894 search hits
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Optically induced orientational transitions in nematic liquid crystals
(2004)
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Dmitry Krimer
- I have presented in this thesis a theoretical study of some dynamical phenomena and orientational transitions induced by intense light in homeotropically oriented nematic layers. A large number of experiments has been performed in such systems and various interesting dynamical regimes have been identified. However, systematical theories capable of describing the observed phenomena have been derived for some cases only. In other cases oversimplified models exist with limited applicability. In Chapter 2 I considered the case of a circularly polarized plane light wave incident perpendicularly on the layer. I have constructed a theory that is capable of describing the observed regimes of director motion and the transitions between them in detail. The first instability is the Freedericksz transition from the homeotropic state to a small-amplitude reoriented state with uniform director precession around the layer normal. With increasing light intensity, this state destabilizes via a supercritical Hopf bifurcation and a new frequency in the time Fourier spectra of the dynamical variables appears. This regime is quasiperiodic and corresponds to a precession and nutation of the director. As the intensity increases further, this state disappears at a certain critical value where the period of nutation becomes infinite. There a strongly hysteretic transition to a state with large reorientation occurs via a homoclinic bifurcation. The homoclinic orbit involved is of the simplest type where a limit cycle collides with a saddle point having one unstable direction. The new state corresponds to a uniform precession of the director, however, with very large period and with large reorientation. I have also investigated the influence of an additional static electric field on the dynamical scenario described above. In Chapter 3 the treatment is generalized to the case of elliptically polarized light. The complete bifurcation diagram with the light intensity and the ellipticity as control parameters has been calculated in the region where rotating states exist. I have shown that for a fairly narrow region of ellipticities close to circular polarization the first periodic rotating state loses its stability in a supercritical Hopf bifurcation. I have found that with increasing light intensity at different ellipticities different sequences of transitions all finally lead to a state with large director distortion as the intensity is increased. The nature of this largely distorted state, as well as intermediate regimes vary with ellipticity. Some of the regimes that appear at lower intensities were studied previously, both experimentally and theoretically, but a complete picture up to the largely distorted regime was missing. In the theoretical treatments developed in the Chapters above, as in all other treatments, the velocity field induced by the director motion (backflow) has been neglected. In Chapter 4 I have investigated the influence of backflow on the dynamical scenario described in Chapter 2 and have shown that the backflow leads to substantial quantitative changes. It turns out that the regime of nonuniform precession shifts to higher light intensities and exists in a larger interval. I have also found unanticipated spatial oscillations of the backflow across the layer for the state with large director distortion. This is a signature of the interference pattern of the light within the layer. Actually, in the theory presented, for the first time, a light-induced dynamical phenomenon has been derived from the full nematodynamic equations. Thus, for the first time, full quantitative comparison with experiments using a transversally extended laser light could be done. Also, in all previous theoretical treatments involving plane wave incident light, it was assumed that the director distortion does not depend on the coordinates in the plane of the layer, i.e. one dealt with a one dimensional situation. In Chapter 5 I have studied the instabilities induced by a linearly polarized ordinary light wave incident at a small oblique angle allowing for spatial variations of the director in the plane of the layer and including the case of a dye-doped nematic. It was previously known that for sufficiently small angles of incidence the homeotropic state looses stability in a stationary, homogeneous pitchfork bifurcation. I have shown that the resulting stationary distorted state looses stability via a secondary Hopf bifurcation to spatially inhomogeneous state (nonzero critical wavenumber) that leads to the formation of travelling waves in the plane of the layer. The wavelength of these waves depend on the angle of incidence and the ratios of the elastic constants. It is typically several times larger than the thickness of the layer.
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Magnetooptische Untersuchungen an Halbleitersystemen mit reduzierter Dimensionalität
(2004)
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Jens Fürst
- Diese Arbeit beschäftigt sich mit der magnetooptischen Untersuchung von niedrigdimensionalen Halbleiterstrukturen, bestehend aus III-V und IV-VI Halbleiternsystemen. Als Vertreter der III-V Halbleiter stehen InAs Quantenpunktproben zur Verfügung. Die elektronischen Eigenschaften der InAs Quantenpunkte werden mit Hilfe von Photolumineszenz- und Hanle-Effekt-Messungen analysiert. Dabei wird der Einfluss einer Vielzahl von Probenparametern wie Dotierung und Zusammensetzung der Quantenpunkte sowie des Matrixmaterials auf die Elektronenspinlebenszeit untersucht. Grundlegende Analysen werden an dem ternären IV-VI Materialsystem PbSeTe durchgeführt. Bei der Entstehung von PbSe Quantenpunkten in PbEuTe Matrix ist es nicht auszuschließen, dass es an der Grenzfläche der Quantenpunkte und des Matrixmaterials zu Durchmischungen dieser beiden Materialien kommt und sich dadurch das System PbSeTe bildet. Deshalb werden die Bandparameter dieses Mischkristalls in einer Probenserie von reinem PbSe zu reinem PbTe mit Hilfe von Magnetotransmissionsmessungen und kohärenten anti-Stokes Ramanstreuung bestimmt. Zur Untersuchung der Emission von PbSe Quantenpunkten sind diese in einen vertikalen Resonator eingebracht. Das von diesen nulldimensionalen Systemen emittierte Licht wird mit der emittierten Strahlung von Resonatoren mit zweidimensionalen und dreidimensionalen aktiven Zonen verglichen. In weiteren Experimenten werden vertikal emittierende Laserstrukturen in einem Spektralbereich nahe 8 Mikrometer bei kontinuierlicher und gepulster Anregung untersucht. Dabei zeigen sich sehr schmale Emissionslinien. In einem longitudinalen Magnetfeld konnte aufgrund der kleinen Halbwertsbreite des emittierten Lichtes eine Aufspaltung beobachtet werden.
