Sedimentology and age determinations on core PS2813-1

Die Rekonstruktion des Einflusses von Strömungen und glazialmarinen Prozessen auf das Sedimentationsgeschehen am Kontinentalhang der Antarktischen Halbinsel im westlichen Weddellmeer basiert auf sedimentologischen und geophysikalischen Daten eines Kolbenlotkerns. Der Sedimentkern wurde während des Fahrtabschnitts ANT-XIV/3 mit dem FS "Polarstern" aus einer mächtigen Levee-Struktur eines Rinnen-Rückensystems gewonnen. Es wurden sedimentologische sowie sedimentphysikalische Untersuchungen an dem Kernmaterial durchgeführt. Die texturellen Änderungen im Kern und die Variationen der gemessenen Parameter ermöglichen eine lithofazielle Gliederung und stratigraphische Einstufung der Sedimentabfolge. Die untersuchten Sedimente umfassen den Zeitraum der vier letzten Klimazyklen bis heute und repräsentieren die Ablagerungsbedingungen von mehr als 340 000 Jahren. Vier Faziestypen wurden unterschieden, die sowohl glaziale als auch interglaziale Ablagerungsräume charakterisieren. (1) Die überwiegend groblaminierten Sedimentabfolgen wurden der Laminitfazies zugeordnet. Unter glazialen Umweltbedingungen kam es infolge schwacher Bodenströmungen zur Ablagerung feinkörniger, laminierter, strömungsbetonter Sedimente. (2) Strukturlose, sehr homogene Sedimentabfolgen des Kems beschreiben einen weiteren, den Kaltzeiten zugeordneten, Faziestyp, der durch geringe Variationen in den Sedimenteigenschaften charakterisiert ist. (3) Kernabschnitte, die weitgehend strukturlos sind bzw. leichte Bioturbationen und relativ viel eistransportiertes Material aufweisen, wurden als IRD-Fazies bezeichnet. Sie repräsentiert den Übergang vom Glazial zum Interglazial, in dem sich das Schelfeis und die Meereisbeckung zurückzogen. In den Sedimenten kam es infolge der gesteigerten Kalbungsrate zur Anreicherung der Eisfracht. (4) Die relativ biogenreichen, hellen Ablagerungen wurden der interglazialzeitlichen Karbonatfazies zugeteilt. Der signifikant erhöhte Anteil planktischer Foraminiferen weist auf eine gesteigerte Bioproduktivität im Oberflächenwasser hin, die aus verstärkten jahreszeitlichen Schwankungen der Meereisbedeckung resultiert. Die betrachteten Sedimentationsprozesse, wie biologische Produktivität, Umlagerungsprozesse durch Meeresströmungen, gravitativer Sedimenttransport und Eistransport, sind das Abbild komplexer Wechselwirkungen aus Meeresspiegelschwankungen, Änderungen ozeanographischer Bedingungen und der Vereisungsdynamik. Das Sedimentationsgeschehen im Untersuchungsgebiet wurde folglich durch die Variationen der vorherrschenden Umweltbedingungen bestimmt. Im Glazial kam es unter einer geschlossenen Meereisbedeckung zur Ablagerung feinkörniger, geschichteter Sedimente. Vorwiegend Turbiditströmungen kontrollierten das Sedimentationsgeschehen innerhalb des betrachteten Rinnen-Rückensystems. Unter dem Einfluß der Coriolis-Kraft und wahrscheinlich einer Konturströmung wurden die suspendierten, feinkörnigen Partikel aus dem zentralen Bereich der Rinne verdriftet und über dem nördlichen Uferwall abgelagert. Höherenergetische gravitative Prozesse beeinflußten das Sedimentationsgeschehen episodisch und sind durch gut sortierte Ablagerungen mit erhöhten Gehalten im Mittel- bis Grobsiltbereich dokumentiert. Höhere Sedimentationsraten in den Glazialen trugen verstärkt zur Bildung des Uferwalls bei. Die Ablagerungen der ebenfalls glazialzeitlichen homogenen Fazies belegen unterschiedliche Ablagerungsbedingungen und eine Verschiebung der dominierenden Prozesse. Während des Übergangs vom Glazial zum Interglazial nahm die Bodenwasserbildungsrate durch das Aufschwimmen des Schelfeises zu, wodurch die Strömungsintensität gesteigert wurde. Eine verstärkte Eisbergaktivität wird durch die Anreichung des IRD-Materials dokumentiert. Während interglazialer Zeiten ermöglichten offen-marine Bedingungen im Südsommer eine leicht erhöhte biologische Produktivität, so daß der Ablagerungsraum durch die Sedimentation biogener Komponenten verstärkt beeinflußt wurde.

