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Taxonomic studies on adult and larval ascidians from CaliforniaHaugsten, Robert Christian 01 January 1958 (has links)
The primary purpose of this research is to further morphological studies on larval ascidians and to encourage greater reliance on larval structures in ascidian taxonomy. This may necessitate some revisions in current classifications, but it is hoped that such revisions will lead to a better understanding of the group. Some general considerations of ascidians are here included for the benefit of those who may not be familiar with them. All specimens used in this study were collected at the Pacific Marine Station area at Dillon Beach, California, during June, July, and August of 1957.
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Chemical Investigations of Great Barrier Reef Ascidians - Natural Product and Synthetic StudiesDavis, Rohan Andrew, davis_rohan@hotmail.com January 2000 (has links)
This thesis describes the chemical investigations of several ascidian species collected from the Great Barrier Reef, Queensland, Australia. The thesis is divided into two separate components, Part A focuses on the isolation and structure elucidation of 11 previously undescribed ascidian metabolites. All structures were assigned using a combination of spectroscopic and/or chemical methods. Part B relates to the isolation and chemical conversion of a natural product to a combinatorial template. The natural product template was subsequently used in the generation of a solution-phase combinatorial chemistry library. A further two combinatorial libraries were generated from a synthesised model compound that was related to the natural product template. Part A. Investigation of Aplidium longithorax collected from the Swains Reefs resulted in the isolation of two new para-substituted cyclofarnesylated quinone derived compounds, longithorones J (30) and K (31). The former compound had its absolute stereochemistry determined by the advanced Mosher method. From an Aplidium longithorax collected from Heron Island, two new cyclofarnesylated hydroquinone compounds, longithorols C (46) and D (47) and a novel macrocyclic chromenol, longithorol E (48) were isolated. Longithorol C (46) had its absolute stereochemistry determined by the advanced Mosher method. Chemical investigation of the deep-purple colonial ascidian, Didemnum chartaceum collected from Swains Reefs led to the isolation of five new lamellarin alkaloids, which included the 20-sulfated derivatives of lamellarins B (94), C (95) and L (96), the 8-sulfated derivative of lamellarin G (97) and the non-sulfated compound, lamellarin Z (98). The known lamellarins A (63), B (80), C (64), E (65), G (67), and L (71) plus the triacetate derivatives of lamellarin D (82) and N (83) were also isolated. An aberration in the integration of signals in the 1H NMR spectra of the 20-sulfated derivatives (94-96) led to NMR relaxation studies. T1 values were calculated for all protons in the sulfated lamellarins (94-97) and their corresponding non-sulfated derivatives (80, 64, 71, 67). The protons ortho to the sulfate group in compounds (94-97) had T1 values up to five times larger than the corresponding protons in their non-sulfated derivatives (80, 64, 71, 67). A specimen of Eudistoma anaematum collected from Heron Island was shown to contain a new b-carboline alkaloid, eudistomin V (130), in addition to the two known metabolites, eudistomin H (105) and I (106). Part B. The known natural products, 1,3-diphenethylurea (29), 1,3-dimethylxanthine (30), 1,3-dimethylisoguanine (31) and the salts of tambjamine C (16), E (18) and F (19) were isolated from the ascidian, Sigillina signifera collected in Blue Lagoon, Lizard Island. Base hydrolysis on mixtures of the salts of tambjamine C (16), E (18) and F (19) resulted in the production of 4-methoxy-2,2-bipyrrole-5-carbaldehyde (26). This natural product template (26) was used in the generation of an enamine combinatorial chemistry library (98, 103-111) using solution-phase parallel synthesis. The biaryl compound, 4-(2-thienyl)-1H-pyrrole-2-carbaldehyde (59) was successfully synthesised using Suzuki-Miyaura coupling conditions and subsequently used as a template in the generation of an amine (67, 77, 80-87) and imine (78, 92-95) combinatorial library using solution-phase parallel synthesis.
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Environmental impacts and the ecology of sponges and ascidians in south-eastern Australian coastal lakes and lagoonsBarnes, Peter Brendan. January 2009 (has links)
Thesis (Ph.D.)--University of Wollongong, 2009. / Typescript. Includes bibliographical references: leaf 146-171.
