138 resultados para Schlosser


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Published also as Inaug.-diss.--Heidelberg.

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Vol. 7 based on articles first published in the "Archiv für geschichte und literatur" under the title "Ueber Napoleon und dessen lobredner und tadler": published at Frankfort. 1832, under title "Zur beurtheilung Napoleons und seiner neuesten tadler und lobredner", 3 vols., 8'. Pref., v. 7; also Kayser. Neues bücher-lexicon.

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Mode of access: Internet.

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Mode of access: Internet.

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Mode of access: Internet.

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Extracted from Jahrbuch der kunsthistorischen Sammlungen der Allerhöchsten Kaiserhauses, Bd. 15, 1893.

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Thesis (doctoral)--Ruprecht-Karls-Universitat Heidelberg.

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At four sites in the central equatorial Pacific Ocean the flux of extraterrestrial 3He, determined using the excess 230Th profiling method, is 8 * 10**-13 cm**3 STP/cm**2/ka. This supply rate is constant to within 30%. At these same sites, however, the burial rate of 3He, determined using chronostratigraphic accumulation rates, varies by more than a factor of 3. The lowest burial rates, which occur north of the equator at 1°N, 139°W are lower than the global average rate of supply of extraterrestrial 3He by 20% and indicate that sediment winnowing may have occurred. The highest burial rates, which are recorded at the equator and at 2°S, are higher than the rate of supply of extraterrestrial 3He by 100%, and these provide evidence for sediment focusing. By analyzing several proxies measured in core PC72 sediments spanning the past 450 kyr we demonstrate that periods of maximum burial rates of 230Th, 3He, 10Be, Ti, and barite, with a maximum peak-to-trough amplitude of a factor of 6, take place systematically during glacial time. However, the ratio of any one proxy to another is constant to within 30% over the entire length of the records. Given that each proxy represents a different source (234U decay in seawater, interplanetary dust, upper atmosphere, continental dust, or upper ocean), our preferred interpretation for the covariation is that the climate-related changes in burial rates are driven by changes in sediment focusing.

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This thesis details the design, development and execution of innovative methodology in the total synthesis of the terpene-derived marine natural product, furospongolide. It also outlines the synthetic routes used to prepare a novel range of furanolipids derivatives and subsequent evaluation of their potential as antitumour agents. The first chapter is a review of the literature describing efforts undertaken towards the synthesis of biologically active furanosesterterpenoid marine natural products. A brief discussion on the sources and biological activity exhibited by furan natural products is also provided. In addition, a concise account of the role of hypoxia in cancer, and the increasing interest in HIF-1 inhibition as a target for chemotherapeutics is examined. The second chapter discusses the concise synthesis of the marine HIF-1 inhibitor furospongolide, which was achieved in five linear steps from (E,E)-farnesyl acetate. The synthetic strategy features a selective oxidation reaction, a Schlosser sp3-sp3 cross-coupling, a Wittig cross-coupling and an elaborate one-pot selective reduction, lactonisation and isomerization reaction to install the butenolide ring. The structure-activity relationship of furospongolide was also investigated. This involved the design and synthesis of a library of structurally modified analogues sharing the same C1-C13 subunit. This was achieved by exploiting the brevity and high level of convergence of our synthetic route together with the readily amenable structure of our target molecule. Exploiting the Schlosser cross-coupling allowed for replacement of furan with other heterocycles in the preparation of various furanolipid and thiophenolipid derivatives. The employment of reductive amination and Wittig chemistry further added to our novel library of structural derivatives. The third chapter discusses the results obtained from the NCI from biological evaluation From a collection of 28 novel compounds evaluated against the NCI-60 cancer cell array, six drug candidates were successfully selected for further biological evaluation on the basis of antitumour activity. COMPARE analysis revealed a strong correlation between some of our design analogues and the blockbuster anticancer agent tamoxifen, further supporting the potential of furanolipids in the treatment of breast cancer. The fourth chapter, details the full experimental procedures, including spectroscopic and analytical data for all the compounds prepared during this research.