Distribution of Uvigerina proboscidea in Late Neogene sediments of DSDP Hole 22-214 in the northern Indian Ocean (Table 1)

This study attempts to understand the significance of Uvigerina proboscidea in paleoceanographic reconstructions at the northern (tropical) Indian Ocean DSDP Site 214 from the Late Miocene through the Pleistocene. In this interval at this site, U. proboscidea is the most abundant species of the benthic assemblage and shows abrupt frequency changes (about 1-74%). Based on relative percentages of U. proboscidea calibrated with oxygen and carbon isotope record and the sediment accumulation rates, the modern distribution of the species in the Indian Ocean, and other evidence, the peaks of abundance of U. proboscidea are inferred to represent times of high-surface productivity, This productivity is related to intensified trade winds during strong southwest (SW) Indian monsoons, causing widespread upwelling along equatorial divergemce in the Indian Ocean. The sudden increase of U. proboscidea abundance at approximately 8.5-7.5 Ma reflects significant upwelling at the equatorial divergence. This event corresponds to the permanent build-up of West Antarctic ice sheets, and a major increase in SW Indian monsoons related upwelling in the northwestern Indian Ocean. The Chron-6 carbon shift at approximately 6.2 Ma is marked by another peak of abundance, reflecting widespread ocean fertility. The highest abundances of U. proboscidea and highest sediment accumulation rates occur between 5.8 and 5.1 Ma, which coincidies with the greatest development of Antarctic ice sheets and strong southwest monsoons. The higher percentages at 3.2-3.1 Ma, approximately 2.4 Ma, and 1.6 Ma all represent phases of high productivity at the equatorial divergence.

Isotope characterization and estimated temperature of formation of calcite veins in ODP Sites 124-768 and 124-770 (Table 1)

Secondary carbonate minerals were recovered within the basalts at both ODP Sites 768 and 770 in the Sulu and Celebes seas. Petrographic and X-ray diffraction analyses indicate that the carbonates are calcites. Other alteration products recognized in the thin sections are smectites, iron oxides, and gypsum. The 13C values of carbonates from both sites range from 1.6 per mil to 2.3 per mil, which are indicative of inorganic carbonate formation with no contributions from 13C-depleted sources such as oxidized organic carbon or methane. The oxygen isotopes at Site 770 range from 30.8 per mil to 31.6 per mil, which indicates a pervasive circulation of cold seawater (9° to 12°C) during alteration of the Celebes Sea basalts. In contrast, carbonates associated with Site 768 basalts have less positive d18O values (21.0 per mil to 27.3 per mil). A lighter 18O isotopic signature indicates the formation of secondary calcite at either higher temperatures or in a system closed to seawater. The rapidly deposited pyroclastic flows at Site 768 would have limited water access to the crust very soon after its formation, which leads us to speculate that the carbonates in the Sulu Sea basalts were formed by isotopically modified fluids resulting from basalt alteration in a closed system.

Twelve original melodies : book 1 : for piano forte /

Volume contains nos. 1-6.

Selective service regulations, September 23, 1940, to February 1, 1942.

Vols. 1-6 and index first issued separately in 1940; v. 2-3 revised and reissued separately in 1941.

Sushui ji wen : 16 juan, bu yi : 1 juan /

Double leaves, oriental style, in case.

Minutes of the right worshipful Grand lodge of the most ancient nad honorable fraternity of Free and accepted masons of Pennsylvania and masonic jurisdiction thereunto belonging. v. 1-12: 1779 to 1880.

Vols. 1-6 compiled by Joshua L. Lyte.

Enzymatic cyclization of a potent Bowman-Birk protease inhibitor, sunflower trypsin inhibitor-1, and solution structure of an acyclic precursor peptide

