The focus of this thesis was to study the chemotaxonomic relationship of selected southern Australian marine brown algae of the genera Cystophora and Sargassum. Consequently, this resulted in the isolation and structure elucidation of six new terpenoids from two southern Australian marine brown algae Cystophora moniliformis and Sargassum fallax together with 10 previously reported natural products. As a result of the re-isolation of these known secondary metabolites, updated and complete structural characterisation data could be provided for the first time for 7 of these compounds. Chemotaxonomic studies of Cystophora moniliformis resulted in the isolation of two new cyclic epimeric terpene diols moniliforminol A (3.25) and moniliforminol B (3.26), a new linear farnesyl acetone derivative (3.27) and the previously described terpenoids (3.19)-(3.24). This study also resulted in the first complete 2D NMR characterisation for compounds (3.21) to (3.24) as well as the first report of (3.24) occurring as a natural product. All structures were elucidated by detailed spectroscopic analysis with the relative configurations of (3.25) and (3.26) being established by selective 1D nOe NMR experiments. The proposed biosynthetic pathway for the above compounds has also been described. Chemical investigation of the Southern Australian marine brown alga Sargassum fallax resulted in the isolation of three new meroditerpenoids fallahydroquinone (4.8), fallaquinone (4.9) and fallachromenoic acid (4.10), together with the previously reported compounds sargaquinone (4.1) (isolated and identified in a mixture with sargaquinoic acid), sargahydroquinoic acid (4.2), sargaquinoic acid (4.3) and sargachromenol (4.11). As a result of this study the complete 2D NMR characterisation for sargahydroquinoic acid (4.2) and sargaquinoic acid (4.3) could also be reported for the first time. All structures were elucidated by detailed spectroscopic analysis. Sargahydroquinoic acid (4.2) and sargaquinoic acid (4.3) displayed moderate antitumour activity.

The role of antioxidants in the prevention of neurodegenerative diseases has been well documented. The use of synthetic antioxidants has decreased due to the ssociation of these compounds with certain cancers. Thus, the search for novel natural antioxidants has gained much focus in research. Most common methods of determining antioxidant capacity are the radical generated assays and biological assays such as lipid peroxidation and the nitroblue tetrazolium assay. Electrochemical methods have been proposed for the determination of bio-active compounds such as antioxidants. The electrochemical methods of cyclic voltammetry and square wave voltammetry were evaluated for the determination of antioxidant capacity initially examining known antioxidants and then using plant extracts of Sutherlandia frutescens as a case study. The antioxidant properties determined by electrochemical methods were validated utilising the non-biological methods of the DPPH, TEAC, ferrozine and FC assay and biological pharmacological methods. The results indicated that Sutherlandia frutescens contains potent antioxidant compounds that are able to reduce lipid peroxidation. The electrochemical techniques of square wave voltammetry and cyclic voltammetry were applied for the screening of a large number of extracts of various algae for the detection of antioxidant compounds. The results indicated that electrochemistry can be used as a preliminary method for the rapid screening of a large number of crude samples for antioxidant compounds. Electrochemical methods were also evaluated as a method for guiding the isolation and purification of antioxidant metabolites in Sargassum elegans. Solvent partitioning and fractionation of the marine alga allowed for the purification of antioxidant compounds. At each step of purification electrochemical methods were utilized to determine which fractions contained the more potent antioxidant compounds and thus guide further purification. The purified antioxidant compounds were elucidated using NMR to determine the structure of the antioxidant compounds.

