TY - THES A1 - Wichura, Henry T1 - Topographic evolution of the East African Plateau : a combined study on lava-flow modeling and paleo-topography T1 - Die topographische Entwicklung des Ostafrikanischen Plateaus : eine kombinierte Studie über Lavastrommodellierung und Paläotopographie N2 - The East African Plateau provides a spectacular example of geodynamic plateau uplift, active continental rifting, and associated climatic forcing. It is an integral part of the East African Rift System and has an average elevation of approximately 1,000 m. Its location coincides with a negative Bouguer gravity anomaly with a semi-circular shape, closely related to a mantle plume, which influences the Cenozoic crustal development since its impingement in Eocene-Oligocene time. The uplift of the East African Plateau, preceding volcanism, and rifting formed an important orographic barrier and tectonically controlled environment, which is profoundly influenced by climate driven processes. Its location within the equatorial realm supports recently proposed hypotheses, that topographic changes in this region must be considered as the dominant forcing factor influencing atmospheric circulation patterns and rainfall distribution. The uplift of this region has therefore often been associated with fundamental climatic and environmental changes in East Africa and adjacent regions. While the far-reaching influence of the plateau uplift is widely accepted, the timing and the magnitude of the uplift are ambiguous and are still subject to ongoing discussion. This dilemma stems from the lack of datable, geomorphically meaningful reference horizons that could record surface uplift. In order to quantify the amount of plateau uplift and to find evidence for the existence of significant relief along the East African Plateau prior to rifting, I analyzed and modeled one of the longest terrestrial lava flows; the 300-km-long Yatta phonolite flow in Kenya. This lava flow is 13.5 Ma old and originated in the region that now corresponds to the eastern rift shoulders. The phonolitic flow utilized an old riverbed that once drained the eastern flank of the plateau. Due to differential erosion this lava flow now forms a positive relief above the parallel-flowing Athi River, which is mimicking the course of the paleo-river. My approach is a lava-flow modeling, based on an improved composition and temperature dependent method to parameterize the flow of an arbitrary lava in a rectangular-shaped channel. The essential growth pattern is described by a one-dimensional model, in which Newtonian rheological flow advance is governed by the development of viscosity and/or velocity in the internal parts of the lava-flow front. Comparing assessments of different magma compositions reveal that length-dominated, channelized lava flows are characterized by high effusion rates, rapid emplacement under approximately isothermal conditions, and laminar flow. By integrating the Yatta lava flow dimensions and the covered paleo-topography (slope angle) into the model, I was able to determine the pre-rift topography of the East African Plateau. The modeling results yield a pre-rift slope of at least 0.2°, suggesting that the lava flow must have originated at a minimum elevation of 1,400 m. Hence, high topography in the region of the present-day Kenya Rift must have existed by at least 13.5 Ma. This inferred mid-Miocene uplift coincides with the two-step expansion of grasslands, as well as important radiation and speciation events in tropical Africa. Accordingly, the combination of my results regarding the Yatta lava flow emplacement history, its location, and its morphologic character, validates it as a suitable “paleo-tiltmeter” and has thus to be considered as an important topographic and volcanic feature for the topographic evolution in East Africa. N2 - Das Ostafrikanische Plateau ist ein eindrucksvolles Beispiel für aktive, kontinentale Grabenbildung, aber auch für geodynamische Hochebenenbildung mit weitreichendem klimatischen Einfluss auf die gesamte