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Synthesis, Molecular Structure and Reactivity of Di(1-cyclohepta-2,4,6-trienyl) thioether, S(C7H7)2 and Tri(1-cyclohepta-2,4,6-trienyl) amine, N(C7H7)3
(2004)
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Jinnan Liu
- This thesis describes the synthesis, characterization and coordination chemistry of di(1-cyclohepta-2,4,6-trienyl) thioether, S(C7H7)2 (1), tri(1-cyclohepta-2,4,6-trienyl) amine, N(C7H7)3 (24), and di(1-cyclohepta-2,4,6-trienyl) amine, NH(C7H7)2 (25). The reaction of tropylium bromide, C7H7Br, with the gas hydrogen sulfide (H2S) leads to the di(1-cyclohepta-2,4,6-trienyl) thioether, S(C7H7)2 (1), which can undergo Diels-Alder reactions with maleic anhydride, maleimide and N-phenyl maleimide to give the adducts S(C7H7)(C7H7C4H2O3) (4a), S(C7H7)(C7H7C4H3NO2) (4b) and S(C7H7)(C7H7C10H7NO2) (4c), respectively. In these three compounds, one cyclohepta-2,4,6-trienyl ring has remained intact, whereas the other seven-membered ring was involved in the Diels-Alder reaction. The advantage of the potential ligand S(C7H7)2 (1) in comparison to other simple sulfanes is that it can act as a chelate ligand, using one of the non-planar seven-membered rings. In general, the central double bond of one of the seven-membered rings becomes coordinated to the metal. The disadvantage of the sulfane 1 is its sensitivity towards oxidation and its low thermal stability. The reactions of either Cr(CO)5(thf) or Cr(CO)4(eta4-C7H8) with one equivalent of 1 lead to the monosubstituted derivative Cr(CO)5[PhCH2S(C7H7)] (7), in which one seven-membered ring has remained unchanged and the other seven-membered ring has been transformed into a benzyl substituent. From the reaction of 1 with a mixture of chromium(carbonyl)(acetonitrile) complexes, Cr(CO)6-x(CH3CN)x (x = 1, 2, 3), the pentacarbonyl Cr(CO)5[S(C7H7)2] (6) could be obtained, in which both cycloheptatrienyl ring substituents are freely pending. Using the same method as for the chromium complexes, tetracarbonyl molybdenum Mo(CO)4[(eta2-C7H7)S(C7H7)] (10) was obtained from the reactions of either Mo(CO)5(thf) or Mo(CO)4(eta4-C7H8) with the sulfane 1. In complex 10 the ligand S(C7H7)2 is coordinated to the metal both through a lone pair of electrons at the sulfur atom and the central C=C double bond of a cyclohepta-2,4,6-trienyl substituent. Mo(CO)5[S(C7H7)2] (9) could be obtained from Mo(CO)6-x(CH3CN)x (x = 1, 2, 3); in analogy to 6, the sulfane ligand in 9 is coordinated to molybdenum exclusively through a lone pair of electrons at the sulfur atom. From the intermediate W(CO)5(thf), the pentacarbonyltungsten complex W(CO)5[S(C7H7)2] (13) was obtained, which could be converted thermally to the benzyl complex W(CO)5[PhCH2S(C7H7)] (14). In the reaction with the mixture of tungsten(carbonyl)(acetonitrile) complexes, W(CO)6-x(CH3CN)x (x = 1, 2, 3), the compounds W(CO)4[(eta2-C7H7)S(C7H7)] (15) and W(CO)5[S(C7H7)2] (13) were obtained; complex 15 was the main product. The reactions of either Mn2(CO)10 (under irradiation) or Mn(CO)5X (X = Cl, Br) with di(1-cyclohepta-2,4,6-trienyl) thioether (1) led to the organothiolato-bridged dimer Mn2(CO)8[S(C7H7)]2 (17) in addition to ditropyl, (C7H7)2. Subsequent substitution of two carbonyl ligands in 17 by stronger sigma-donor-pi-acceptor ligands such as tert-butyl isocyanide and trimethyl phosphite (tBuNC and P(OMe)3) gave the complexes Mn2(CO)6[tBuNC]2[S(C7H7)]2 (18) and Mn2(CO)6[P(OMe)3]2[S(C7H7)]2 (19). Both 17 and 18 contain a planar Mn2S2 core with the 1-cyclohepta-2,4,6-trienyl substituents in anti-position. In addition, some investigations with tri(1-cyclohepta-2,4,6-trienyl) amine, N(C7H7)3 (24), and di(1-cyclohepta-2,4,6-trienyl) amine, NH(C7H7)2 (25) were carried out. In analogy to the sulfane S(C7H7)2 (1), 24 and 25 can undergo Diels-Alder reactions with maleimide and N-phenyl maleimide to give the educts (C7H7)2N(C7H7C4H3O2N) (26b), (C7H7)N(C7H7C10H7NO2)2 (26c), (C7H7)NH(C7H7C4H3O2N) (27b) and (C7H7)NH(C7H7C10H7NO2) (27c), respectively. Similar to the synthesis of 24 and 25, the mixed tertiary amines di(1-cyclohepta-2,4,6-trienyl)phenylamine, N(Ph)(C7H7)2 (28), and (1-cyclohepta-2,4,6-trienyl)diphenylamine, N(Ph)2(C7H7) (29) were prepared using aniline or diphenylamine. The reaction of N(C7H7)3 (24) with [C7H7]BF4 (1:1) leads to the N-tropylidene-N-(1-cyclohepta-2,4,6-trienyl)immonium tetrafluoroborate salt, [(C7H6)N(H)(C7H7)]BF4 (30). Compound 30 has also been