The most potent known naturally occurring Bowman-Birk inhibitor, sunflower trypsin inhibitor-1 (SFTI-1), is a bicyclic 14-amino acid peptide from sunflower seeds comprising one disulfide bond and a cyclic backbone. At present, little is known about the cyclization mechanism of SFTI-1. We show here that an acyclic permutant of SFTI-1 open at its scissile bond, SFTI-1[ 6,5], also functions as an inhibitor of trypsin and that it can be enzymatically backbone-cyclized by incubation with bovine beta-trypsin. The resulting ratio of cyclic SFTI-1 to SFTI1[6,5] is similar to9:1 regardless of whether trypsin is incubated with SFTI-1[ 6,5] or SFTI-1. Enzymatic resynthesis of the scissile bond to form cyclic SFTI-1 is a novel mechanism of cyclization of SFTI-1[ 6,5]. Such a reaction could potentially occur on a trypsin affinity column as used in the original isolation procedure of SFTI-1. We therefore extracted SFTI-1 from sunflower seeds without a trypsin purification step and confirmed that the backbone of SFTI-1 is indeed naturally cyclic. Structural studies on SFTI-1[ 6,5] revealed high heterogeneity, and multiple species of SFTI-1[ 6,5] were identified. The main species closely resembles the structure of cyclic SFTI-1 with the broken binding loop able to rotate between a cis/trans geometry of the I7-P8 bond with the cis conformer being similar to the canonical binding loop conformation. The non-reactive loop adopts a beta-hairpin structure as in cyclic wild-type SFTI-1. Another species exhibits an isoaspartate residue at position 14 and provides implications for possible in vivo cyclization mechanisms.

Disulfide bond mutagenesis and the structure and function of the head-to-tail macrocyclic trypsin inhibitor SFTI-1

SFTI-1 is a novel 14 amino acid peptide comprised of a circular backbone constrained by three proline residues, a hydrogen-bond network, and a single disulfide bond. It is the smallest and most potent known Bowman-Birk trypsin inhibitor and the only one with a cyclic peptidic backbone. The solution structure of [ABA(3,11)]SFTI-1, a disulfide-deficient analogue of SFTI-1, has been determined by H-1 NMR spectroscopy. The lowest energy structures of native SFTI-1 and [ABA(3,11)]SFTI-1 are similar and superimpose with a root-mean-square deviation over the backbone and heavy atoms of 0.26 +/- 0.09 and 1.10 +/- 0.22 Angstrom, respectively. The disulfide bridge in SFTI-1 was found to be a minor determinant for the overall structure, but its removal resulted in a slightly weakened hydrogen-bonding network. To further investigate the role of the disulfide bridge, NMR chemical shifts for the backbone H-alpha protons of two disulfide-deficient linear analogues of SFTI-1, [ABA(3,11)]SFTI-1[6,5] and [ABA(3,11)]SFTI-1[1,14] were measured. These correspond to analogues of the cleavage product of SFTI-1 and a putative biosynthetic precursor, respectively. In contrast with the cyclic peptide, it was found that the disulfide bridge is essential for maintaining the structure of these open-chain analogues. Overall, the hydrogen-bond network appears to be a crucial determinant of the structure of SFTI-1 analogues.

Raman fiber source for the 1.6–1.75 μm spectral region

We propose and experimentally realize a composite Raman converter based on P-doped and Gedoped fibers. The converter has an emission wavelength of 1.649 μm and an output power of 1.2 W. Numerical simulation of the configuration suggested was performed. A similar converter scheme can be used to build sources with any emission wavelength in the range from 1.6 to 1.75 μm.

Novel glucagon-like peptide-1 (GLP-1) analog (Val8)GLP-1 results in significant improvements of glucose tolerance and pancreatic β-cell function after 3-week daily administration in obese diabetic (ob/ob) mice

This study evaluates the antidiabetic potential of an enzyme-resistant analog, (Val8)GLP-1. The effects of daily administration of a novel dipeptidyl peptidase IV-resistant glucagon-like peptide-1 (GLP-1) analog, (Val8)GLP-1, on glucose tolerance and pancreatic β-cell function were examined in obese-diabetic (ob/ob) mice. Acute intraperitoneal administration of (Val8)GLP-1 (6.25-25 nmol/kg) with glucose increased the insulin response and reduced the glycemic excursion in a dose-dependent manner. The effects of (Val8)GLP-1 were greater and longer lasting than native GLP-1. Once-daily subcutaneous administration of (Val8)GLP-1 (25 nmol/kg) for 21 days reduced plasma glucose concentrations, increased plasma insulin, and reduced body weight more than native GLP-1 without a significant change in daily food intake. Furthermore, (Val8)GLP-1 improved glucose tolerance, reduced the glycemic excursion after feeding, increased the plasma insulin response to glucose and feeding, and improved insulin sensitivity. These effects were consistently greater with (Val8)GLP-1 than with native GLP-1, and both peptides retained or increased their acute efficacy compared with initial administration. (Val8)GLP-1 treatment increased average islet area 1.2-fold without changing the number of islets, resulting in an increased number of larger islets. These data demonstrate that (Val8)GLP-1 is more effective and longer acting than native GLP-1 in obese-diabetic ob/ob mice.