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Nitrogen fixation, the biological reduction of dinitrogen gas (N2) to ammonium (NH4+), is quantitatively the most important external source of new nitrogen (N) to the open ocean. Classically, the ecological niche of oceanic N2 fixers (diazotrophs) is ascribed to tropical oligotrophic surface waters, often depleted in fixed N, with a diazotrophic community dominated by cyanobacteria. Although this applies for large areas of the ocean, biogeochemical models and phylogenetic studies suggest that the oceanic diazotrophic niche may be much broader than previously considered, resulting in major implications for the global N-budget. Here, we report on the composition, distribution and abundance of nifH, the functional gene marker for N2 fixation. Our results show the presence of eight clades of diazotrophs in the oxygen minimum zone (OMZ) off Peru. Although proteobacterial clades dominated overall, two clusters affiliated to spirochaeta and archaea were identified. N2 fixation was detected within OMZ waters and was stimulated by the addition of organic carbon sources supporting the view that non-phototrophic diazotrophs were actively fixing dinitrogen. The observed co-occurrence of key functional genes for N2 fixation, nitrification, anammox and denitrification suggests that a close spatial coupling of N-input and N-loss processes exists in the OMZ off Peru. The wide distribution of diazotrophs throughout the water column adds to the emerging view that the habitat of marine diazotrophs can be extended to low oxygen/high nitrate areas. Furthermore, our statistical analysis suggests that NO2- and PO43- are the major factors affecting diazotrophic distribution throughout the OMZ. In view of the predicted increase in ocean deoxygenation resulting from global warming, our findings indicate that the importance of OMZs as niches for N2 fixation may increase in the futur

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We present a helium isotope record for core TT013-114PC from the central equatorial Pacific (140°W, 4°N, 4432 m water depth) spanning a period of 1 million years. We focus on the time interval from 560 to 800 kyr, largely coinciding with the mid-Pleistocene climate transition (MPT) when the dominant period of the Earth's climate variability shifted from 41 kyr to 100 kyr. The terrigenous 4He concentrations from our study correlate very well with published titanium concentrations in this core strongly supporting the use of terrigenous 4He as a monitor of continental dust. Normalizing titanium and terrigenous 4He concentrations to 3He suggests that the dust supply during the MPT was approximately 30% lower compared to the subsequent period (560-100 kyr). The 3He-normalized barium, aluminum and phosphorus concentrations, trace elements with a predominantly biogenic source in these sediments, are relatively constant. This is in contrast to previous studies that reported an apparent rise of titanium-normalized productivity proxies. Rather than a significant increase in productivity during the MPT, we conclude that the dust flux to the central equatorial Pacific was reduced and that the export productivity was approximately constant during this period of climate reorganization.

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Inorganic nitrogen depletion restricts productivity in much of the low-latitude oceans, generating a selective advantage for diazotrophic organisms capable of fixing atmospheric dinitrogen (N2). However, the abundance and activity of diazotrophs can in turn be controlled by the availability of other potentially limiting nutrients, including phosphorus (P) and iron (Fe). Here we present high-resolution data (~0.3°) for dissolved iron, aluminum, and inorganic phosphorus that confirm the existence of a sharp north-south biogeochemical boundary in the surface nutrient concentrations of the (sub)tropical Atlantic Ocean. Combining satellite-based precipitation data with results from a previous study, we here demonstrate that wet deposition in the region of the intertropical convergence zone acts as the major dissolved iron source to surface waters. Moreover, corresponding observations of N2 fixation and the distribution of diazotrophic Trichodesmium spp. indicate that movement in the region of elevated dissolved iron as a result of the seasonal migration of the intertropical convergence zone drives a shift in the latitudinal distribution of diazotrophy and corresponding dissolved inorganic phosphorus depletion. These conclusions are consistent with the results of an idealized numerical model of the system. The boundary between the distinct biogeochemical systems of the (sub)tropical Atlantic thus appears to be defined by the diazotrophic response to spatial-temporal variability in external Fe inputs. Consequently, in addition to demonstrating a unique seasonal cycle forced by atmospheric nutrient inputs, we suggest that the underlying biogeochemical mechanisms would likely characterize the response of oligotrophic systems to altered environmental forcing over longer timescales.