OPUS 4 | Search

The complex foraging strategy of the specialised gallfly Urophora cardui (Diptera: Tephritidae) for host plants (Cirsium arvense, Asteraceae) (2004)

Wiltrud Daniels

Nearly all herbivorous insects in terrestrial ecosystems depend on plants for their survival and reproduction. They dominate terrestrial ecosystems due to species and individual abundance. Interactions between these two groups are thus of a high significance for the analysis and the understanding of complex interactions in terrestrial ecosystems. Foraging for host plants by herbivorous insects is of a central importance. In the present thesis the foraging strategy of the specialised gall fly Urophora cardui on the creeping thistle, Cirsium arvense, was investigated as an example for the foraging of a specialised herbivorous insect. Males and females of U. cardui use the larval host plant as rendezvous place. The males establish territories on the plant, which they defend against conspecifics. The females lay eggs into axillary buds in order to initiate gall development. Male and female body size, measured as weight at eclosure or capsule width, was not correlated with male respectively female longevity. Males lived shorter than females. Capsule width of males and females was not significantly different, while weight at eclosure and fresh weight at death was. Females weighed more, which may be due to their higher need of energy during adult life. Both sexes lost body weight during life. All behaviours, which are performed by males and females on the host plant were defined, recorded and analysed. Females spent most of the time on resting, probing axillary buds, running on the plant and grooming. Males spent most of the time on copulation and patrolling their territory. The behaviour of both sexes was highly variable between individuals. Concerning the movement pattern on an already chosen host plant, females concentrate on the upper parts of the host plant. They were mainly occupied with extensive probing of various axillary buds, which occurred in a suitable developmental stage at the top of the plant. In contrast males patrolled the whole plant, although only the upper leaves became marked. If they encountered another male threatening and fighting were inevitable. Fights lasted several hours interrupted by threatening periods. Mating of males and females usually followed oviposition. Neither females nor males accepted modified host plants or models of thistles. Their behaviour on modified thistles was reduced mainly to running around the plant and grooming. These results indicate a rigid host plant template using the input of several senses, the flies always recognise models and modified plants as a non-host plant. Both sexes were able to discriminate host plants and non-host plants from a distance of 0.8-2m. The time male and female flies needed until they selected one of the host plants in a particular host plant stand depended on the number of non-host plants, host plants and the number of suitable hosts. The decision-time became shorter, if there were not too many suitable host plants. This may be due to decreasing sampling time of the host plants present. U. cardui females did not prefer plants of a certain height. In contrast the branching level, which indicates the number of axillary buds, and the number of flower buds played a significant role during foraging for host plants. Plants with an intermediate branching level were preferred, while those with many flower buds were avoided. Males of U. cardui were able to select their territorial plant on olfactory cues or on visual cues likewise. In contrast, emales were not able to recognise their host plant on olfactorial cues alone. But, if male-marked and unmarked host plants were available they significantly preferred the marked thistles. The differentiation between marked and unmarked C. arvense was made according to olfactorial cues, since plants did not differ in their height, nor in their branching level, nor in the number of flower buds. Thus, female selection of larval host plants depended on male choice for territories. This result is remarkable, especially in evolutionary terms, since males select the larval host for the offspring of their predecessor. Interestingly males preferred plants marked by conspecifics also. On the tip of the females’ ovipositor there is a receptor field with several morphological different receptor types. Mainly they seem to have mechanoreceptive as well as chemosensory functions. These receptors enable the females to measure and analyse the inner structure of the plant tissue at the axillary bud. The width of the apical meristem of the axillary buds was proven to influence female choice of the oviposition site. Axillary buds with an apical meristem-diameter above 0.62mm had a higher probability to became chosen by the U. cardui females. The clutch size was adjusted to the diameter of the apical meristem, indicating, that females were able to estimate the quality of the respective axillary bud influencing larval performance. These results were summarized in a model of the foraging strategy of U. cardui.