obtained using NH(C7H7)2 (25) as the educt. As expected, the tertiary amine N(Ph)(C7H7)2 (28) reacted with [C7H7]BF4 to give the dark-red salt [(C7H6)N(Ph)(C7H7)]BF4 (31). Attempts to use the amine N(C7H7)3 (24) as a ligand in transition metal complexes were unsuccessful. However, NH(C7H7)2 (25) reacts with the mixture of tungsten(carbonyl)(acetonitrile) derivatives to give the chelate tetracarbonyl complex W(CO)4[(C7H7)NH(eta2-C7H7)] (32), which is similar to the sulfane complexes 10 and 15. Compared with the versatile phosphane ligand tri(1-cyclohepta-2,4,6-trienyl) phosphane, P(C7H7)3, the analogous amine N(C7H7)3 (24) is unable to act as a coordination ligand, probably as a result of the steric shielding of the lone pair of electrons at the nitrogen atom.
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Template-Controlled Synthesis of Magnetic/Semiconducting Nanoparticles within Amphiphilic Core-Shell Cylindrical Polymer Brushes
(2004)
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Mingfu Zhang
- Core-shell cylindrical polymer brushes with poly(t-butyl acrylate)-b-poly(n-butyl acrylate) (PtBA-b-PnBA) diblock copolymer side chains were synthesized via the “grafting from” technique using a combination of anionic polymerization (for the synthesis of the backbone) and atom transfer radical polymerization (ATRP, for the synthesis of the side chains). The formation of well-defined brushes was confirmed by 1H-NMR and GPC. The selective hydrolysis of the PtBA block of the side chains resulted in novel amphiphilic core-shell cylindrical polymer brushes with poly(acrylic acid)-b-poly(n-butyl acrylate) (PAA-b-PnBA) side chains. The characteristic core-shell cylindrical structure of the brushes was directly visualized on mica by scanning force microscopy (SFM). Amphiphilic brushes with 1500 block copolymer side chains and a length distribution of lw/ln = 1.04 at a total length ln = 179 nm were obtained. These amphiphilic polymer brushes can be regarded as unimolecular cylindrical micelles, because of the core-shell structure and the amphiphilicity of side chains. The amphiphilic brushes can be used as single molecular templates for the synthesis of inorganic nanoparticles, because the carboxylic acid groups (or carboxylate groups, after neutralization) in the polymer core can coordinate with various metal ions. The hydrophilic core of polymer brushes, poly(acrylic acid), was neutralized by NaOH and afterward iron cations (Fe3+ and Fe2+) were loaded into the polymer core via ion exchange. The formation of the polychelates of polymer brushes and iron cations was confirmed and characterized by various techniques such as Fourier transform infrared spectroscopy (FTIR), UV/vis spectroscopy, transmission electron microscopy (TEM) and SFM. A peculiar “pearl necklace” morphology was observed for the polychelates, which is caused by the physical cross-linking of the side chains via multivalent iron cations. Formation of crystalline alpha-Fe2O3 (hematite) was observed during the He-Ne laser irradiation in the confocal Raman microscopy measurement of the polychelate containing Fe3+ ions. Magnetic nanoparticles were successfully produced from the coordinated iron cations within polymer brushes via single molecule templating technique, as confirmed by various techniques such as SFM, TEM, and UV/visible spectroscopy. Superconducting quantum interference device (SQUID) magnetization measurements show that the hybrid nanocylinders are superparamagnetic at room temperature. The polymer shell provides not only the stability of the nanoparticles but also the solubility of the hybrid nanocylinders. After the formation of the magnetic nanoparticles, the carboxylate coordination sites within the polymer brushes are liberated and ready for further coordination with more iron ions, thus it is possible to increase the amount and/or particle size of the nanoparticles by multi-cycles of iron ion loading and particle formation. The as-prepared hybrid nanocylinders combine the promising properties of polymers and superparamagnetic nanoparticles, and may find potential applications such as in ferrofluids. Similarly, using the amphiphilic core-shell cylindrical polymer brush with PAA core and PnBA shell as template, wire-like assemblies of CdS nanoparticles were successfully synthesized under mild solution conditions, as confirmed by various characterization techniques. Quantum confinement of the CdS nanoparticles was observed, indicated by the blue shift of the absorbance edge in UV/visible spectrum. The technique using a single cylindrical molecule as template for inorganic nanoparticle fabrication presented in this thesis is not restricted to magnetic/semiconductor nanoparticles, but can also be used for the preparation of a number of metal, metal oxide, and metal chalcogenide nanoparticles.