The West Indies have during recent years been experiencing large quantities of washed up Sargassum seaweed on beaches and coastlines causing many issues for local communities such as unpleasant odours, making beaches inaccessible and largely affecting tourism and fisheries. The issue has caused money loss for the communities both in cleaning costs and decreasing incomes from tourism and fishing. In an attempt to turn this destructive debris into a useful resource, this study aimed to determine the potential for Sargassum that has been anaerobically digested to be used as a liquid fertiliser on Grenada. Sargassum seaweed was collected from the Atlantic coast of Grenada and transported and fed to a biogas plant where the algae was anaerobically digested. The residues were collected and fed to Pak Choi crops in a cultivation experiment where the fertiliser was compared with other treatment methods in order to determine its efficiency as a fertiliser. Interviews of farmers on Grenada were also conducted during the project to examine the potential and usefulness of the biofertiliser on the local Grenada farms. It was found that the digestate product from the anaerobic digestion showed good potential as a biofertiliser, producing larger and healthier crops than the other methods of treatments, among them artificial fertiliser. A potential market for the product was also identified as all the interview subjects reported that artificial fertilisers can be hard or impossible to find on Grenada sometimes of the year, due to the island's high reliance on shipping containers for import, leading to a demand of alternative fertilisers. / Under de senaste åren har algblomningarna ökat runt om i Västindien och numera är flertalet stränder  fyllda av Sargassotång. Ett av länderna som har påverkats negativt är Grenada. Stora mängder Sargassum når östkusten av Grenada under större delen av året till skillnad från tidigare år då algerna enbart sköljdes in under vissa perioder och i mindre kvantiteter. Algmassorna leder till lokal övergödning i de drabbade områdena, vilket i sin tur leder till minskad syrekoncentration i vattnet och en stor påverkan på djur och växter i ekosystemet. I Grenada påverkar makroalgerna även inkomstkällan för fiskare då de inte kan arbeta när det är som mest alger eftersom båtarna inte kan ta sig förbi massorna i vattnet. Även lokalbefolkning och turister påverkas då nedbrytningen av algerna skapar en motbjudande lukt vilket leder till att människor flyttar från dessa områden och att turistnäringen minskar. Grenada har ett behov av att minska mängden alger längs stränderna och samtidigt finns en möjlighet att ta tillvara en lokal bioresurs. En möjlighet är att använda algmassan till produktion av biogas och biogödningsmedel eftersom nedbrytning av makroalgeralger både kan producera metangas samt att  återstående restbiomassa innehåller de viktigaste näringsämnen som växter behöver för att växa. Därför  har algerna använts i ett försök på True Blue Bay Boutique Resorts anläggning på Grenada för att producera biogas och gödsel med hjälp av en mindre biogasanläggning. Anläggningen matas med biomassa och därefter har en gas och en restprodukt producerats. Restprodukten har därefter används som gödningsmedel i ett odlingsförsök med Pak Choi för att fastlägga dess kvalitet som växtnäring. Plantor gödslades med restprodukter från biogasanläggningen, både när anläggningen matats med grisgödsel och hushållskompost i början samt när födan successivt övergick till alger. Andra plantor fick konstgödsel eller färska alger. Utöver det fanns det en grupp med plantor vilka inte tog del av någon form av gödsel för att fungera som en kontrollgrupp. Vid slutet av odlingsförsöket skördades Pak Choi grödorna och produktivitet och kvalitet på grödorna bedömdes baserat på olika kriterier. Resultaten visade att de växter som blivit gödslade med resterna från biogasanläggningen var störst och av bäst kvalitet. Därutöver har en undersökning genomförts för att få en större förståelse för hur tillgången på alger ser ut och för att få en bild över hur lantbrukares behov av gödningsmedel ser ut på Grenada. Lantbrukare har tillfrågats om tillgång och efterfrågan på olika sorters gödsel, hur de använts och om de har några erfarenheter från Sargassotång. Deras åsikter har varierat, men en gemensam nämnare är att alla är intresserade av lokalproducerade gödningsmedel. Konstgödsel är kostsamt och det kan vara svårt eller omöjligt att få tag på under vissa delar av året, då landet förlitar sig på import. Genom detta har en potentiell marknad för gödselmedel producerat med alger fastställts.

