Abstract Five demosponges belonging to the order Axinellida: Axinella corrugata, Dragmacidon alvarezae, Dragmacidon reticulatum, Ptilocaulis walpersi, Myrmekioderma rea and one sponge belonging to the order Scopalinida: Scopalina ruetzleri were analyzed to assess their fatty acid composition in the phospholipid fraction. Additionally, the seasonal and intraspecific variation in fatty acids composition was assessed in M. rea and D. alvarezae. Fatty acid identification was conducted using an HRGC-MS with an ECL value of methyl ester derivatives, and analyzing their mass spectra. To confirm double bound location, N-acylpyrrolidide derivatives were used studying their mass spectra. In total, 83 fatty acids were identified with chain lengths ranging from C14 to C32. Interestingly, brominated fatty acids were identified, previously suggested for sponges. Polybranched fatty acids such as 4,8,12-trimethyltridecanoic acid (4,8,12-TMTD) and 3,7,11,15-tetramethylhexadecanoic (phytanic acid) were found, without a clear distribution pattern. A predominance of iso-acids (i-15:0 and i-17:0) on anteiso acids were observed. Some seasonal variations in fatty acid (FA) compositions for M. rea and D. alvarezae were observed. The hierarchical Clusters Analysis (HCA) showed that the FA composition was species-specific but not informative at the family or order level.

Antecedentes: Los productos naturales aislados de microorganismos marinos han demostrado tener un amplio rango de actividades biológicas incluyendo inhibidores de quorum sensing. Objetivos: Estudiamos quince cepas bacterianas del phylum Firmicutes aisladas del coral blando Antillogorgia elisabethae que fueron evaluadas como una nueva fuente sostenible de compuestos inhibidores de quorum sensing (IQS). Métodos: Se prepararon cultivos en cuatro medios diferentes y extraídos usando una resina no iónica. Todos los extractos fueron probados con el fin de establecer su actividad inhibitoria de quorum sensing (IQS) usando Chromobacterium violaceum ATCC 31532 como biosensor. Los extractos activos fueron fraccionados mediante cartuchos RP-18. Cada fracción fue evaluada mediante bioensayo y analizada por HPLC. Resultados: Las fracciones metanólicas de Jeotgalicoccus halophilus y Oceanobacillus profundus fueron las más activas, lo cual sugiere que los compuestos no polares pueden ser los responsables de esta actividad. Conclusiones: El estudio químico del extracto orgánico de O. profundus cultivado en medio LBS permitió aislar los compuestos tirosol (1) y acetato de tirosol (2) como los responsables de la actividad IQS.

Background:Natural products isolated from marine microorganisms have demonstrated a wide range of biological activities included quorum sensing inhibitors. Objectives: We study fifteen marine Firmicutes bacterial strains isolated from the Caribbean soft coral Antillogorgia elisabethae that were evaluated as a novel and sustainable source of quorum sensing inhibitor compounds. Methods: Cultures were made in four different culture media and further extracted using a non-ionic resin. All these extracts were tested in order to establish its quorum sensing inhibition (QSI) activity using Chromobacterium violaceum ATCC 31532. The active extracts were fractionated by RP-18 cartridge. Each fraction was tested and evaluated for its composition by HPLC-PDA. Results: Methanol fractions of Jeotgalicoccus halophilus and Oceanobacillus profundus were the most active ones, suggesting that non-polar compounds could be the responsible for the QSI activity of the bacterial extracts here tested. Conclusions:The chemical study of the organic extract of Oceanobacillus profundus cultured in LBS, yielded the compounds tyrosol (1) and tyrosol acetate (2) as responsible of QSI activity showed by the organic extract.

AbstractIn this study, 39 extracts from marine organisms were evaluated as quorum sensing inhibitors, collected in the Colombian Caribbean Sea and the Brazilian Coast including 26 sponges, seven soft corals, five algae and one zooanthid. The results showed that crude extracts from the soft coral Eunicea laciniata, and the sponges Svenzea tubulosa, Ircinia felix and Neopetrosia carbonaria were the most promising source of quorum sensing inhibitors compounds without affecting bacterial growth, unlike the raw extracts of Agelas citrina, Agelas tubulata, Iotrochota arenosa, Topsentia ophiraphidites, Niphates caycedoi, Cliona tenuis, Ptilocaulis walpersi, Petrosia pellasarca, and the algae Laurencia catarinensis and Laurencia obtusa, which displayed potent antibacterial activity against the biosensors employed. The crude extract from the sponge I. felix was fractionated, obtaining furanosesterterpenes which were identified and evaluated as quorum sensing inhibitors, showing a moderate activity without affecting the biosensor's growth.