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Molekularsystematische Untersuchungen an Vertretern der pflanzenparasitischen Gattung Exobasidium (Basidiomycota)
(2003)
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Heidi Döring
- Artabgrenzungen und Phylogenie in der pflanzenparasitischen Pilzgattung Exobasidium wurden mit molekularen Markern untersucht. Das allgemein akzeptierte Artkonzept für die europäischen Arten dieser Pflanzenparasiten basiert auf Wirtsspezifität und den hervorgerufenen Befallsbildern. Erste molekulare Studien (GC-Gehalt, DNA-DNA-Homologie) bestätigten dies jedoch nicht in allen Fällen. Daher wurden in dieser Arbeit Artabgrenzungen im Kontext phylogenetischer Zusammenhänge mit Hilfe von RFLPs und Sequenzdaten untersucht. Der Schwerpunkt liegt auf Pilzstämmen von europäischen Wirtsarten der Gattungen Vaccinium und Rhododendron, wozu hefeartig wachsende Kulturen der saprotrophen Lebensphase dieser Pilze bearbeitet wurden. Zur molekularen Charakterisierung wurden mit 6 Restriktionsenzymen RFLPs eines PCR-Amplifikates ermittelt. Der amplifizierte Genabschnitt kodiert ca. 2.2 kb des 5’-Bereichs der 26S rRNA. Darüber hinaus wurden Sequenzvergleiche der Domäne I der 26S rDNA, der 18S rDNA und der ITS-Region durchgeführt. Übereinstimmung in den PCR-RFLP-Mustern des 5’-Bereichs der 26S rDNA zeigt Konspezifität an, da solche Stämme einen ähnlichen GC-Gehalt und hohe DNA-DNA-Homologien aufweisen. Insgesamt wurden über alle 6 Enzyme bei 51 untersuchten Stämmen 20 RFLP-Gruppen gefunden. Jedoch finden sich Stämme von einer Wirtspflanze oder solche mit hoher DNA-DNA-Homologie auch in verschiedenen RFLP-Gruppen. Zusätzlich zeigen sich in Dendrogrammen auffallende Unterschiede in den Distanzen zwischen einzelnen RFLP-Mustern. Eine nachfolgende Analyse der Sequenzen der Domäne I der 26S rDNA bestätigte, daß Stämme einer RFLP-Gruppe Angehörige einer Art sind, daß aber Stämme einer Art durchaus unterschiedlichen RFLP-Gruppen angehören können. Unter Berücksichtigung der DNA-DNA-Homologie-Daten kann beim Auftreten von weniger als 3 bp Unterschied in der Domäne I der 26S rDNA Konspezifität festgestellt werden. Unterschiede in den RFLP-Mustern können somit Konspezifität nicht widerlegen. Für z.T. unerwartete Ergebnisse der RFLP-Analysen ließen sich in Sequenzanalysen 2 Gründe feststellen. Die amplifizierte Region der 26S rDNA kann Group-I-Introns enthalten (an Position 929/930 bzw. 1.127/1.128 der 26S rDNA bezogen auf Saccharomyces cerevisiae). Die Verteilung der Group-I-Introns zwischen Stämmen, welche aufgrund der übereinstimmenden Sequenzen der Domäne I der 26S rDNA und ihrer DNA-DNA-Homologie als konspezifisch anzusehen sind, zeigt, daß sie bei Exobasidium spp. nicht artspezifisch auftreten. Außerdem gruppieren einige Stämme (3 Arten) in phylogenetischen Analysen in anderen Verwandtschaftskreisen der Ustilaginomyceten, wodurch sie als kontaminierende Pilze identifiziert werden. Diese Stämme waren früher mit biochemisch-physiologischen Merkmalen nicht gegen Exobasidium spp. abzugrenzen. Stämme einer Art stammen dabei von verschiedenen Wirtspflanzen und widersprachen so früher einem auf hoher Wirtsspezifität basierenden Artkonzept. Datenbankvergleiche der Domäne I der 26S rDNA und deren phylogenetische Analyse im Kontext der Ustilaginomyceten ergaben Affinitäten zu den Entylomatales (Tilletiopsis washingtonensis, Entyloma spp.) bzw. Ustilaginales (Ustilago maydis). Analysen der 18S rDNA und ITS-Region ausgewählter Stämme bestätigten dies. Für phylogenetische Analysen der Gattung Exobasidium wurden Sequenzen der Domäne I der 26S rDNA ausgewählter Stämme untereinander und mit GENBANK-Einträgen verglichen. Hierbei korrespondieren Exobasidium-Arten gut mit den Wirtspflanzen. Sie zeigen eine hohe Wirtsspezifität. Konspezifische Stämme lösen auch dasselbe Befallsbild aus, wobei E. vaccinii eine Ausnahme zu bilden scheint, da Stämme, die auf Vaccinium vitis-idaea eine lokale Gallbildung hervorrufen, sich nicht von Stämmen unterscheiden, welche eine systemische Infektion verursachen. Auch zeigt sich, daß von europäischen Rhododendren isolierte