Pattern Formation in Rotating Fluid Systems under the Influence of Magnetic Fields (2004)

Erol Kurt

Patterns are observed in many different systems in nature. They are seen in the cloud streets, in sand ripples, in the morphology of plants and animals, on weather maps, in chemical reactions. In all these cases one deals with open, continuous dissipative systems which are driven out of equilibrium by an external stress. If this stress is larger than a certain threshold value, the symmetry of the temporally and spatially homogeneous ground state is spontaneously broken. The resulting patterns show then periodicity in space and/or in time. One of the best studied examples is the convection instability when a fluid layer is subjected to a temperature gradient. For instance, in a horizontal fluid layer heated from below and cooled from above a striped patterns of convection rolls develop. This scenario describes the famous Rayleigh- Benard convection (RBC), as a standard paradigm of pattern formation. Many concepts and mathematical tools to analyze the patterns have been developed and tested for this case. This thesis deals with two different pattern forming systems, namely a particular example of a convection instability and the case of a shear flow driven instability. In the first part of the thesis, a variation of the standard RBC is investigated. We consider the problem of convection induced by radial buoyancy in an electrically conducting fluid contained in a rotating (angular frequency, Omega) cylindrical annulus which is cooled at the inner surface and heated from outside. In addition, an azimuthal magnetic field (B) is applied for instance by an electrical current through the cylinder axis. The motivation of this study has come originally from the geophysical context. This setup is hoped to capture some important features of convection patterns in rotating stars and planets near the equatorial regions. The problem is also of considerable interest from a more general point of view in that it is concerned with formations of patterns in the presence of two competing directional effects, in this case rotation and the magnetic field. The second part of the thesis is devoted to the the pattern formation by a shear flow between two rotating and infinitely electrically conducting plates with a magnetic field perpendicular to the plates. This geometry is called the magnetic Ekman-Couette layer and has been a basic model for magnetic activities at the boundary of the Earth's liquid core or at the tachocline in the Sun below the convection zone for a few decades. To analyze the forementioned problems, various codes and computational tools had to be developed, for instance, we were able to describe complex spatio-temporal patterns by the direct simulations of the underlying hydrodynamic equations for our problems. The discussion of the physical details of the systems are postponed to the introductory sections of the corresponding parts of the thesis. In Chapter 1, a general formulation of the linear and nonlinear analysis, methods, which are applicable to both pattern forming systems in this work will be presented. The investigation of thermal convection in a plane layer which is a geometry equivalent to the cylindrical annulus will be discussed in Chapter 2. The next chapter (Chapter 3) covers both the linear and nonlinear analyses in the case of magnetic Ekman-Couette layer problem. Finally, in Chapter 4, we will present the general conclusions on both of the systems.

The Allatoregulatory Neuropeptides and their Genes in the fall armyworm, Spodoptera frugiperda (Lepidoptera: Noctuidae) (2004)

Mohatmed Abdel-latief

The genes encoding the S. frugiperda allatotropin (Spofr-AT), allatostatin (Spofr-AST), allatostatin type-A (Spofr-AST A) peptide family and allatotropin 2 (Spofr-AT 2) peptides were isolated from S. frugiperda brain cDNA. The Spofr-AT gene is expressed in three mRNA isoforms with 134, 171, and 200 amino acids, respectively, differing from each other by alternative splicing. The Spofr-AST cDNA encodes 125 amino acid residues including one copy of the Manse-AST mature peptide (type-C allatostatin). The deduced precursor sequence of Spofr-AST A gene contains 231 amino acids and allowed unambiguous identification of nine (or ten) peptides of YFXFGL-a peptide family, which are tandemly arranged in three blocks. A cDNA that encodes 53 amino acids was cloned from S. frugiperda brain cDNA, including one copy of a non-amidated decapeptide (Arg-Val-Arg-Gly-Asn-Pro-Ile-Ser-Cys-Phe-OH). This peptide strongly stimulates the synthesis and release of juvenile hormone (JH) in vitro by the corpora allata (CA) of S. frugiperda adult females and was code-named Spofr-AT 2. The primary structure of Spofr-AT 2 is identical at its C-terminus (-NPISCF) with the M. sexta type-C allatostatin (Manse-AST). One-step RT-PCR for semi-quantification of the gene expression, it is demonstrated that both genes (Spofr-AT and Spofr-AST) are expressed in brain, digestive tract, and reproductive organs of larvae, pupae, and adults of S. frugiperda in a time-, tissue-, and sex specific manner. The tissue-specific localization of the prohormone expression, as demonstrated by whole-mount in situ hybridization, confirms the overall tissue distribution of the prohormones as shown by RT-PCR and supports the pleiotropic functions of the peptides. Spofr-AST type-A gene is expressed in the brain, midgut, and reproductive organs of S. frugiperda larvae and adults in a time- and tissue-specific manner. Data confirm the nature of the allatostatin type-A peptides as brain/gut myoregulatory hormones. Northern blotting and RT-PCR analyses revealed that the Spofr-AT 2 gene is expressed as one transcript in the brain, midgut, and ovary in a tissue- and developmental-specific manner. Treating the CA with the synthetic peptide caused an up to tenfold increase in the release of JH. The stimulation of JH release was dose-dependent with an apparent EC50 of ca. 10-7 M. CA that were activated with Spofr-AT 2 could be inhibited by the addition of synthetic Manse-AST. In conclusion, the presented date strengthen the hypothesis that “allatoregulating” neuropeptides are diverse in structure, widely distributed and exhibit multiple functions. The functions may be tissue-specific as well as specific to particular developmental stages of insects. Knowledge of the various peptide precursor sequences has opened the way for synthesis of these peptides for detailed physiological and functional studies. Further quantitative experiments formulated in context of the life history of the animals will certainly yield a more detailed understanding of the mode of action of these peptides in S. frugiperda. Other major challenges in the future will be to clone the receptors for these peptides and to study the receptor distribution in the fall armyworm.