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The chemistry of Algoa Bay ascidiansBromley, Candice Leigh January 2016 (has links)
This thesis investigates the chemistry of 25 ascidian species collected from Algoa Bay, South Africa with a concerted focus on metal accumulation by these ascidians and the possible interaction of these metals with ascidian metabolites. Chapter 2 details the screening techniques employed to establish the presence of nitrogenous metabolites (1H- 15N HMBC), hyper-accumulated metal ions (ICP-MS) and potential metal ion/ ascidian metabolite complexes (LC-ICP-MS/ESI-MS). Unfortunately, exhaustive attempts to detect intact metal ion/ascidian metabolite complexes through the use of liquid chromatography with parallel inductively coupled plasma mass spectrometry/electrospray mass spectrometry (LC-ICPMS/ ESI-MS) were unsuccessful. However, the LC-ICP-MS/ESI-MS data obtained for the crude organic extracts of six of the Algoa Bay ascidian species, Distaplia skoogi, Aplidium monile, Aplidium sp., Didemnum sp., Leptoclindines sp. and Polycitor sp. enabled identification of a number of ten halogenated metabolites, namely the indoles 2.28-2.30, and the tyramine and tyrosine derivatives (2.31-2.33, 2.41, 2.43, 2.44 and 2.46), within the ascidian extracts. This study confirmed that LC-ICP-MS/ESI-MS is a powerful tool for the dereplication of halogenated metabolites in complex mixtures especially where these compounds are present in very small amounts. This study is also the first report of these compounds (eight of which are known) in African ascidians. Compounds 2.32 and 2.46 have not been reported before from a marine source. Compounds 2.28-2.30 and 2.33 were present in sufficient amounts in the respective ascidian extracts to allow their isolation and structure elucidation using standard spectroscopic techniques Chapter 3 explores the ability of ascidians to accumulate a wide range of metal ions at concentrations which are often orders of magnitude higher than those of the surrounding sea water. Inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the total ion concentrations of 24 metals in 25 Algoa Bay ascidian species. To the best of our knowledge this is the largest and most extensive investigation of metal concentrations in a group of different ascidians occurring in the same area. Hypotheisizing that the metal ion concentrations for each ascidian specimen screened may represent a unique fingerprint for each specimen principal component analysis (PCA) was used in an attempt to establish whether there were spatial, temporal or phylogenetic relationships associated with the metal concentration fingerprints of the ascidians that formed part of this study. The PCA results showed that there were no statistically significant relationships between ascidian metal ion concentrations and either the collection year or the collection site of the ascidians. However, species from the family Didemnidae provided the clearest statistical evidence supporting a phylogenetic relationship between these ascidians and their hyperaccumulated metal ion profiles. Furthermore, these results suggested that ascidian species are indeed actively concentrating metal ions from the surrounding sea water and are not simply sinks for passively accumulated metal ions. Interestingly, the concentration of vanadium in the set of ascidians studied did not appear to correlate with any of the other metals accumulated by these ascidians suggesting that there is possibly a unique method employed for the accumulation of vanadium by ascidians. Chapter 4 investigated this possibility further after the nucleosides 4.10, 4.11, 4.13, 4.15, 4.17 and 4.40 were isolated from the vanadium accumulating ascidian Aplidium monile. Studies into the interactions between nucleosides and vanadyl are unfortunately rare and usually qualitative in nature with limited information provided about the stability or structures of the complexes formed. The vanadyl accumulating aplousobranch ascidians e.g. Aplidium monile dominated our study of Algoa Bay ascidians therefore providing us with the rationale to investigate the relatively little studied binding ability and stability of vandyl-nucleoside complexes. Potentiometric studies were conducted to determine the stability constants of complexes formed between the oxovanadium ion vanadyl (VO2+) and the commercially available nucleosides 4.10-4.14. The data afforded by this analysis clearly confirmed the complexity of the vanadyl/nucleoside complexation and suggested that guanosine (4.12) formed the most stable complex with oxovanadium ions. We were also able to establish a third protonation constant for the hydroxyl moiety in 4.12 with a logK 8.87 which has not been previously reported. Finally, Chapter 5 revisited the cytoxicity two Algoa Bay ascidians, Clavelina sp. and Atriolum marinense the extracts from which produced promising bioactivity results in