Stämme, die traditionell E. rhododendri zugeordnet werden, distinkte, nicht konspezifische Gruppen bilden. In phylogenetischen Analysen im Kontext der Ustilaginomyceten bilden die Exobasidiales eine gut gestützte Gruppe. Innerhalb der Ordnung werden mit verschiedenen Verfahren zur Stammbaumrekonstruktion unterschiedliche phylogenetische Hypothesen wiedergegeben. Die Exobasidiaceae bilden nur in Distanzanalysen eine monophyletische Gruppe. Zudem gruppieren die Gattungen Arcticomyces und Muribasidiospora immer innerhalb der Exobasidium-Arten und die Eigenständigkeit dieser Gattungen erscheint fraglich. Insgesamt legen die phylogenetischen Analysen eine Kospeziation oder Koevolution zwischen exobasidialen Pilzen und ihren Wirten nahe. Jedoch zeigen sich komplexe Speziationsprozesse in der Evolution dieser pflanzenparasitischen Pilze. Bei Exobasidien von Wirten der Vaccinioideae ergeben sich Muster, die nur mit Wirtswechseln erklärbar sind, und innerhalb des Exobasidium rhododendri-Komplexes muß von der Speziation auf einer Wirtsart ohne Veränderung des Befallsbildes ausgegangen werden.
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Biomass and Nutrient Studies of Selected Tree Species of Natural and Plantation Forests: Implications for a Sustainable Management of the Munessa-Shashemene Forest, Ethiopia
(2004)
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Asferachew Abate
- Plantation forests with exotic tree species have been introduced to alleviate the problems of deforestation in Ethiopia. In the future, more plantation forests with fast growing species should be grown for coping with the ever-increasing demands for fuelwood and other forest products. However, it is not known whether plantation forests are sustainable or not. For the sustainability of plantation forests with exotic tree species, it is of paramount importance to thoroughly understand their ecological and social attributes through a holistic approach. For this reason, a multidisciplinary project was initiated in the Munessa-Shashemene Forest. Such an approach gives valuable information about the sustainability of plantation forests when the basic ecological features of the natural forests are compared with plantation forests. As an integral part of the multidisciplinary project, the objectives of this study are to: 1) quantify the fine roots and aboveground biomass of selected tree species in both natural and plantation forests; 2) quantify the macronutrient stocks of the fine roots and aboveground components of selected trees species in both natural and plantation forests; and 3) evaluate the implication of the changes in the biomass and macronutrient stocks for a sustainable management of forests. The study focused on four tree species, Podocarpus falcatus (Thunb.) Mirb., Podocarpaceae and Croton macrostachys Hochst. ex Del. Euphorbiaceae, were selected from a natural forest. Cupressus lusitanica Miller, Cupressaceae and Eucalyptus globulus Labill. Myrtaceae were selected from plantation forests. Root architectures of the study trees were studied by excavation. The live fine root biomass (<2 mm in diameter) of the dry and wet seasons was determined from samples collected at the distances of 1, 2 and 3 meters from the bole of the study trees. At each of the distances, root cores were taken at the depth intervals 0-10, 10-35, 35-60, 60-85 and 85-100 cm using a hand auger. Linear regression equations were used to estimate the aboveground biomass on the basis of the relation between DBH and dry weights of the aboveground plant components. Macronutrient concentrations were determined following a standard laboratory procedure. Studies on the root architecture revealed that C. lusitanica has a shallow root and is more susceptible to windthrow compared to E. globulus. With the exception of E. globulus, the dry season live fine root (LFR) biomass was higher for all trees studied. The seasonal variation in the fine root biomass was attributed to the changes in soil moisture of the study area. For all trees investigated, the mean annual LFR biomass was highest at the depth interval 0-10 cm at all distances. The favorable soil texture, pH and organic matter content at the depth interval 0-10 cm might be responsible for higher LFR biomass. The significantly higher LFR biomass of P. falcatus (1.34 kg m-2) coupled with its higher macronutrient stocks compared to C. macrostachys (0.32 kg m-2) suggest the importance of P. falcatus in the