In this thesis I review how Sargassum muticum (Yendo) Fensholt, an invasive alga from Asia, has spread globally due to human activities and describe how this species can affect seagrass ecosystems. Abiotic factors such as nutrient and substratum availability may facilitate the spread of S. muticum into Zostera marina L. meadows, but analyses of seawater nutrients, and sediment particle size and % organic content revealed no significant differences between experimental quadrats in seagrass meadows either with, or without the presence of S. muticum. Phenolic compounds were examined because they form the basis of defensive mechanisms in plants and algae, therefore any change in phenolic content may affect the ability of Z. marina to protect itself from disease, herbivory and invasive species through allelopathic interactions. Results from a four year field study and multiple annual laboratory experiments showed significant reductions (p = 0.034 and p = 0.002, respectively) in the caffeic and tannic acids equivalents content of Z. marina when in the presence of S. muticum. As the abundance of S. muticum increases, other changes in the physiology of Z. marina may occur including variations in growth rates, nutrient partitioning and chlorophyll fluorescence, but data from multiple laboratory experiments illustrated no significant differences in growth. Chlorophyll fluorescence analyses revealed significant differences between treatments with and without S. muticum (p = 0.008), but pairwise comparisons indicated these differences only occurred in 2008 (p < 0.001). Significant differences were also found in nutrient partitioning amongst functional regions of the shoots (p = 0.024), but pairwise comparisons detected these differences between a biomass control treatment (ZZ: Zostera + Zostera) and the ZS (with S. muticum) and ZM (Z. marina on its own at a lower biomass per replicate) treatments (p = 0.013 and p = 0.019, respectively), but not between ZS and ZM. Previous in situ research has found negative effects of S. muticum presence on densities of kelp and other algae. Results from the long-term field study indicated significantly lower mean in situ Z. marina densities within the ZS treatment (p < 0.001). Epibiota found living on the blades of Z. marina provide food for organisms within seagrass ecosystems and also create microhabitats for other species to occupy. Alterations in the abundances of epibiota and microhabitats formed could further modify seagrass ecosystems through shifts in timing of food availability, food preferences and microhabitats created. The long-term field study data revealed significantly lower epibiota abundances within the ZS treatment (p = 0.019), but differences in biomass between treatments were not detected. Changes in the biochemistry, physiology, vegetative physiognomy and epibiota assemblages of Z. marina revealed during experimental manipulations are presented and considered within the context of long-term seagrass survival in light of increasing S. muticum invasion.

Orientadora: Profa. Dra. Natália Pirani Ghilardi-Lopes / Coorientador: Prof. Dr. Gustavo Muniz Dias / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Evolução e Diversidade, São Bernardo do Campo, 2018. / Os ecossistemas bentônicos estão entre os ambientes marinhos mais produtivos e também entre os mais afetados por atividades antropogênicas. Em áreas de costão rochoso como o litoral norte de São Paulo - Brasil, um dos maiores impactos é causado devido ao pisoteio. Essa ação mecânica pode promover danos a estruturas importantes ou até mesmo arrancar o organismo do substrato, afetando a dinâmica das populações e indiretamente a diversidade e o funcionamento da comunidade. As algas marinhas do gênero Sargassum são muito comuns em várias regiões costeiras ao redor do mundo, incluindo a região rochosa subtidal do litoral do sudeste do Brasil, desempenhando um papel importante como estruturadora de habitats e fonte de alimento para muitos organismos marinhos. Desta forma, para avaliar possíveis danos morfológicos e fisiológicos causados pelo pisoteamento, utilizamos uma abordagem experimental baseada em um desenho aninhado em bancos de Sargassum spp. de três diferentes locais, utilizando a metodologia de transectos e nove quadrados de 40 x 40 cm divididos em três tratamentos, simulamos diferentes intensidades de pisoteio: controle (sem pisoteio); baixa intensidade de pisoteio (150 passos sobre as unidades de amostragem) e alta