Region. Als integraler Bestandteil des Ostafrikanischen Grabensystems beläuft sich die mittlere Höhe des Plateaus auf durchschnittlich 1000 m ü.NN. Seine Lage korreliert gut mit der Präsenz einer halbkreisförmigen negativen Bouguer-Schwereanomalie, die an den Aufstieg eines Manteldiapirs im Untergrund gekoppelt ist. Dieser prägte die känozoische Krustenentwicklung seit seinem Aufstieg im Eozän-Oligozän. Die Hebungsgeschichte und topographische Entwicklung des Hochlandes steht seither in enger Beziehung zum einsetzenden Vulkanismus, der Bildung erster Abschiebungssysteme und führte schließlich zur Entwicklung des heutigen Vollgrabensystems. Neueste Hypothesen lassen den Schluss zu, dass topographische Veränderungen als dominierende Einflussgrößen atmosphärischer Zirkulationsmuster sowie der regionalen Niederschlagsverbreitung anzusehen sind. Zusätzlich werden diese Prozesse durch die äquatoriale Lage des Ostafrikanischen Plateaus verstärkt und die Hebung dieser Region oft mit wichtigen Klima- und Umweltveränderungen in Ostafrika und angrenzende Gebiete in Verbindung gebracht. Während der weitreichende klimatische Einfluss des Hochlandes größtenteils akzeptiert ist, sind Zeitpunkt und Ausmaß seiner Heraushebung nicht eindeutig bestimmt und daher noch immer Grundlage bestehender Diskussionen. Diese Zwangslage hat ihre Ursache im Fehlen aussagekräftiger und datierbarer Referenzhorizonte. Um den Hebungsbetrag zu quantifizieren und Beweise signifikanten Reliefs vor der Entwicklung des Grabensystems entlang des Ostafrikanischen Hochlandes zu erbringen, analysierte und modellierte ich einen der längsten terrestrischen Lavaströme. Dieser vor 13,5 Ma abgelagerte Yatta-Lavastrom hat mit 300 km Länge seinen Ursprung in der Region der heutigen östlichen Grabenschulter des zentralen Kenia-Rifts. Die phonolitische Lava ergoss sich entlang eines Flussbettes, das einst die östliche Flanke des Hochlandes entwässerte. Aufgrund unterschiedlicher Erosionspotentiale bildet der Lavastrom gegenwärtig ein positives Relief und befindet sich oberhalb des Athi Flusses, der parallel zum Paläofluß, und somit versetzt zu seinen früheren Verlauf, strömt. Mein Ansatz der Lavastrom-Modellierung basiert auf einer Methode, die das Fließverhalten einer beliebigen Lava in Abhängigkeit von Temperatur und Magmenzusammensetzung in einem rechtwinkligen Kanal berechnet. Die wesentlichen Wachstumsmuster des Lavastroms sind durch ein eindimensionales Modell beschrieben, wobei Newtonsches Fließverhalten im Innern hinter der Lavastromfront von der zeitlichen Entwicklung der Viskosität und/oder der Fließgeschwindigkeit bestimmt wird. Vergleiche meiner Resultate mit verschiedenen Magmenzusammensetzungen zeigen, dass sich lange, kanalisierte Lavaströme mit hohen Ergussraten und schneller Platznahme bilden können. Dies geschieht unter annähernd isothermalen Bedingungen und erfordert laminares Fließen. Die Integration der Yatta- Lavastrom-Dimensionen und der bedeckten Paläotopographie (Neigungswinkel) in das Modell, erlaubte es mir die Topographie des Ostafrikanischen Hochlandes vor der Grabenbildung zu modellieren. Das Ergebnis der Modellierung ergibt einen Neigungswinkel von mindestens 0,2° und impliziert, dass der Lavastrom seinen Ursprung in einer Höhe von mindestens 1400 m ü.NN gehabt haben muss. Somit existierte bereits vor 13,5 Ma hohe Topographie in der heutigen Region des zentralen Kenia-Rifts. Diese abgeleitete regionale Hebungsgeschichte im mittleren Miozän korreliert mit der zweistufigen Ausbreitung der Graslandschaften, sowie dem Aufkommen neuer Arten im tropischen Afrika. Die Kombination aus Fließverhalten, Entstehungsort und morphologischer Eigenschaften macht den Yatta-Lavastrom zu einem “Paläoneigungsmesser” und wichtigen vulkanischen Untersuchungsobjekt für die topographische Entwicklung in Ostafrika. KW - Ostafrika KW - Plateau KW - Paläotopographie KW - Miozän KW - Yatta KW - East African Plateau KW - paleo-topography KW - Miocene KW - Yatta Y1 - 2011 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-52363 ER - TY - JOUR A1 - Westermann, Antje A1 - Stadie, Nicole A1 - Frank, Ulrike T1 - Messung der Atem-Schluck-Koordination während normalem Schluck und unter Anwendung des Mendelsohn-Manövers JF - Spektrum Patholinguistik Y1 - 2011 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-54286 SN - 1869-3822 SN - 1866-9433 IS - 4 SP - 143 EP - 147 ER - TY - JOUR A1 - Westermann, Antje A1 - Stadie, Nicole A1 - Frank, Ulrike T1 - Messung der Atem-Schluck-Koordination während normalem Schluck und unter Anwendung des Mendelsohn- Manövers Y1 - 2011 ER - TY - JOUR A1 - Wessig, Pablo A1 - Wawrzinek, Robert A1 - Moellnitz, Kristian A1 - Feldbusch, Elvira A1 - Schilde, Uwe T1 - A new class of fluorescent dyes based on 1,3-benzodioxole and [1,3]-dioxolo[4.5-f]benzodioxole JF - Tetrahedron letters N2 - We report on synthesis and photophysical properties of a new class of fluorescent dyes. They are characterized by large Stokes-shifts, long fluorescence lifetimes in organic solvents and a pronounced dependency of the fluorescence lifetime on the solvent polarity. Also worthy of note is the high bleaching stability. To provide access to biochemical and medical applications a series of derivatives were prepared, which exhibit specific reactivity towards different biologically relevant functional groups (carboxylic acids, amines, maleimides, N-hydroxysuccinimide esters). Furthermore, two alkynes were prepared, which could be used in 'Click' chemistry. KW - Fluorescent dyes KW - Fluorescence lifetime KW - Large Stokes-shifts KW - Heterocycles Y1 - 2011 U6 - https://doi.org/10.1016/j.tetlet.2011.09.058 SN - 0040-4039 VL - 52 IS - 46 SP - 6192 EP - 6195 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Wessig, Pablo A1 - Pick, Charlotte A1 - Schilde, Uwe T1 - First example of an atropselective dehydro-Diels-Alder (ADDA) reaction JF - Tetrahedron letters N2 - A new concept of a stereoselective synthesis of axially chiral biaryls, formed in the course of the dehydro-Diels-Alder (DDA) reaction, has been disclosed. It is based on asymmetric induction of the newly formed chirality axis by a chirality center, which is present in the two synthesized DDA reactants. Depending on the different length of the linkers joining the alkyne moieties the DDA reaction may be triggered photochemically or thermally, where only the thermal variant was stereoselective. KW - Cycloaddition KW - Atropselecrivity KW - Biaryls KW - Alkynes KW - Photochemistry Y1 - 2011 U6 - https://doi.org/10.1016/j.tetlet.2011.06.024 SN - 0040-4039 VL - 52 IS - 32 SP - 4221 EP - 4223 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Wessig, Pablo A1 - Pick, Charlotte T1 - Photochemical synthesis and properties of axially chiral naphthylpyridines JF - Journal of photochemistry and photobiology : A, Chemistry N2 - Five alkynyl pyridines were prepared and cyclized to naphthylpyridines as the main products in the course of a Photo-Dehydro-Diels-Alder reaction. Four of the final products are axially chiral and the determination of the rotational barrier by DFT calculations, dynamic NMR and H PLC experiments is demonstrated. (C) 2011 Elsevier B.V. All rights reserved. KW - Photochemistry KW - Axial chirality KW - Photo-Dehydro-Diels-Alder reaction KW - Dynamic NMR KW - Dynamic HPLC KW - Molecular modeling Y1 - 2011 U6 - https://doi.org/10.1016/j.jphotochem.2011.06.006 SN - 1010-6030 VL - 222 IS - 1 SP - 263 EP - 265 PB - Elsevier CY - Lausanne ER - TY - JOUR A1 - Wessig, Pablo A1 - Möllnitz, Kristian A1 - Kelling, Alexandra A1 - Schilde, Uwe T1 - Crystal structure of 1r,2c,3c,4t,5t,6t-1,2,3,4,5,6-hexakis-trimethylsilanyloxy-cyclohexane, C24H60O6Si6 JF - Zeitschrift für Kristallographie : international journal for structural, physical and chemical aspects of crystalline materials ; New crystal structures N2 - C24H60O6Si6, triclinic, P (1) over bar (no. 2), a = 11.307(2) angstrom, b = 12.159(2) angstrom, = 16.576(2) angstrom, alpha = 109.47(1)degrees, beta = 94.64(1)degrees, gamma = 111.65(1)degrees, V = 1942.3 angstrom(3), Z = 2, R-gt(F) = 0.043, wR(ref)(F-2) = 0.118, T = 210 K. Y1 - 2011 U6 - https://doi.org/10.1524/ncrs.2011.0105 SN - 1433-7266 VL - 226 IS - 2 SP - 228 EP - 230 PB - De Gruyter Oldenbourg CY - München ER - TY - JOUR A1 - Wessig, Pablo A1 - Matthes, Annika A1 - Pick, Charlotte T1 - The photo-dehydro-Diels-Alder (PDDA) reaction JF - Organic & biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry N2 - The photo-dehydro-Diels-Alder (PDDA) reaction is a valuable extension of the classical Diels-Alder (DA) reaction. The PDDA reaction differs from the DA reaction by the replacement of one of the C-C-double bonds of the diene moiety by a C-C triple bond and by the photochemical triggering of the reaction. This entails that, in contrast to the DA reaction, the PDDA reaction proceeds according to a multistage mechanism with biradicals and cycloallenes as intermediates. The PDDA reaction provides access to a considerable variety of compound classes. For example, 1-phenylnaphthlenes, 1,1'-binaphthyls, N-heterocyclic biaryls, and naphthalenophanes could be obtained by this reaction. Y1 - 2011 U6 - https://doi.org/10.1039/c1ob06066j SN - 1477-0520 VL - 9 IS - 22 SP - 7599 EP - 7605 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Wessig, Pablo A1 - Matthes, Annika T1 - Preparation of Strained Axially Chiral (1,5)Naphthalenophanes by Photo-dehydro-Diels-Alder Reaction JF - Journal of the American Chemical Society N2 - The preparation of 10 (1,5)naphthalenophanes (10a-j) by photo-dehydro-Diels-Alder (PDDA) reaction is described. Owing to hindered rotation around the biaryl axis, compounds 10 are axially chiral and the separation of enantiomers by chiral HPLC was demonstrated in three cases (10a,b,e). The absolute configuration of the isolated enantiomers could be unambiguously determined by comparison of calculated and measured circular dichroism (CD) spectra. Furthermore, we analyzed ring strain phenomena of (1,5)naphthalenophanes 10. Depending on the length of the linker units, one can distinguish three classes of naphthalenophanes. Compounds 10a-c are highly strained (E-STR = 7-31 kcal/mol), and the strain is caused by small bond angles in the linker unit and deformation of the naphthalene moiety. Another type of strain is observed if the linker unit becomes relatively long (10g,h) originating from transannular interactions and is comparable with the well-known strain of medium sized rings. The naphthalenophanes 10d-f with a linker length of 10-14 atoms are only marginally strained. To clearly discriminate the different sources of strain, we defined two geometrical parameters (average central dihedral angle delta(C) and naphthalene thickness D-N) and demonstrated that they are well-suited to indicate naphthalene deformation of our naphthalenophanes 10 as well as of ten model naphthalenophanes (I-X) with different linker lengths and linking positions. Y1 - 2011 U6 - https://doi.org/10.1021/ja109118m SN - 0002-7863 VL - 133 IS - 8 SP - 2642 EP - 2650 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Weskott, Thomas A1 - Fanselow, Gisbert T1 - On the informativity of different measures of linguistic acceptability JF - Language : journal of the Linguistic Society of America N2 - This article deals with the claim that the MAGNITUDE ESTIMATION (ME) method of gathering acceptability judgments produces data that are more informative for linguists than binary or n-point scale judgments. We performed three acceptability-rating experiments that directly compared ME data to binary and seven-point scale data. The results clearly falsify the hypothesis that data gathered by the ME method carry a larger amount of information about the acceptability of a given linguistic phenomenon. The three measures are largely equivalent with respect to informativity. Moreover, ME judgments are shown to be more liable to producing spurious variance under certain circumstances.* KW - acceptability judgments KW - empirical syntax KW - magnitude estimation KW - informativity Y1 - 2011 SN - 0097-8507 VL - 87 IS - 2 SP - 249 EP - 273 PB - Linguistic Society of America CY - Washington ER -