El presente trabajo, describe el desarrollo de una estrategia metodológica para acelerar y simplificar la detección e identificación de los compuestos producidos en cuatro medios de cultivo diferentes, por 14 bacterias del phylum Firmicutes simbiontes del octocoral Pseudopterogorgia elisabethae de la Isla de Providencia, Caribe Sur-Occidental. El proceso involucró la miniaturización de los cultivos bacterianos, la extracción en fase sólida de los productos usando la resina DiaionTM HP-20, el análisis por UPLC-MS de los mismos y finalmente la generación de una librería que permitió descartar los componentes o productos de descomposición de los medios de cultivo, además de detectar 46 compuestos producidos por el total de las bacterias y la posterior identificación de 10 de ellos, haciendo uso de la base de datos Antibase 2007TM como herramienta de derreplicación de las sustancias detectadas.

This paper describes a convenient strategy to accelerate and simplify the detection and identification of compounds produced in four different culture media, by 14 bacteria of the phylum Firmicutes, symbionts of the octocoral Pseudopterogorgia elisabethae collected at Providencia Island, South-West Caribbean. The process involved: bacterial culture miniaturization, solid phase extraction of the products using the resin DiaionTM HP-20, the analysis by UPLC-MS of the products and finally the generation of the library, that allows to discard culture media components detecting 46 compounds produced by all bacteria and the subsequent identification of 10 of them, using the database Antibase 2007TM as a tool for dereplication of these substances.

The exploration of marine environment represents a promising strategy in the search for new active antiviral compounds. The isolation and characterization of the nucleosides spongothymidine and spongouridine from the sponge Cryptotethia crypta used as models for the synthesis of ara-A (vidarabine), that has been used therapeutically against herpetic encephalitis, was the most important contribution since the late 1970s. This paper describes the in vitro antiviral evaluation of 26 organic extracts obtained from eleven octocoral species and fifteen marine sponges. Cytotoxicity was evaluated on Vero cells by MTT assay and the antiviral activity was tested against Herpes Simplex Virus type 1 (HSV-1, KOS strain) by plaque number reduction assay. Results were expressed as 50% cytotoxic (CC50) and 50% inhibitory (IC50) concentrations, respectively, in order to calculate the selectivity index (SI= CC50/IC50) of each extract. Among the tested marine octocoral species, only three extracts showed antiviral activity, but with low selectivity indices (<3.0). Among the tested marine sponges, eight extracts showed SI values higher than 2.0, and three can be considered promising (Aka cachacrouense, Niphates erecta and Dragmacidon reticulatum) with SI values of 5.0, 8.0 and 11.7, respectively, meriting complementary studies in order to identify the bioactive components of these sponge extracts, which are in course now.

As configurações dos carbonos C-24 nos compostos (22E)-24-etil-24-metilcolesta-5,22-dien-3β-ol (1) e 24-etil-24-metilcolest-5-en-3β-ol (2), isolados da esponja do caribe colombiano Topsentia ophiraphidites foram determinadas como R e S, respectivamente, com base na comparação dos seus dados de RMN com aqueles de amostras de configurações já definidas 24R e 24S, as quais foram sintetizadas em rotas envolvendo ortoésteres provenientes do rearranjo de Claisen de álcoois Δ23-22 alílicos. Este é primeiro estudo de síntese, em que o rearranjo de Claisen é utilizado para introduzir um centro quaternário em C-24, de maneira estereoespecífica e com rendimento aceitável. Análises por difração de raio X de 1 confirmaram essas atribuições estereoquímicas.

The C-24 configurations of (22E)-24-ethyl-24-methylcholesta-5,22-dien-3β-ol (1) and 24-ethyl-24-methylcholest-5-en-3β-ol (2), isolated from the Colombian Caribbean sponge Topsentia ophiraphidites, were determined to be R and S, respectively, by comparing their NMR data with those of stereodefined (24R)- and (24S)-samples that were synthesized in routes involving the orthoester Claisen rearrangement of Δ23-22-allylic alcohols. This is the first synthetic study where the Claisen rearrangement is used to introduce a C-24 quaternary center in a stereospecific manner with acceptable yield. X-ray analysis of 1 confirmed these stereochemical assignments.

Del extracto orgánico de la esponja marina Cliona tenuis, recolectada en las Islas del Rosario (Colombia, mar Caribe), fue obtenida la fracción lipídica, la cual presentó propiedades antifouling en pruebas en campo. Esta fracción fue separada por CC sobre gel de sílice hasta obtener fracciones de ésteres metílicos, glicéridos, glicolípidos, fosfolípidos y ácidos grasos libres, las cuales fueron identificadas por CCD y técnicas de de-replicación (RMN 1H y 13C). Posteriormente, las fracciones de glicéridos, glicolípidos y fosfolípidos fueron hidrolizadas, y los ácidos obtenidos, junto con los provenientes de la fracción de ácidos grasos libres, fueron transformados en ésteres metílicos, y todos se analizaron por CGAR-EM. Para ubicar las insaturaciones y ramificaciones, los ésteres metílicos se transformaron luego en sus correspondientes pirrolididas, las cuales también se analizaron por CGAR-EM. El estudio cromatográfico (valores de ECL) y de los espectros de masas de los ésteres metílicos y de sus derivados pirrolididas permitió identificar 81 ácidos grasos diferentes, de los cuales no habían sido previamente reportados: los ácidos 4,8-hexadecadienoico, 11-metil- 4,10-octadecadienoico, 6,9,12,14- icosatetraenoico, y 6,9,12,14,17-icosapentanoico.