intensidade de pisoteio (300 passos sobre as unidades de amostragem), para testar os impactos esperados em diferentes períodos do ano. Foram quantificados: 1) a performance fotossintética; 2) a concentração de pigmentos fotossintetizantes e compostos fenólicos totais e 3) parâmetros morfológicos e reprodutivos como comprimento, biomassa seca e esforço reprodutivo, imediatamente após o pisoteio e após 90 e 180 dias, totalizando nove conjuntos de tratamento (três intensidades de pisoteio x três períodos de coleta). O pisoteio alterou os padrões fisiológicos causando uma diminuição no desempenho fotossintético e na concentração de pigmentos e aumento de compostos fenólicos totais dependendo do local onde foi realizado o estudo. Considerando os parâmetros morfológicos e reprodutivos, não foram observadas diferenças devido ao pisoteio no comprimento e na biomassa seca, mas o experimento diminuiu significativamente o esforço reprodutivo independente do período ou local estudado. O pisoteio é uma ação humana, por isso é importante conhecer a visão das pessoas sobre o ambiente marinho para a sugestão de medidas mitigadoras de forma mais eficiente. Desta forma, um estudo de percepção ambiental foi realizado com base na escala NEP (New Environmental Paradigm) através do uso de questionários on-line, cujas respostas foram comparadas através do teste de Kruskal-Wallis, considerando gênero, idade, nível educacional, área de trabalho, local de residência, freqüência que visita à praia, número de dias que passam na praia e tipo de atividade ao visitar este ambiente como fatores de agrupamento. Os resultados demonstraram uma consciência dos participantes da pesquisa de que estamos atingindo o limite de recursos que a Terra pode oferecer e que a maioria da interferência humana no meio ambiente é negativa, no entanto, ainda existe uma crença de que os homens são capazes de dominar a natureza e de que os recursos marinhos são ilimitados. Além disso, a maioria dos entrevistados considera que as mudanças climáticas; o aumento do nível do mar e a acidificação do oceano são assuntos tratados com exagero. Entre os fatores avaliados, a idade, o nível educacional, a freqüência de visita à praia e a área de trabalho resultaram em diferenças significativas para algumas das questões, indicando a necessidade do investimento em educação ambiental desde o início da idade escolar e a importância de uma divulgação científica de boa qualidade. Desta forma, as principais conclusões do presente trabalho são: 1) as respostas morfológicas e fisiológicas em Sargassum spp ao pisoteio, dependem do local e do período; 2) a reprodução desta alga é negativamente afetada pelo pisoteio, independentemente do local e do período e 3) a percepção em relação ao ambiente marinho foi influenciada por algumas características das pessoas que participaram do estudo, como idade, nível educacional, área de trabalho e frequência com que visitam a praia. Assim, um gerenciamento eficiente de nossas áreas marinhas e costeiras, deve levar em conta parâmetros ecológicos e sociológicos de cada caso não sendo possível um procedimento generalizado. / Benthic ecosystems are among the most productive marine environments and also among those most affected by anthropogenic activities. In areas of rocky shores as in the northern coast of São Paulo - Brazil, one of the greatest impact is caused due to trampling. This mechanical action can promote damage to important structures or even detach the organisms from the substrate, affecting the dynamics of the populations and indirectly the community diversity and functioning. The seaweeds of the genus Sargassum are very common in several coastal regions around the world including the subtidal rocky-shores from southeastern Brazil, playing an important role as a habitat engineer and food source to many marine organisms. Thus, in order to establish possible morphological and physiological damages caused by trampling on this seaweed, we used an experimental approach based on a nested design. In three diferent sites, using the transect methodology and nine quadrat points of 40 x 40 cm divided into three treatments, we simulated different intensities of trampling: control (no trampling); low trampling intensity (150 steps over the sampling units) and high trampling intensity (300 steps over the sampling units), to mimic the impacts expected along different periods of the year and quantified: 1) the photosynthetic performance; 2) pigment and total phenolics