The synthesis of p-lactams has been of foremost importance since the discovery of penicillin by Sir Alexander Fleming, in 1928, and its susequent structure elucidation in 1945. Ethyl N-2-bromo-alkylcarbamates show considerable potential as precursors to p- lactams. In the past, p-lactams have been prepared by many methods, none of which have involved 2-3 bond formation. The proposed ring closure using ethyl N-2-bromoalkylcarbamate involves 2-3 bond formation, making this method of synthesis novel. This work describes two attempted methods of cyclisation. The first using a Grignard reagent, and the second, using abstraction of an acidic proton a to a phosphonate group. These methods of intramolecular cyclisation were based on analogous intermolecular additions, which are also described. The second method was also used to determine the general potential of ethyl N-bromo- alkylcarbamtes as precursors to other heterocyclic systems. / Thesis (M.Sc.)-University of Natal, Durban, 2001. / NRF & NRF/DEA & T.

The projects described in this dissertation are focused on compounds derived from the marine environment. Chapter 1 gives an introduction to the study of marine natural products to treat human ailments and a thorough review on compounds from lithistid sponges that have been isolated or synthesized since 2000. Chapter 2 describes the isolation and structure elucidation of two sesquiterpene substituted benzoquinone derivatives, petrosiquinones A and B, from a deep-water marine sponge from the Family Petrosiidae. Although initially purified following activity in a (Sb(B-catenin/Tcf4 assay they were later followed using tumor cell line cytotoxicity assays. Petrosiquinone A was the more active of the two compounds with moderate cytotoxicity in the DLD-1, PANC-1, and AsPC-1 cell lines. In Chapter 3, the isolation and structure elucidation of two new marine-derived macrolides, madeirolide A and B, isolated from a deep-water lithistid sponge of the genus Leiodermatium is described. / They were isolated using numerous chromatographic techniques and the structures were elucidated on the basis of 1D and 2D NMR spectra coupled with high resolution-mass spectrometry (HR-MS) data. Madeirolide A and B inhibited the growth of the fungal pathogen Candida albicans with minimum inhibitory concentrations (MIC) of 12.5 and 25 (So(Bg/mL, respectively, but were not cytotoxic in tumor cell assays under the conditions tested. Chapter 4 describes work performed to determine the molecular target of lasonolide A using affinity chromatography. The target of lasonolide A is of interest since lasonolide A is known to kill cancer cells in vitro through a unique mechanism. / This chapter highlights the research performed to create an affinity matrix with immobilized lasonolide. A target has not been confirmed but there are a number of interesting hits that are being pursued. In Chapter 5, a liquid chromatography-mass spectrometry (LC-MS) screening method was established in order to rapidly identify the metabolites from numerous collections of Lyngbya spp. obtained from Broward and Lee County, Florida sites that may help marine ecologists assess the effects of Lyngbya spp. blooms on the environment. A link between the metabolites produced and nutrients from both the algal tissue and water column was also explored. / by Priscilla L. Winder. / Thesis (Ph.D.)--Florida Atlantic University, 2009. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2009. Mode of access: World Wide Web.