previous studies against oesophageal cancer cells. The HP-20 fractionated extracts of Clavelina sp. and Atriolum marinense proved to be similalrly cytotoxic to breast cancer cells. With the exception for the 100% acetone(aq)fractions the NMR data for both species suggested that most active non polar fractions were dominated by what appeared to be structurally unremarkable fatty acid glycerides and as such were not pursued further. Purification of the 100% acetone(aq)fraction of A. marinense resulted in the isolation of a styrene trimer, 5.1, common to both ascidian extracts. The NMR simulation software WIN-DAISY was employed to confirm the structure of 5.1. Attempts to establish if 5.1 was an isolation artefact or a product of marine pollution were inconclusive
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Biofouling Management in the Pacific Northwest and Predation on Native versus Non-native AscidiansKincaid, Erin Suzanne 06 July 2016 (has links)
Marine non-native species threaten economic and environmental health, making it crucial to understand factors that make them successful. Research on these species, therefore, allows for greater preparedness and informed management of biological invasions and increases understanding of elements structuring biological communities. Among the marine non-native species, and particularly the fouling community, non-native ascidians are a taxon of particular concern because they can crowd out native benthic species and smother mariculture products. This thesis addresses management for ascidians and other fouling organisms and includes research on the invasiveness of this taxon in addition to the invasibility of recipient fouling communities. On the West Coast of the U.S., limited efforts have been made to coordinate biofouling management across states, despite the myriad vectors increasing propagule pressure over time along coastal states. Building on recent state and local efforts, I developed a Pacific Regional Biofouling Plan for the states of Oregon and Washington to help start a consensus-driven process by which these states could create a forum for more comprehensive coordination efforts, following California's lead. As states address authority gaps, the biofouling management framework I've written is meant to be used to guide the conversation between managers as various stages of coastal management are realized.
To better inform the scope and efficacy of management and regulatory efforts, the study of invasions ecology asks and aims to answer questions regarding recipient community interactions and characteristics of the non-native species themselves. Studies that identify characteristics that make ascidians successful (invasiveness) and determine the influence native communities have on their success (invasibility) are important for assessing overall risk of establishment and spread from non-native ascidians. Therefore, I aimed to: 1) explore the hypothesis that fouling communities on suspended, artificial structures are more invasible than benthic habitats; and 2) identify characteristics influencing predation patterns on the native Distaplia occidentalis versus non-native ascidian species using mensurative and experimental studies in Charleston Marina, Oregon. I conducted a series of feeding assays, surveys, and a caloric content analysis. Feeding assays were conducted with a suite of predators. The flatworm predator (Eurylepta leoparda) was found to be highly selective on the native ascidian Distaplia occidentalis, and only preyed on whole colony samples. Feeding assay data suggest that test (tunic) structure or thickness may be an influential factor affecting nudibranch (Hermissenda crassicornis) predation rates on native versus non-native ascidians, with greater predation on the native ascidian species. Non-native ascidians may escape predation in floating but not benthic environments on the Oregon coast due to their palatability characteristics, likely tunic structure and low caloric content. In this case, this suite of predators may indirectly facilitate the invasion of docks but provide at least partial resistance to the invasion of natural benthic areas.
The chapters herein address gaps in management and scientific knowledge regarding non-native species of the marine fouling community. Future work enhanced by my efforts could include the development of the coastal biofouling management plan, coordinated by the Western Regional Panel on Aquatic Invasive Species Coastal Committee, and broadening the geographic and taxonomic scope of my research with a more comprehensive study of predator-prey interactions involving non-native ascidians and a diverse suite of predators. These interactions may be an important factor in explaining the success of ascidians and other fouling organisms on floating structures and lack of success on nearby benthic substrata.
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