Tritrophische Interaktionen zwischen transgenem, insektenresistentem Bacillus thuringiensis-Mais, dem Herbivoren Chilo partellus (Lepidoptera: Crambidae) und dem Parasitoiden Cotesia flavipes (Hymenoptera: Braconidae) (2004)

Gernot Prütz

Die Untersuchung der Wirkung transgener insektenresistenter Pflanzen auf entomophage Insekten ist von Bedeutung, denn Räuber und Parasitoide können eine wichtige Rolle als Gegenspieler von phytophagen Schädlingen spielen. In der vorliegenden Arbeit wurde exemplarisch die wirtsvermittelte Wirkung von transgenem insektenresistentem Bacillus thuringiensis-Mais („B.t.-Mais“) auf den gregären koinobionten larvalen Endoparasitoiden Cotesia flavipes (Hymenoptera: Braconidae) unter Laborbedingungen untersucht. Als Wirt diente Chilo partellus (Lepidoptera: Crambidae). C. partellus ist einer der wirtschaftlich bedeutendsten Schädlinge an Mais und Hirse in Afrika, der mittlerweile in Kenia von C. flavipes wirksam dezimiert wird. B.t.-Mais synthetisiert ein bakterielles Protein mit insektizider Wirkung, das B.t. delta-Endotoxin. Das B.t.-Toxin schädigt das für die Verdauung wichtige Mitteldarmepithel von Insekten, daher wurden die Waldbauerschen Verdaungsparameter von C. partellus nach Aufnahme von B.t.- bzw. Kontrollmais bestimmt. Ferner wurden life history Parameter von C. flavipes ermittelt. Da C. partellus-Larven nach Aufnahme von B.t.-Mais starben, bevor der Parasitoid seine Larvalentwicklung vollenden konnte, wurde mit verdünnten B.t.-Mais-Suspensionen gearbeitet, die auf Blätter von Kontrollmaispflanzen aufgetragen bzw. in Stängelstückchen von Kontrollmaispflanzen injiziert wurden. Jüngere C. partellus-Larven fressen an Blättern, ältere in Stängeln, deswegen wurde mit beiden Pflanzenteilen experimentiert. Nicht parasitierte C. partellus-Larven verschiedener Stadien nahmen in der B.t.-Gruppe weniger Nahrung auf als in der Kontrolle. Die Ursache der verringerten Nahrungsaufnahme lag möglicherweise in einer gegenüber der Kontrolle verlangsamten Darmpassage der Nahrung. Auch das Wachstum war gegenüber der Kontrolle verringert. Dies könnte die Folge der verringerten Nahrungsaufnahme, eines Mangels an Wasser oder eines Mangels an Proteinen sein, denn das B.t.-Toxin kann die Absorption von Aminosäuren blockieren und zu Flüssigkeitsverlust führen. Ferner war der Anteil der verdauten Nahrung, der in Körpermasse umgewandelt wurde, gegenüber der Kontrolle reduziert. Ein Grund dafür könnte in dem gegenüber der Kontrolle erhöhten energetischen Aufwand für die Regeneration des Mitteldarmepithels liegen. Die Wirkungen der B.t.-Mais-Suspension auf die Verdauungsparameter von C. partellus waren bei Gabe von Blatt- und Stängelfutter ähnlich und stimmen mit Literaturdaten überein. Wurden jedoch parasitierte C. partellus-Larven mit Maisblättern gefüttert, konnte kein einziger Parasitoid seine Lavalentwicklung im Wirt vollenden und sich verpuppen. Daher wurden parasitierte C. partellus-Larven im folgenden nur noch mit Stängelstückchen gefüttert. Diese sind möglicherweise aufgrund ihres gegenüber Blättern erhöhten Proteingehaltes für ältere C. partellus-Larvalstadien ernährungsphysiologisch geeigneter als Blätter. Parasitierte C. partellus-Larven nahmen während der ersten 4 Tage des Versuchs in der B.t.-Gruppe weniger Nahrung auf als in der Kontrolle. Ab dem fünften Tag war der Unterschied jedoch nicht mehr signifikant. Dies lag möglicherweise am Schlupf der Parasitoid-L1-Larven im Wirt, denn Parasitoiden können die Nahrungsaufnahme des Wirtes in Abhängigkeit von ihrem Larvalstadium beeinflussen. Verschiedene life history Parameter von C. flavipes waren gegenüber der Kontrolle beeinträchtigt. So konnte der Parasitoid nur in wenigen Wirten seine Entwicklung erfolgreich beenden, wenn der Wirt B.t.-Mais-Suspension aufgenommen hatte. Ferner war das Gewicht von Puppen, Kokons, Kokonspinnseide und adulten Parasitoiden gegenüber der Kontrolle verringert. Das Gewicht von Parasitoidweibchen ist ein Maß für Fitness, denn größere Weibchen haben oft eine längere Lebensdauer und produzieren mehr Eier als kleinere. Nur in der B.t.-Gruppe ergaben sich hochsignifikant negative Korrelationen zwischen der vom Wirt aufgenommenen Nahrungsmenge und der Anzahl an Parasitoid-Kokons pro Wirt. Darüberhinaus war die vom Wirt aufgenommene Nahrungsmenge nur in der B.t.-Gruppe mit der Entwicklungsdauer des Parasitoids positiv korreliert. Wahrscheinlich nahm die Menge des aufgenommenen B.t.-Toxins mit der aufgenommenen Nahrungsmenge zu. Höhere Toxinmengen führten dabei zu einer Erhöhung der Mortalität der Parasitoidlarven im Wirt bzw. verlangsamten die Entwicklung des Parasitoids. Die anhand des tritrophischen Modellsystems der vorliegenden Studie gezeigten Methoden könnten auch auf andere tritrophische Systeme mit verschiedenen Arten von transgenen Pflanzen übertragen werden, die insektizide Proteine synthetisieren. Da diese Proteine auf das Verdauungssystem wirken, wäre eine Bestimmung der Verdauungsparameter bei Herbivoren und Prädatoren sinnvoll. Wie in der vorliegenden Studie angedeutet, kann die Bestimmung der Verdauungsparameter zu einem genaueren Verständnis der Faktoren beitragen, die die Entwicklung des Parasitoids (oder Prädators) bestimmen.