concentration and 3) morphological and reproductive parameters as length, dry biomass and reproductive effort, immediately after the trampling procedures and after 90 and 180 days, totalizing nine treatment sets (three trampling intensities x three times). Trampling changed physiological patterns causing a decrease in the photosynthetic performance and pigment concentration and increasing total phenolics compounds depending on the local where this kind of impact occurs. Considering the morphological and reproductive parameters, trampling significantly decreased the reproductive effort, despite site and period. Trampling is a human action, so it is important to know people's view about the marine environment in order to suggest mitigating measures more efficiently. In this way, an environmental perception study was carried out based on the NEP (New Environmental Paradigm) scale using online questionnaires which responses were compared using the Kruskal-Wallis test considering gender, age, educational level, branch of work, place of residence, frequency of beach attendance, number of days spent on the beach, and type of activity when visiting this environment as grouping factors. The results demonstrated an awareness on the part of the respondents that we are reaching the Earth`s limit and that the majority of the human interference on the environment is negative, however, there was still a belief that men is able to dominate nature and that the marine resources are unlimited. Besides that, most respondents think that climate change; sea level rise and ocean acidification has been treated with exaggerated concern. Amongst the factors tested, the age, educational level, frequency of beach attendance and branch of work resulted in significant differences for some of the questions, indicating the necessity of educational investment since the beginning of the school age and the importance of a scientific dissemination of good quality. The main conclusions of the present work are: 1) morphological and physiological responses to trampling are site and period dependent; 2) reproduction is negatively affected by trampling regardless of site and period and 3) the perception regarding the marine environment was influenced by some characteristics of the people which participated in the study. So, in order to efficiently manage our marine and coastal areas both ecological and sociological parameters must be taken into account and no generalized procedure is possible.

Quatre genres de Sargassaceae présentant de forte biomasse en Bretagne et/ou dans le Pacifique Sud ont été choisi comme modèles de cette étude. Les objectifs étant i) de mieux comprendre l'écologie chimique des Sargassaceae en milieu tempéré et en milieu tropical, ii) de rechercher des chimiomarqueurs spécifiques à certaines espèces et iii) de rechercher de molécules potentiellement bioactives. Ainsi, un travail pluridisciplinaire a été entrepris avec l'étude de l'écologie chimique des Sargassaceae, en Bretagne d'une part, via l'étude des variations spatio-temporelles de certains composés de défenses synthétisés par Sargassum muticum, Bifurcaria bifurcata et Cystoseira baccata associé à un suivi écologique de ces espèces et dans le Pacifique Sud d'autre part, via l'étude de ces mêmes composés de défenses au sein de Turbinaria sp. et Sargassum sp provenant de différents sites. Parallèlement, deux études de chimiotaxonomie ont été menées. D'une part sur le genre Turbinaria afin d'identifier un ou des chimiomarqueur(s) permettant de discriminer T. ornata et de T. conoides. Et d'autre part sur B. bifurcata afin de mieux comprendre la répartition géographique des types chimiques existants au sein de cette espèce. Puis, pour répondre au troisième objectif de cette thèse, trois activités biologiques ont été recherchées en priorité au sein des espèces étudiées: la cytotoxicité, l'activité anti-inflammatoire et la neurotoxicité. Les résultats de cette étude ont permis i) de mettre en évidence l'impact des conditions environnementales sur les variables biologiques et écologiques étudiées chez ces espèces en milieu tempéré comme en milieu tropical ; ii) d'identifier l'acide turbinarique comme étant un chimiomarqueur de l'espèce T. conoides et de mettre en évidence l'existence d'écotypes chez B. bifurcata ; iii) de rapporter l'activité anti-phospholipase A2 d'acides gras issus d'algues du Pacifique Sud et l'activité antiradicalaire et antioxydante de l'éléganolone isolée chez B. bifurcata.