The lipid fraction obtained from the marine sponge Cliona tenuis, collected at the Islas del Rosario (Colombia, Caribbean Sea), showed antifouling activity using field bioassays. This fraction was separated by CC on silica gel obtaining a mixture of methyl esters, and enriched fractions of glycerides, glycolipids, phospholipids and free fatty acids. All of them were identified by TLC and dereplication techniques (NMR). The glyceride, glycolipid, and phospholipid fractions were hydrolyzed and the fatty acids obtained, together with the initial fatty acids fraction, were converted into their methyl esters and analyzed by HRGC-MS. To locate unsaturations and alkyl branches in fatty acids, their methyl esters derivates were transformed to pyrrolidides and subsequently analyzed by HRGC-MS. The identity of the fatty acids was carried out using their ECL value as methyl esters, and particularly the study of their pirrolidide spectra was used to locate unsaturations and alkyl branch positions. This study allowed us to identify 81 fatty acids, four of them never reported before: 4,8-hexadecadienoic acid, 11-methy l-4, 10-octadecadienoic acid, 6,9,12,14-icosatetraenoic acid, and 6,9,12,14,17-icosapentanoic acid.

A partir do extrato orgânico da esponja marinha Cliona tenuis, coletada nas ilhas do Rosario (Colombia, Mar Caribe), foi obtido uma fração lipídica, que apresentou propriedades antifouling in situ. Esta fração foi separada através de CC em gel de sílica para obter as frações de ésteres metílicos, glicerídeos, glicolipídeos, folfolipídeos e ácidos libres, as quais foram identificadas por CCD e técnicas espectroscópicas de RMN 1H e 13C. Posteriormente, as frações contendo glicerídeos, glicolipídeos e folfolipídeos foram hidrolizadas e os ácidos obtidos, juntamente com os ácidos obtidos das frações que continham ácidos livres foram transformadas em ésteres metílicos e analisados por CGAR-EM. Para identificar as insaturações e ramificações, os ésteres metílicos foram transformados em derivados pirrolidínicos para serem analisadas por CG-EM. Através da análise cromatográfica (valores de ECL) e dos espectros de massas dos ésteres metílicos e seus derivados pirrolidínicos foi possível identificar 81 ácidos graxos diferentes, sendo que quatro são compostos ainda não relatados: os ácidos 4,8-hexadecadienóico, 11-metil-4,10-octadecadienóico, 6,9, 12, 14- icosatetraenóico, e 6,9,12,14,17-icosapentanóico.

Las mariposas de la tribu Troidini (Lepidoptera: Papilionidae) capturan los ácidos aristolóquicos (AAs) provenientes de su alimentación larval en plantas de Aristolochiaceae para su protección. En este estudio se detectó la presencia de los ácidos aristóloquicos I y II (AAI y AAII) en hojas jóvenes de Aristolochia maxima (Aristolochiaceae) y en larvas de las mariposas Battus polydamas polydamas y Parides panares erythrus (Papilionidae, Papilioninae) por Cromatografía Líquida de Alta Eficiencia (CLAE). De acuerdo con los resultados de los perfiles cromatógraficos por CLAE, el AAI fue el ácido aristolóquico mayoritario encontrado tanto en las larvas como en las hojas jóvenes de la planta, seguido por cantidades menores del AAII. Estos resultados permiten afirmar que la interacción plantaanimal entre las mariposas de las especies B. polydamas y P. panares y las plantas de A. maxima, está mediada, por los ácidos aristóloquicos I y II.

Most butterflies of the tribe Troidini (Lepidoptera: Papilionidae) sequester aristolochic acids (AA) for their protection. These acids are derived from their host plants family Aristolochiaceae upon which they feed on during their larval stages. Using analytical High Performance Liquid Chromatography (HPLC) methods we were able to detect the presence of aristolochic acids I and II both in the young leaves of Aristolochia maxima (Aristolochiaceae) and in the caterpillars of the butterflies Battus polydamas polydamas and Parides panares erythrus (Papilionidae, Papilioninae). Aristolochic acid I was the major constituent found, followed by lesser amounts of Aristoloquic acid II. These results confirm that the hostanimal interaction among butterflies of the studied species and A. maxima plants is mediated, by aristolochic acids.