Synthesis, characterisation and application of low molecular weight and polymeric 1,3-di-2-thienylbenzo[c]thiophenes (2004)

Roman Kisselev

The synthesis and characterisation of the new class of compounds, dithienylisothianaphthene phenyldiamines (DTITNPDs) is described. These bifunctional hole transport dyes combine well-known hole-transport property of triaryl amines and thiophenes as well as low band gap nature of isothianaphthene (ITN) moiety. The synthetic strategy is chosen in such a way to obtain low molecular weight and polymeric DTITNPDs. Low molecular weight DTITNPDs are synthesised by Pd-catalysed amination of dibromo dithienylisothianaphthene with secondary amines. On the other hand, poly(DTITNPD)s are obtained via polycondensation of diiodo dithienylisothianaphthene and bis(secondary amine)s using a modified Ullmann reaction. The multi-step syntheses of dibromo dithienylisothianaphthene and novel diiodo dithienylisothianaphthene are optimised. The preparation of new bis(secondary amine)s are also described. Moreover, the influence of substituents on optical, electro-chemical and thermal properties of DTITNPDs and poly(DTITNPD)s is also investigated. The low molar mass (monomers) and polymeric DTITNs are also obtained. These compounds also possess hole transport property of thiophene and low band gap nature of ITN. Poly(DTITN)s are synthesised from corresponding monomers using FeCl3 oxidative polymerisation. Multi-step syntheses of DTITN monomers are also presented here. The main highlight of this work is the realisation of solution processable and film-forming and air-stable poly(DTITN) and poly(DTITNPD)s in addition to the model compounds DTITNs and DTITNPDs. The model compounds, polymeric DTITNPDs as well as poly(DTITN)s are characterised by means of 1H-NMR-, FT-IR-, MS- and UV-Vis- spectroscopy. Their thermal and electro-chemical behaviour is studied using TGA, DSC and CV measurements. All intermediates, synthesised in this work are also fully characterised by spectroscopic methods discussed above, except UV-Vis spectroscopy. Novel DTITNs and DTITNPDs show good thermal and electro-chemical stability as well as ability to form smooth thin films. DTITNPDs show lower band gap, solubility in common organic solvents and better thermal stability compared to DTITNs. For the application in organic electro-optical devices materials with improved optical and charge transport properties are required. Moreover, these hole transport dyes should match the energy levels (HOMO/LUMO) of the electron transport partner for efficient charge transfer/injection. In this respect, the main attention is placed on variation of energy levels in synthesised molecules by structure modification. The structure modification in DTITN usually changes the LUMO level in the molecule. In contrast to the DTITN, the introduction of different substituents into diphenylamine allows manipulation of HOMO level in DTITNPDs. Thus, the combination of DTITN and triarylamines leads to DTITNPD, where the values of both energy levels can be varied. Novel DTITNPDs exhibit smaller band gap compared to DTITNs. The better delocalised HOMO level in the DTITNPDs compared to DTITNs leads to novel hole transport dyes with Eg less than 1.8 eV. The low molar mass DTITNPDs are tested in plastic solar cells and multi-layer solar cells in combination with electron transport perylene bisimide derivatives and fullerene (C60). The poly(DTITN) is used in plastic solar cell in combination with a soluble fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). All of these compounds show good performance in solar cells. External quantum efficiency (IPCE spectrum) for the last solar cell shows a maximum of 40 % at 350 nm and a maximum of 15 % at 540 nm, at maximum wavelength of absorption. A promising result is obtained using low molar mass DTITNPD as red-emitter in OLEDs. When the red emitter doped in Alq3 at concentration of 1 % is used as emitting layer in OLED, the pure red electroluminescence with maximum brightness of 13830 cd/m2 at operating voltage of 12 V is observed. This device exhibits a high efficiency of 3.8 cd/A at 6 V bias, emitting bright red electroluminescence with CIE coordinates of x = 0.66 and y = 0.34, closely resembling the desired standard red colour (NTSC standard: x = 0.67 and y = 0.34) set for RGB displays.

Complex nanostructures in triblock terpolymer thin films (2004)

Sabine Ludwigs