sustainability of the natural forest by transferring more macronutrients to the soil through its fine roots. Similarly, the significantly higher total LFR biomass of C. lusitanica (0.88 kg m-2) coupled with its higher macronutrient stock compared to E. globulus (0.27 kg m-2) indicated less depletion of soil nutrients by the former. The stand structure of the natural and plantation forests differed largely. In the natural forest, the density of C. macrostachys was much higher (143 ± 72 trees ha-1) than the density of P. falcatus (73 ± 39 trees ha-1). Generally, the structural change of the natural forest due to selective cutting of P. falcatus was found to have negative implications on the sustainability of the natural forest. The differences in the structure of C. lusitanica and E. globulus, despite their similar densities, resulted in a significantly lower understory ground cover by herbaceous and shrub species in the former. The effect of a poor understory growth on the floor litter thickness and thereby on nutrient capital of the soil may negatively affect the sustainability of C. lusitanica plantation. The harvesting of the stemwood of C. lusitanica and E. globulus removes a substantial amount of nutrients from the plantation sites. Furthermore, the current practice of collecting foliage, twigs and branches for firewood by the local people results in a higher depletion of nutrients. In order to make the plantation forests sustainable, the silvicultural practice in the future should consider on site conservation of foliage and bark. It is recommended that more studies on aboveground and belowground biomass, fine root turnover, and nutrient concentrations of the plantation forests should be carried out in a chronosequence in order to gain more insight on their sustainability.
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Pigment-Pigment Interactions and Protein Dynamics in Light-Harvesting Complexes: a Single-Molecule Study
(2004)
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Clemens Hofmann
- Light harvesting complexes that are involved in the first steps of photosynthesis in purple bacteria were studied with low-temperature optical single molecule spectroscopy. In one series of experiments the spectral properties of the bacteriochlorophyll a molecules within the complexes were studied in the view of model systems of molecular aggregates. It was found that the excitations in the B800 band of the light harvesting 2 complex are mainly localised on individual chromophores although evidence was found for an electronic coupling in the weak to intermediate range between individual bacteriochlorophyll a molecules. In contrast, for the B850 band of the light harvesting complex 2 as well as for the B870 band of the light harvesting complex 1 it was found that the assembly of bacteriochlorophyll molecules represents a strongly coupled system and that the excitation is coherently delocalised over a substantial part of the chromophores. By performing Monte-Carlo simulation an estimate on the amount of random and correlated energetic disorder in the site energies of the chromophores as well as on structural properties of the complexes could be given. In experiments on individual LH2-LH1-RC complexes, the energy transfer within a single photosynthetic unit was observed. In further experiments the chromophores were used as local probes to monitor conformational fluctuations of the protein residues in their binding pocket. Looking at the spectral diffusion of individual chromophores allowed to elucidate the organisation of the protein-energy landscape in tiers. In addition a clear correlation for the transition rates between those states and the energy separation of the levels involved could be uncovered. To simplify and automatise the analysis of a large number of consecutively recorded spectra a pattern recognition approach using multivariate statistical analysis proved to be a very useful tool. Apart from elucidating spectral diffusion processes detailed information about the line shape of individual chromophore absorptions could be gained from which it was inferred that the electron-phonon coupling in the B800 pigment pool is very weak. In summary, this thesis demonstrates that low-temperature single-molecule spectroscopy provides a unique method to reveal details of pigment-pigment interactions in the weak to intermediate as well as strong coupling limit that are inaccessible by other experimental methods.