Esponjas (filo Porifera) são consideradas representantes atuais dos primeiros metazoários, com origens evolutivas próximas da transição de uma organização unicelular para aquela multicelular. Toda sua fisiologia é baseada em células especializadas, sem órgãos ou tecidos verdadeiros como encontrados em outros animais. No entanto, a presença de um sistema fortemente integrado pode ser constatada em sua habilidade de contrair o corpo de maneira rítmica e coordenada, ainda que a dinâmica e o controle desse processo sejam pouco conhecidos. Neste trabalho, análises de imagens em time-lapse sob um ciclo claro-escuro (12:12h) e sob luz constante mostram que as espécies Hymeniacidon heliophila e Tethya maza exibem padrões distintos de contrações corpóreas rítmicas, com variações circadianas em suas amplitudes. Diferenças observadas nos perfis das curvas das duas espécies podem ser devidas a diferenças em seus habitats de origem e/ou a diferenças em suas estruturas corpóreas. A manutenção desses ritmos sob luz constante indica a presença de um relógio endógeno em ambos os animais. Entre as vias envolvidas na sinalização desses processos a mais ubíqua é a da melatonina, um hormônio cuja presença tem sido demostrada em muitos filos animais, dos quais o mais basal é o Cnidaria. Considerando a ampla ação da melatonina como um sinalizador circadiano e a ausência de um sistema nervoso em esponjas, não seria surpreendente constatar um papel da molécula na coordenação dos movimentos desses animais. Ademais, o papel da molécula nas respostas imunes também já foi demonstrado ser de ampla distribuição. Nossas tentativas de revelar uma ação da molécula na reagregação celular de H. heliophila via receptores do tipo MT1 e MT2 não foram conclusivas. Alguns fatores que podem ter influenciado nas respostas divergentes da molécula são o estado imunitário e a presença de contaminantes no ambiente de origem do animal. Ainda, outros mecanismos de ação e/ou processos candidatos à ação da melatonina não devem ser descartados. Ainda que preliminares, nossos resultados são o primeiro relato da presença da melatonina no filo mais basal dentre os Metazoa / Sponges (phylum Porifera) are considered current representatives of the first metazoans, with evolutionary origins close to the transition from a unicellular to a multicellular organization. All of its physiology is based on specialized cells, without organs or real tissues as found in other animals. However, the presence of a strongly integrated system can be verified in its ability to contract the body in a rhythmic and coordinated way, althouth the dynamic and the control of this process are little known. In this work, time-lapse image analysis under a light-dark cycle (12:12h) and constant light shows that the species Hymeniacidon heliophila and Tethya maza display different patterns of body contractions, with circadian variations in their amplitudes. These dissimilar contraction profiles of the two species can be due to their original habitats and/or in their body structures. The maintenance of these rhythms under constant light indicates the presence of an endogenous clock in both animals. Among the pathways that participate in this process the most ubiquitous is that of melatonin, a hormone whose presence has been demonstrated in several animals phyla, of which the most basal until now is Cnidaria. Considering the melatonin action as a circadian signal and the absence of a nervous system in sponges, it would not be surprising that this molecule participates in coordination in these animals. In addition, the melatonin role in the immune responses has also been shown to be widely distributed. Our attempts to reveal a molecule action in the H. heliophila cellular reaggregation via MT1 and MT2 receptors were inconclusive. Some of the factors that may have influenced the molecule divergent responses are the immunity condition and the presence of contaminants in the original environment of the animals. Still, other mechanisms and/or processes that are candidates for melatonin action should not be discarded. Although preliminary, our results are the first report of the presence of melatonin in the most basal phylum among the Metazoa

Current research in natural products has heavily focused on the identification of potent biologically active compounds, specifically for drug development. The project detailed in this thesis focuses on the extraction of compounds from marine invertebrates as well as defining the absolute configuration for a compound. Utilizing marine invertebrates, the sonications method developed in this thesis provides an alternative approach to rapidly extract compounds for primary screening. This method is viable compared to a traditional overnight extraction method, without suffering compound degredation... Previously, clathric acid was isolated from an unknown Clathria sp. This compound is a bibyblic C-21 terpenoid shown to have mild antimicrobial activity against gram positive bacteria. With only its relative configuration established, additional amounts of clathric acid were required to define the overall absolute configuration. Identifying the Clathria sp. to be Clathria compressa, through spicule analysis, additional sponge tissues were then collected off the coast of Boca Raton, Florida to isolate additional quatities of clathric acid. The absolulte configuration was determined through circular dichroism and the octant rule to establish a final configuration for clathric acid's four carbon stereocenters to be: (3S, 7S, 8R, and 12S). / by Rolando Rueda de Leâon. / Thesis (M.S.)--Florida Atlantic University, 2012. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