The thin film phase behavior of poly(styrene)-block-poly(2-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P2VP-b-PtBMA) triblock terpolymers with volume fractions f(PS) : f(P2VP) : f(PtBMA) = 1 : 1.2 : x, with x ranging from 3.05 to 4, is studied with a combinatorial gradient approach. Gradients in film thickness are prepared via thin film flow coating of dilute solutions in chloroform. Upon controlled annealing in nearly saturated solvent vapor the films form terraces of well-defined step height. The dependence between morphology and film thickness is studied with optical microscopy, tapping mode SFM, and SEM. Though showing different morphologies in the bulk, the same sequence of surface structures is found with increasing film thickness for the whole range of compositions: a disordered phase in the thinnest regions, a liquid-like distribution of upright standing cylinders, cylinders oriented parallel to the film, and finally a hexagonally ordered perforated lamella structure (PL) on the first terrace with a thickness of d = (37+3) nm. Higher terraces also exhibit PL as surface structures. Due to the chemical nature of the block components and the particular stoichiometry of the polymer a wetting layer with a PtBMA-rich top layer is formed next to the substrate. By imposing an additional gradient in substrate surface energy, orthogonal to the gradually increasing film thickness, the perforated lamella is shown to be a stable phase, regardless of the chemical nature of the substrate, which makes this structure and methodology robust for application in nanotechnology. The complex phase behavior observed in thin films is supported by mesoscale computer simulations based on dynamic density functional theory. Thin films of the above mentioned triblock terpolymers are modeled as a melt of A3B4C12 Gaussian chains which is confined in a slit with film thickness H. By adjusting the interaction parameters between the polymer components and the surfaces, the experimentally observed sequence of surface structures as function of the film thickness can be successfully modeled. At well-defined film thickness the perforated lamella structure is formed. In analogy with earlier work on a two-component system these structures are identified as surface reconstructions of the bulk structure. In particular, the core-shell PL can be seen as analogue to the PL surface reconstruction of cylinder-forming AB and ABA systems. The influence of film thickness, surface field, and the interaction parameters between the different polymer components on the phase behavior is also explored. A large spectrum of surface structures is observed in analogy to the experiments. Further attention has been given to the perforated lamella structure. This structure can be visualized as P2VP/PS/P2VP lamellae which are perforated by channels of PtBMA interconnecting between two outer layers of PtBMA. A highly ordered PL structure could be prepared with a very small number of defects over an area of about 12 x 4 µm2. Because of the special functionalities of the triblock terpolymer a rather versatile nanostructure was produced. By selective UV-depolymerization of the PtBMA matrix phase, the PL phase might potentially be used for lithographic applications similar to the case of perpendicularly oriented poly(methyl methacrylate) (PMMA) cylinders in PS-b-PMMA block copolymer thin films. Furthermore, a responsive membrane can be created by selective removal of the matrix phase. The remaining PL has a P2VP shell which might be either switched via the pH-value or loaded with metal components. A polymer-analogous reaction of the matrix phase of the PL to poly(methacrylic acid) via acid-catalyzed hydrolysis leads to a pH-responsive nanostructure without altering the overall structure. With SFM in aqueous environment structural changes of the PL phase are studied as function of the pH-value. Upon changing the pH of the surrounding medium a strong swelling of the original film thickness is observed at pH-values > 6 to a maximum degree of 7.5-fold swelling. This swelling is explained with a conformational change of the matrix phase poly(methacrylic acid). The hexagonal arrangement of the pattern is not affected. The first two blocks PS and P2VP act as skeleton of the PL phase which withstands the mechanical forces exerted on the strongly swollen PMAA. In contrast to the PL phase core-shell cylinders oriented parallel to the interfaces cannot withstand these forces and are solubilised at high pH-values.

