredging. In recent years, natural product chemists have been turning to the deep sea where the physio-chemical conditions are extreme in comparison with other ecosystems with the aim of discovering new chemical structures. 1 A rapid review of the literature on deep-sea natural products reveals a particular focus on microorganisms like bacteria and fungi that have already led to new chemical architectures. 2 However, chemical studies on marine invertebrates are still scarce, mainly because of the difficulties in collection and identification of the samples, compounded by the scarcity of taxonomists, and the high percentage of novel species. Several worldwide programs have recently been funded to fill the gaps in our knowledge of the marine biodiversity present below 500 m. We undertook the first chemical screening of sponges collected from deep water off the southwest coast of Ireland. In order to make best use of the samples and within the context of sustainable exploitation, we did not choose a bioguided approach, but rather we aimed at a broad description of the metabolome of each collected specimen. A UPLC-DAD-MS/MS chemical screening prioritized the marine sponge Characella pachastrelloides 3 as a rich source of chemical diversity. Molecular networking showed a high level of novelty among the different clusters present. Interestingly, a large diversity of poecillastrins recently identified in a species of this genus were uncovered. 4 Nevertheless, the presence of other clusters of major metabolites with high molecular Received: November 18, 2018 Published: December 20, 2018 Letter pubs.acs.org/OrgLett Cite This: Org. Lett. 2019, 21, 246-251 © 2018 American Chemical Society 246 DOI: 10.1021/acs.orglett.8b03684 Org. Lett. 2019, 21, 246−251 Downloaded via UNIV DE SANTIAGO DE COMPOSTELA on January 15, 2019 at 19:34:31 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.