Sponges are an important source of bioactive marine natural products, or secondary metabolites. The common Caribbean reef sponge, Axinella corrugata, produces an antitumor and antibacterial chemical, stevensine. This study determined whether environmental stressors, such as elevated temperature and exposure to Amphibalanus amphitrite larvae, affect the production of stevensine by A.corrugata and if the stressors caused A.corrugata to exhibit differential gene expression. Temperature stress resulted in no significant change in the production of stevensine; only two genes were significantly differentially expressed, including hsp70. Larval stressed resulted in increased production of stevensine and significant differential gene expression (more than seventy genes). This study suggests that A.corrugata may be resilient to elevations in temperature and that one of stevensine's roles in nature is as an antifoulant. / by Jennifer Grima. / Thesis (M.S.)--Florida Atlantic University, 2013 / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

Marine sponges interact and coexist with many different organisms. A two-sponge association between Amphimedon erina and Geodia gibberosa commonly occurs in the Florida Keys. Previous studies have only focused on the ecological influence of the association; they did not examine the cellular basis of the association. This association between A. erina and G. gibberosa was used in the development of an in vitro model to further the understanding of the cellular basis of natural sponge-sponge associations. In this study, sponge cells were cultured individually and in co-cultures and their responses related to apoptosis, cell death, and proliferation were monitored using high content imaging. Co-cultured cells of species that form sponge-sponge associations did not have the same cellular responses compared to co-cultured cells of species that do not form sponge-sponge associations. Protein expression analyses demonstrated that the model that was established does not mimic the cellular response of the association in nature, but this model can be used to test in vitro cellular interactions of sponge species that do not form associations in nature. In addition, the protein expression data that were obtained revealed that sponges use similar apoptotic pathways as humans and suggest that sponge cells may shut down cell cycling in order to repair damaged DNA. This research is a small piece to the puzzle that is sponge cell culture research. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2017. / FAU Electronic Theses and Dissertations Collection

Populations of a marine invertebrate symbiont were found on the outer surface and internal spaces of a keratose sponge from a shallow bay in the Florida Keys in May 2014. A total of 24 specimens of the seagrass and reef-dwelling sponge were collected between May 2014 and August 2015 to provide material to identify both host and symbiont, and elucidate information on the nature of the association. Based on a morphological analysis via light microscopy, histology, and scanning electron microscopy (SEM), and 99% similarity in aligned partial sequences from 28S and 18S nuclear ribosomal genes (rDNA), the symbiont was identified as the solitary entoproct Loxosomella vivipara Nielsen, 1966 (Entoprocta: Loxosomatidae). A partial sequence from the Internal Transcribed Spacer Region 2 (ITS2) of L. vivipara was registered to GenBank for the first time. The identity of the host sponge, based on a morphological investigation, is resolved as “velvet sponge” Hippospongia cf. gossypina Duchassing and Michelotti, 1864 (Demospongiae: Spongiidae). This is the first report of an entoproct commensal from Hippospongia cf. gossypina, a sponge that formerly had great commercial value when it was abundant throughout the Bahamas, Florida Keys and Gulf of Mexico. Other common sponge species at the study site were collected to investigate the host specificity of L. vivipara. Evidence that L. vivipara favorably selects the sponges Hippospongia cf. gossypina and Chondrilla nucula over other potential host sponges at the study site is provided. Commensalism is the most plausible justification for this relationship: L. vivipara is dependent on sponges for protection and food particles, while the sponges are unaffected by its presence. Further evidence of host-specific inquilinism is provided for L. vivipara associated with Hippospongia cf. gossypina, but not for L. vivipara associated with C. nucula. An inquilinistic association between an entoproct and sponge is a rare discovery only mentioned in one previous study. Sponge aquiferous qualities such as aperture and canal size, canal and choanocyte chamber arrangement, seawater pumping rate, and food particle size selection are likely factors that inhibit or enable inquilinism in sponge-entoproct associations – a potential topic for future researc / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2016. / FAU Electronic Theses and Dissertations Collection