Water in the Earth’s Interior: Thermodynamics and kinetics of hydrogen incorporation in olivine and wadsleyite (2004)

Sylvie Demouchy

(1) Hydrogen diffusion in olivine The kinetics of hydration of dry single crystals of San Carlos olivine was determined by performing experiments under water-saturated conditions. The experiments were performed at 1.5 GPa, 1000°C for 5 hours in a piston cylinder apparatus, or at 0.2 GPa, 900°C, for 1 and 20 hours in TZM cold-seal vessels. Polarized Fourier-transform infrared spectrometry (FTIR) was employed to quantify the hydroxyl distributions in the samples after the experiments. The new data obtained show a strong anisotropy of diffusion, with the diffusion coefficient D[100]>D[010]> D[001] at 900°C for short duration experiments. This initial mechanism of diffusion possibly involved a redox-exchange between proton and polaron. After longer duration experiment, the anisotropy of diffusion is different with D[001]>D[010]» D[100]. For this second stage of diffusion a model of hydrogen-metal vacancy associated defects is proposed, where the vacancies are the slower diffusing species with the diffusion laws: [100], [010] = 10-(5.6±3.2) exp [-(175 ± 76)/RT] [001] = 10-(1.4±0.5) exp [-(258 ± 31)/RT] (2) Hydrogen diffusion in forsterite The kinetics of hydration linked to magnesium-vacancy diffusion within dry synthetic forsterite single crystals was determined by performing similar experiments and analyses as in the previous section. The experiments were performed at 1.5 GPa, 1000°C for 3 hours in piston cylinder apparatus, or at 0.2 GPa, 900-1110°C, for 3-20 hours in TZM cold-seal vessels. The chemical diffusion coefficients are marginally slower than in iron-bearing olivine for the same diffusion process, but the anisotropy of diffusion is the same, with the [001] axis the fastest direction of diffusion and [100] the slowest. Fits of the diffusion data to an Arrhenius law yield similar activation energies for each of the crystallographic axes; a global fit to all the diffusion data gave an activation energy around 211 ± 18 kJmol-1. Thus hydration likely occurs by coupled diffusion of protons and octahedrally coordinated metal vacancies. The diffusion rates are fast enough to modify water contents within xenoliths ascending from the mantle but they are probably too slow to permit a total equilibration in a new dry or wet environment. (3)Dehydration profiles in natural mantle-derived olivine within basalt First evidence for water diffusion in a natural mantle-derived olivine are presented from peridotite samples. The samples are olivine crystals within lherzolite xenoliths from the Quaternary alkali basalts of the Pali-Aike volcanic field in Patagonia. Water content and distribution was studied using unpolarized and polarized FTIR and analyses shows that olivine, Cr-diopside and orthopyroxene contain a significant amount of water, with up to 13 wt ppm H2O for olivine and up to 250 wt ppm H2O in the pyroxenes. In contrast, analysis of optically clear-parts of small garnet crystals indicates that they are dry. Oriented Infrared profiles show that olivine grains larger than 0.5 mm have hydroxyl-depleted rims. These water concentration profiles suggest that partial dehydration occurred during the ascent of the xenolith-bearing magma to the Earth’s surface, confirming that dehydration is occurring in the nature. From a combination of analyses of natural xenoliths with experimental diffusion works, ascent duration of the host magma is estimated to several hours, suggesting a fast rise up to the surface. (4)Temperature and pressure dependence of water solubility in iron-free wadsleyite Previous experimental studies indicate that the maximum solubility of water in wadsleyite may vary as a function of pressure and temperature. Therefore wadsleyite samples were synthesized using a multi-anvil press. One series of experiments were performed at a fixed pressure of 15 GPa and at various temperatures and in a second series the temperature was fixed at 1200°C and pressure was varied from 13 to 18 GPa. The starting material corresponds to a composition of Mg2SiO4 + 5wt% H2O. The water content was quantified by ion probe (SIMS). Results show that at 15 GPa, the water concentration decreases significantly with increasing temperature from 2.5 wt% H2O at 900oC down to 0.93 wt% H2O at 1400oC; the corresponding wadsleyite Mg/Si ratios increase from 1.79 to 1.93 over this temperature range. Up to 17 GPa, no significant effect of pressure on the water content was observed. Moreover, together with previous results on ringwoodite, these data imply a strong decrease of the water partition coefficient between wadsleyite and ringwoodite with temperature. (5) Computer simulation on hydrous point defect in iron-free wadsleyite The general utility lattice program (GULP), a semi-empirical method, was used to simulate the formation of point defects (Mott-Littleton method) in wadsleyite and especially hydrogen incorporation and their corresponding infrared frequencies.