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Convection and Magnetic Field Generation in Rotating Spherical Fluid Shells
(2004)
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Radostin D. Simitev
- The dissertation reports results from numerical and analytical studies of convection and dynamo action in rotating fluid spheres and spherical shells. This research is motivated by the geophysical problem of the origin and properties of the Earth's magnetism. Extensive numerical simulations are performed in order to advance the understanding of the basic physical components and mechanisms believed to be responsible for the generation and the variations in time of the main geomagnetic field. Questions such as linear onset and nonlinear finite-amplitude properties of rotating convection, generation and equilibration of magnetic fields in electrically conducting fluids, nonlinear feedback effects of the generated magnetic fields on convection, spatio-temporal structures of magnetic and velocity fields, oscillations and coherent processes in turbulent regimes and other questions are studied in dependence on all basic parameters of the problem, as well as for various choices of the magnetic, thermal and velocity boundary conditions and for some secondary assumptions such as a finitely-conducting inner core and various basic temperature profiles. Because of the lack of knowledge of the properties of the Earth's core and the uncertain details of the processes that take place there, this research is necessary in order to provide the tools for extrapolation to realistic models of the geodynamo. Of particular interest are various types of oscillations of dipolar fields. In contrast to quadrupolar and hemispherical dynamos dipolar dynamos have been originally considered to be non-oscillatory. But the six different types of dipolar oscillations, among which is the ``invisible'' one, reported in this dissertation alter this view. Generation of magnetic fields by convection shows a strong dependence on the Prandtl number P of the fluid. But this fact has received little attention in the past. Convection-driven dynamo action at Prandtl numbers larger than unity is studied with the goal to test the validity of the magnetostrophic approximation. The latter is found to be poorly satisfied for P < 300. Dynamos in this regime require magnetic Prandtl numbers Pm which increase with P. The same trend continues to hold for values of P less then unity and this regime thus seems to be best suited to reach the goal of minimal values of Pm. For Pm=P=0.1 a hemispherical dynamo is obtained in the case of a rotation parameter tau=10**5. A further reduction of Pm leads to a decay of magnetic field irrespective of the Rayleigh numbers used. Apart from numerical simulations and parameter studies of basic physical mechanisms, the dissertation includes an analytical study of inertial convection in rotating spheres in the limit of small Prandtl numbers and large rotation rates. Explicit expressions for the dependence of the Rayleigh number on the azimuthal wavenumber and on the product of P tau are derived and new results for the case of a nearly thermally insulating boundary are obtained. Limited comparisons with actually observed features of the geomagnetic field are also presented. An example are the torsional Alfven waves found in the numerical simulations of this dissertation. They are geophysically relevant as a possible cause for the observed secular variation impulses of the Earth's magnetic field. Reversals of the magnetic field polarity have also been observed in our simulations. Dynamo intermittency and interaction between dipolar and quadrupolar components are preconditions for aperiodic dipolar reversals similar to those of the Earth's main field. However, the opportunities for quantitative comparisons with geophysical observations are rather limited by the complexity of the self-consistent dynamo problem and by the computational restrictions of our numerical simulations.
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The signal transduction of the adipokinetic hormone and regulation of energy metabolism in the cricket, Gryllus bimaculatus de Geer (Ensifera: Gryllidae)
(2004)
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Anurag N. Anand
- The fat body from the cricket, Gryllus bimaculatus incorporates acetate, glycerol or palmitate into lipid in vitro. Adipokinetic hormone (AKH) inhibits acetate incorporation into lipid by the fat body from adult crickets in vitro. AKH inhibits palmitate incorporation into lipid to a small extent, however, it does not influence the incorporation of palmitate into different lipid classes. In the presence of AKH, glycerol incorporation into lipid by the adult cricket fat body increases by several fold. AKH does not influence the incorporation of glycerol into different lipid classes. The fat body incorporates glycerol mainly into triacylglycerol (TAG) and almost exclusively into the backbone. AKH inhibits fatty acid (FA) synthesis but not the coupling of FAs with the glycerol backbone. Triacylglycerol lipase (TGL) from the fat body, in last larval instar and adult crickets, shows an age-dependent pattern of activity. AKH activates TGL, but does not regulate ACCase, ACL and FAS upon treatment of the fat body for a short period, under the assay conditions. The FAS and acetate incorporation activities are highly correlated in an age-dependent manner and are highest on day 2 of the adult stage. The activation of the formation of sn-1,2-DAG from TAG, in the fat body by AKH seems to be via the removal of FAs at positions 1 and 3, followed by reacylation of 2-MAG. The presence of calcium in the incubation medium is crucial for the inhibition of acetate incorporation by AKH; possibly it is essential for the binding of AKH to the receptor. The influx of acetate and calcium into and efflux of calcium from the cytosol are not affected by AKH. The release of calcium from intracellular calcium stores in the fat body, caused by thapsigargin, inhibits acetate incorporation irreversibly and shows a tendency for the activation of TGL. The calcium ionophore ionomycin inhibits acetate incorporation by the fat body reversibly and shows a tendency for TGL activation. Another ionophore, A23187 also inhibits acetate incorporation. Caffeine and theophylline inhibit acetate incorporation by the fat body in a reversible manner and tend to activate TGL. Caffeine seems to act via the release of calcium from intracellular stores and not via increase in the cellular cAMP concentrations. cAMP analogues and agonists do not influence acetate incorporation, however, the agonists, IBMX and forskolin cause a multifold increase in the cAMP concentrations in the fat body. AKH does not affect the cAMP concentrations in the fat body suggesting that cAMP is not involved in the signal transduction. As the activation of protein kinase C by PMA (a phorbol ester) does not affect acetate incorporation, diacylglycerol does not seem to be involved in the AKH signal transduction. The activation and/or translocation of TGL and inhibition of fatty acid synthesis by AKH seems to be via the release of calcium from intracellular calcium stores. Lipid and protein form a major part of the fat body in the penultimate larval instar crickets, while glycogen forms a minor part. However, in comparison with the adult (glycogen content of fat body about 1%) and last larval instar crickets (glycogen content about 3%), the penultimate larval instar crickets contain higher amounts of glycogen (about 9%). AKH inhibits acetate incorporation into lipid by the fat body from penultimate larval instar crickets. The patterns of acetate incorporation and inhibition by AKH are similar in both, males and females. The inhibition is dose-dependent with an EC50 of 79 pM AKH. AKH seems to play an important role in the development and reproduction of insects, in addition to its role during flight metabolism.