Esponjas de cozinha podem promover contaminação cruzada ao transferirem microrganismos de superfícies variadas para os alimentos. Os objetivos deste estudo foram avaliar a contaminação microbiológica e a eficácia de dois procedimentos de desinfecção de esponjas utilizadas em serviços de alimentação, bem como avaliar a transferência microbiana a partir de esponjas para o aço inoxidável e polietileno. Na primeira parte deste estudo, 80 esponjas naturalmente contaminadas foram coletadas em serviços de alimentação e então transferidas para o laboratório, onde foram divididas em três partes iguais. Uma das partes foi submetida à contagem de microrganismos heterotróficos (MH), coliformes a 45 oC (CF), Staphylococcus coagulase positiva (SA) e à pesquisa de Salmonella sp. (SAM). As outras duas partes foram submetidas, separadamente, à fervura em água durante cinco minutos e à desinfecção por hipoclorito de sódio 200ppm, por 10 minutos, adicionada de enxágue com água potável. Na segunda parte do estudo, 24 esponjas naturalmente contaminadas foram friccionadas sobre superfícies de aço inoxidável AISI 316 e polietileno, separadamente, a fim de investigar o número de microrganismos transferidos e sua sobrevivência. Os resultados demonstraram contaminações médias por MH de aproximadamente 9,1 LogUFC/esponja, e 76,25% delas apresentaram contagens médias de CF de aproximadamente 8,4 Log UFC/esponja. Apenas 2,5% das amostras apresentaram SA e SAM. Ambos os procedimentos de desinfecção foram capazes de reduzir significativamente as contagens bacterianas, porém a fervura demonstrou reduções maiores (6,7 Log UFC/esponja) que a desinfecção por hipoclorito de sódio a 200ppm (2,7 Log UFC/esponja ). A média de transferência de microrganismos variou entre 3,3 e 5,5 LogUFC/cm2, para aço inoxidável, entre 3,5 e 5,6 LogUFC/cm2, para o polietileno, sendo que os microrganismos transferidos foram perdendo sua viabilidade sobre ambos materiais. Nas primeiras quatro horas de exposição em temperatura ambiente a redução do número de microrganismos foi mais acentuada, e em 24 horas restaram cerca de 1 a 2 logUFC/cm2 de microrganismos viáveis. / Kitchen sponges can promote cross-contamination by transferring microorganisms from various surfaces to food. The objectives of this study were to evaluate the microbiological contamination and effectiveness of two procedures for disinfection of sponges used in food services, and to assess the microbial transfer from sponges to stainless steel and polyethylene. In the first part of this study, 80 sponges were collected in food services and then transferred to the laboratory where they were divided into three equal parts. One part was subjected to quantification of heterotrophic microorganisms (HM), fecal coliforms (CF), Staphylococcus coagulase-positive (SA) and Salmonella sp. (SAM). The other two parts were separately subjected to boilling in water for five minutes, and disinfection by sodium hypochlorite 200ppm for 10 minutes, added by rinse with water. In the second part of the study, 24 naturally contaminated sponges were rubbed on surfaces of AISI 316 stainless steel and polyethylene, separately, to investigate the number of transferred microorganisms and their survival. The results showed contamination averages by HM of approximately 9.1 log CFU/sponge, and 76.25% had average scores of CF of about 8.4 log CFU/sponge. Both disinfection procedures were able to significantly reduce bacterial counts, but the boiling showed greater reductions (6.7 log CFU/sponge) than the disinfection by sodium hypochlorite at 200ppm (2.7 log CFU/sponge) The average transfer of microorganisms varied between 3.3 and 5.5 log CFU/cm2 for stainless steel, and 3.5 to 5.6 log CFU/cm2, for polyethylene, and the transferred microorganisms were losing their viability on both materials. In the first four hours of exposure at room temperature the reduction of the number of microorganisms was more pronounced, and in 24 hours there were about 1 to 2 log CFU/cm2 remaining viable microorganisms.

Este trabalho visou a averiguação do status taxonômico das esponjas bioerosivas do complexo Cliona celata da América do Sul por meio de técnicas moleculares, utilizando como marcadores a subunidade I da Citocromo c oxidase (cox1) e os Espaçadores Internos Transcritos do RNAr nuclear (ITS1 e ITS2), além de testar outros marcadores. Igualmente, avaliou o grau de variabilidade morfológica encontrado nessas espécies, principalmente por meio da morfometria dos tilóstilos, a fim de estabelecer uma diagnose para elas. Ainda, tentou determinar as relações filogenéticas dessas espécies com as demais esponjas bioerosivas utilizando o gene 28S do RNAr nuclear. Foi possível determinar a existência de cinco clados de esponjas bioerosivas do complexo Cliona celata para a América do Sul, e dois outros clados não-sulamericanos, por meio dos marcadores moleculares utilizados. Embora seja discutida a validade desses clados como espécies distintas, continua impossível, por meio de caracteres morfológicos, distingui-los, e dessa forma, a