Measuring juvenile hormone and ecdysteroid titers in insect haemolymph simultaneously by LC-MS: The basis for determining the effectiveness of plant-derived alkaloids as insect growth regulators (2004)

Stephanie Westerlund

Aim of this thesis was to develop a liquid chromatography-mass spectrometry (LC-MS) method to monitor hormones and their metabolites in the haemolymph of insects simultaneously. Furthermore, some plant-derived alkaloids were structurally elucidated, which may be used as insect growth regulators thus affecting haemolymph hormone titers in putative pest species. Juvenile hormones (JHs), JH diols and ecdysteroids were easily separated by high performance-liquid chromatography (HPLC) in less than 20 min using a reversed-phase C18 column and a methanol-water gradient. Subjecting the JH-JHBP (juvenile hormone binding protein) complex to HPLC was sufficient in releasing JH from the JHBP. In order to prevent JH from binding to glass surfaces, it was necessary to include a carrier in the solvent. JHs have a high affinity to polypropylene vials and should therefore be avoided, if no carrier is being used, such as triton X-100. The darkening of the haemolymph due to eumelanin production by phenol oxidases served as a visual indicator of general enzyme activity in the haemolymph. Isooctane:MeOH (1:1, v/v) inactivated the phenol oxidase system when used at a solvent-haemolymph ratio of 10. An isooctane:MeOH extract of haemolymph was most efficient in keeping JH distributed evenly in solution and prevented JH from adhering to the glass vessel. JH concentration in standard solutions was reduced with increasing sonication time. Highest ionization of JH was achieved in MeOH for MS compared to ACN or by using formic acid as an additive. In the positive ESI (electrospray ionization) mode the most abundant ions formed in haemolymph extract of Gryllus bimaculatus was the sodium adduct for JHs, JH diols and JH acids. At higher JH concentrations, the potassium adduct was also observed. The sodium and the potassium adducts were present in ecdysteroid analysis. The same ionization pattern was observed in Spodoptera frugiperda, Myrmicaria eumenoides and Acyrthosiphon pisum haemolymph. Method validation of the LC-MS method confirmed reproducibility and repeatability. The LODs for JHs and JH diols were between 6 to 12 pg, and 93 pg for ecdysteroids. 72 haemolymph samples can be processed per day by the LC-ESI-MS method using an autosampler. JH and ecdysteroid titer measurements showed good agreement between haemolymph titers and developmental events in Spodoptera frugiperda and Gryllus bimaculatus larvae and Gryllus bimaculatus adults. In Gryllus bimaculatus female and male last instar larvae, the JH titers were low and steady until day 6. The ecdysone peak maximum shifted from day 3 to a 20-hydroxyecdysone maximum peak on day 5, coinciding with the onset of adult ecdysis. JH III titers increased on day 3 in paired Gryllus bimaculatus males, occurring simultaneously with spermatophore maturation and deposition. A similar response was seen with ecdysone titers. Mated female crickets experienced a JH III titer increase on day 4 which coincides with egg deposit on day 4. Ecdysone titers reach a maximum on day 3 and ovary weights on day 4. Besides JH III, JH I was found in 5 to 8-day old female adult crickets, and in 6 and 7-day old male adult crickets. 20-Hydroxyecdysone was found neither in female nor in male Gryllus bimaculatus mated adults. The “classical” interplay between JHs and ecdysteroids was observed in 5th instar Spodoptera frugiperda larvae. JH titers decreased towards the end of the larval stadium and 20-hydroxyecdysone gave a sharp peak on the last day of the 5th instar. Extremely low levels of JH were measured in 6th instar larvae. 20-Hydroxyecdysone and ecdysone titers increased simultaneously in prepupae. The already known alkaloids arborinine and arborine, and the for the first time isolated 4-methoxy-1-methyl-2(1H)-quinolinone from Glycosmis pentaphylla, were extracted from Glycosmis pentaphylla leaves and are discussed as possible insect growth regulators affecting hormone titers in the haemolymph of insect pest species.