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Isolierung und Synthese von chinoiden Naturstoffen und Strukturberechnungen an verbrückten 1,1´-Binaphthylen
(2004)
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Burkhard Matthes
- Die vorliegende Arbeit beschäftigt sich mit Strukturberechnungen an synthetisch hergestellten 1,1´-Binaphthylen, die als Verdriller für induzierte cholesterische Phasen eingesetzt werden und der Isolierung und Synthese von bioaktiven Naphthochinonen aus dem Pilz Mollisia caesia Sacc. und der pazifischen Braunalge Dictyopteris undulata Okamura. Cholesterische Phasen können aus nematischen Wirtsphasen durch Zugabe einer chiralen Verbindung erzeugt werden. Dieser Vorgang wird als chirale Induktion bezeichnet. Bei der Substanzklasse der verbrückten 1,1´-Binaphthyle handelt es sich um Verbindungen, welche eine hohe Verdrillungsstärke (HTP) aufweisen. Die verbrückten 1,1´-Binaphthyle unterscheiden sich im Brückensubstituenten, der durch seine Geometrie die Größe des Winkels Theta wesentlich beeinflusst. Es sollte die Abhängigkeit der HTP vom Winkel Theta zwischen den beiden Normalvektoren der Naphthylebenen untersucht werden. Aus dem Pilz Mollisia caesia Sacc. wurden mit Hilfe der HPLC (Normalphase) neben Mollisin die beiden neuen Naphthochinone Mollisin A und Mollisin B isoliert. Die Strukturen der drei Verbindungen wurden mit Hilfe der Massenspektroskopie sowie ein- und zweidimensionaler NMR-Experimente bestimmt. Mollisin enthält als Strukturelemente ein p-Naphthochinonsystem und eine Dichloracetylseitenkette, die das herausragende Merkmal dieser Verbindung ist. Bei den neuen Verbindungen Mollisin A und B handelt es sich um Derivate des Mollisins, welche zusätzlich in Position 11 einfach (Mollisin A) bzw. zweifach (Mollisin B) chloriert sind. Die Umsetzung von 2-Chlor-5-methylanisol mit 3-Methylcrotonsäurediethylamid lieferte 8-Methoxy-3,6-dimethyl-1-naphthol, das in 1,8-Dimethoxy-3,6-dimethylnaphthalin umgewandelt wurde. Acylierung mit Acetylchlorid lieferte 4-Acetyl-1,8-dimethoxy-3,6-dimethylnaphthalin. Die gewünschte Dichlorierung der Acetylgruppe gelang nicht. Die Friedel-Crafts Acylierung mit Dichloracetylchlorid konnte trotz intensiver Bemühungen ebenfalls nicht erreicht werden, so dass die Untersuchungen zur Synthese von Mollisin an dieser Stelle beendet wurden. Als zentraler Baustein der Synthese des Cyclozonarons dient racemischer-8-Oxo-12-nordriman-11-säuremethylester, der aus beta-Ionon aufgebaut wird. Im Zuge mehrerer Reaktionsschritte wird die für die Cyclozonaronsynthese erforderliche (+)-Albicansäure enantiomerenrein erhalten. Die Eliminierung der OH-Funktion von (-)-Albicanol zu einer zweiten exocyclischen Doppelbindung stellt den letzten Schritt in der Synthese des Driman-Grundkörpers dar. Die Diels-Alder Reaktion mit p-Benzochinon ergibt ein Gemisch aus drei Verbindungen aus welchem das natürliche Cyclozonaron durch Oxidation mit 2,3-Dichlor-5,6-dicyano-p-benzochinon (DDQ) gewonnen werden kann.