proposição formal de novas espécies é evitada. Através da reconstrução filogenética do grupo, é possível verificar que as esponjas bioerosivas analisadas se apresentaram como um grupo monofilético, e se separa em três principais clados: Pione, Spirastrellidae, e Clionaidae. Por meio desta, é sugerida a alocação das espécies do complexo C. viridis e C. schimidti dentro de Spirastrella, além de ser necessária a criação de um novo gênero para alocar as espécies do novo complexo identificado aqui, o complexo C. delitrix. / This work intended the validation of the taxonomic status of boring sponges from the Cliona celata complex of South America by molecular techniques, using Cytochrome coxidase, subunit I (cox1), and Internal Transcribed Spacers (ITS) of rRNA nuclear genes as molecular markers. Additionally, the degree of morphological variation necessary to establisha correct diagnosis for the studied species was evaluated, and additional markers were tested. Finally, a phylogenetic analysis comparing this species with other boring sponges, using the 28S rRNA nuclear gene was carried out. It was possible to point out the existence of five clades of boring sponges from the C. celata complex in South America, and two more from Mexico and Australia. Although these clades can comprise new valide species, no morphological evidence was found to separate them, and thus, no formal species descriptions were presented. Through out phylogenetic analyses it was possible to conclude that boring sponges form a monophyletic group, which can be separated in three clades: Pione, Spirastrellidae, and Clionaidae. This work suggests to allocate C. viridis and C. schimidti species complexes inside Spirastrella, and to create a new genus for the new C. delitrix species complex.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2016-10-18T18:36:37Z No. of bitstreams: 1 2015 - Ivan Pierozzi Junior.pdf: 92591526 bytes, checksum: b6f151111ef71de5cd89f7d46f910fff (MD5) / Made available in DSpace on 2016-10-18T18:36:37Z (GMT). No. of bitstreams: 1 2015 - Ivan Pierozzi Junior.pdf: 92591526 bytes, checksum: b6f151111ef71de5cd89f7d46f910fff (MD5) Previous issue date: 2015-11-27 / CAPES / Rhodolith bed has aroused growing interest of the scientific community, not being different to the Fernando de Noronha Archipelago (FNA). FNA rhodolith banks occur at depths of 10 to 100m and are peculiar habitat that increases structural complexity, providing increased associated diversity compared to unconsolidated substrates. The interaction between rhodoliths and sponges is the focus of this study. On the banks of AFN sponges play an important role in the stabilization mechanism of rhodoliths, accounting for coalescing neighbour nodules, which may point to an early stage of an on going process of stabilization in the form of a consolidated reef. The presence of reef-building corals in the adjacent rocky shore can also be related to the rhodolith banks as polyp?s skeletons were found nucleating rhodoliths. This study identified which organisms were agglutinating rhodolith nodules at Cabe?o da Sapata (45m deep) and if is there any relationship between physical characteristics of the bank and the occurrence of agglutinated complex. It was also described the physical structure and the frequency of occurrence of agglutinated rhodolith. Sponges was the main group of sessile fauna found coalescing rhodoliths and this process points to a relationship between size of the nodules and the variation in size between the nodes. The importance of sponges to the rhodoliths beds and potentially to the process of consolidated reefs formation is reinforced by this study. / Os bancos de rodolitos tem despertado interesse cada vez maior da comunidade cient?fica, n?o sendo diferente para o Arquip?lago de Fernando de Noronha (AFN). No AFN os bancos de rodolitos ocorrem em profundidades de 10 a 100m e s?o habitat peculiares que aumentam a complexidade estrutural, propiciando um aumento da diversidade associada quando comparados com substratos n?o consolidados. A intera??o entre os rodolitos e por?feros ? o foco desse estudo. Nos bancos do AFN as esponjas desempenham um importante papel no mecanismo de estabiliza??o dos rodolitos, sendo respons?veis por aglutinar n?dulos pr?ximos, o que pode apontar para um estagio inicial de um processo permanente de estabiliza??o, na forma de um recife consolidado. A presen?a de recifes coral?neos no cost?o rochoso adjacente tamb?m podem ter rela??o com os bancos de rodolitos j? que esqueletos de p?lipos foram encontrados nucleando rodolitos. Neste estudo foram identificados quais organismos foram respons?veis pela aglutina??o de n?dulos do banco de rodolitos do Cabe?o da Sapata (45m de profundidade) e se existe rela??o entre caracter?sticas f?sicas do banco e a ocorr?ncia de aglutinados. Tamb?m foi descrita a estrutura f?sica e a frequ?ncia de ocorr?ncia de aglutinados de rodolitos. Por?fero foi o principal grupo da fauna s?ssil encontrado aglutinando rodolitos e esse processo aponta para uma rela??o entre tamanho dos n?dulos e a varia??o de tamanho entre os n?dulos. A import?ncia das esponjas nos bancos de rodolitos, e potencialmente no processo de forma??o de recifes consolidados, ? refor?ada pelo presente estudo,