Synthesis and Properties of a Series of 1,1,n,n-Tetramethyl[n](2,11)teropyrenophanes

The work described in this thesis revolves around the 1,1,n,ntetramethyl[n](2,11)teropyrenophanes, which are a series of [n]cyclophanes with a severely bent, board-shaped polynuclear aromatic hydrocarbons (PAH). The thesis is divided into seven Chapters. The first Chapter conatins an overview of the seminal work on [n]cyclophanes of the first two members of the “capped rylene” series of PAHs: benzene and pyrene. Three different general strategies for the synthesis of [n]cyclophanes are discussed and this leads in to a discussion of some slected syntheses of [n]paracyclopahnes and [n](2,7)pyrenophanes. The chemical, structural, spectroscopic and photophysical properties of these benzene and pyrene-derived cyclophanes are discussed with emphasis on the changes that occur with changes in the structure of the aromatic system. Chapter 1 concludes with a brief introduction to [n]cyclophanes of the fourth member of the capped rylene series of PAHs: teropyrene. The focus of the work described in Chapter 2 is the synthesis of of 1,1,n,ntetramethyl[n](2,11)teropyrenophane (n = 6 and 7) using a double-McMurry strategy. While the synthesis 1,1,7,7-tetramethyl[7](2,11)teropyrenophane was successful, the synthesis of the lower homologue 1,1,6,6-tetramethyl[6](2,11)teropyrenophane was not. The conformational behaviour of [n.2]pyrenophanes was also studied by 1H NMR spectroscopy and this provided a conformation-based rationale for the failure of the synthesis of 1,1,6,6-tetramethyl[6](2,11)teropyrenophane. Chapter 3 contains details of the synthesis of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7-9) using a Wurtz / McMurry strategy, which proved to be more general than the double McMurry strategy. The three teropyrenophanes were obtained in ca. 10 milligram quantities. Trends in the spectroscopic properties that accompany changes in the structure of the teropyrene system are discussed. A violation of Kasha’s rule was observed when the teropyrenophanes were irradiated at 260 nm. The work described in the fourth Chapter concentrates on the development of gram-scale syntheses of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7–10) using the Wurtz / McMurry strategy. Several major modifications to the orginal synthetic pathway had to be made to enable the first several steps to be performed comfortably on tens of grams of material. Solubility problems severely limited the amount of material that could be produced at a late stage of the synthetic pathways leading to the evennumbered members of the series (n = 8, 10). Ultimately, only 1,1,9,9- tetramethyl[9](2,11)teropyrenophane was synthesized on a multi-gram scale. In the final step in the synthesis, a valence isomerization / dehydrogenation (VID) reaction, the teropyrenophane was observed to become unstable under the conditions of its formation at n = 8. The synthesis of 1,1,10,10-tetramethyl[10](2,11)teropyrenophane was achieved for the first time, but only on a few hundred milligram scale. In Chapter 5, the results of an investigation of the electrophilic aromatic bromination of the 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7–10) are presented. Being the most abundant cyclophane, most of the work was performed on 1,1,9,9-tetramethyl[9](2,11)teropyrenophane. Reaction of this compound with varying amounts of of bromine revealed that bromination occurs most rapidly at the symmetryrelated 4, 9, 13 and 18 positions (teropyrene numbering) and that the 4,9,13,18- tetrabromide could be formed exclusively. Subsequent bromination occurs selectively on the symmetry-related 6, 7, 15 and 16 positions (teropyrene numbering), but considerably more slowly. Only mixtures of penta-, hexa-, hepta and octabromides could be formed. Bromination reactions of the higher and lower homologues (n = 7, 8 and 10) revealed that the reactivity of the teropyrene system increased with the degree of bend. Crystal structures of some tetra-, hexa-, hepta- and octa-brominated products were obtained. The goal of the work described in Chapter 6 is to use 1,1,9,9- tetramethyl[9](2,11)teropyrenophane as a starting material for the synthesis of warped nanographenophanes. A bromination, Suzuki-Miyaura, cyclodehydrogenation sequence was unsuccessful, as was a C–H arylation / cyclodehydrogenation approach. Itami’s recently-developed K-region-selective annulative -extension (APEX) reaction proved to be successful, affording a giant [n]cyclophane with a C84 PAH. Attempted bay-region Diels-Alder reactions and some cursory host-guest chemistry of teropyrenophanes are also discussed. In Chapter 7 a synthetic approach toward a planar model compound, 2,11-di-tbutylteropyrene, is described. The synthesis could not be completed owing to solubility problems at the end of the synthetic pathway.