Physikalische Eigenschaften anionischer Tensidsysteme mit zweiwertigen Gegenionen und ihre Mischungen mit zwitter-ionischen Tensiden und Cotensiden (2004)

Reiner Beck

Die vorliegende Arbeit beschäftigte sich mit dem Phasenverhalten und den physikalischen Eigenschaften von Magnesium- und Calciumtensiden in wässrigen Lösungen. Durch Zusatz von zwitterionischen Tensiden bzw. Cotensiden wurden interessante und teilweise überraschende Phasenfolgen erzeugt. Die Verwendung von zweiwertigen Gegenionen in ionischen Tensidsystemen bewirkt, im Vergleich zu den einwertigen Systemen, eine Vielzahl von Veränderungen, sowohl im Phasenverhalten, als auch bei ihren physikalischen Eigenschaften. Ein seit langem bekanntes Phänomen ist hierbei die Krafftpunkterhöhung bei Calciumsalzen, die in wässrigen Lösungen bei niedrigen Temperaturen als Präzipitat ausfällt. Tenside mit mehrwertigen Gegenionen besitzen eine niedrigere cmc als ihre entsprechenden einwertigen Salze. In Kombination mit anderen Tensiden oder Cotensiden erhöht sich das Mizellwachstum und es kommt zur Ausbildung von vesikulären und lamellaren Strukturen. Durch die doppelte Ladung ist ein höherer Anteil der Gegenionen mit der Bilayermembran assoziiert. Dies erniedrigt deren effektive Oberflächenladungsdichte signifikant, so daß auf diese Weise ihr Phasenverhalten dem von ungeladenen bzw. elektrostatisch abgeschirmten Systemen ähnelt. Einige Eigenschaften sind daher typisch für nichtionische Tenside – wie zum Beispiel die Bildung von geschwollenen lamellaren Phasen oder sogar von Schwamm-Phasen. Die zweiwertigen Ionen wirken dabei teilweise wie Klammern zwischen anionischen Tensiden. Ihr Phasenverhalten ähnelt dem doppelkettiger Tenside. Durch Zusatz von stark verzweigten Cotensiden ist es in dieser Arbeit gelungen, eine völlig neuartige Schwamm-Phase mit erstaunlichen Eigenschaften aus anionischen Ca/Mg-Tensiden herzustellen. Die bisher bekannte Schwamm-Phase besitzt neben ihrer außergewöhnlichen bikontinuierlichen Struktur eine Reihe interessanter Eigenschaften. Trotz der hohen Konzentrationen der einzelnen Komponenten, ist ihre Viskosität relativ niedrig. Sie weist eine hohe Temperaturempfindlichkeit auf. Auf Grund des relativ engen Existenzbereichs bezüglich des Cotensid/Tensid-Verhältnises sind die technischen Einsatzmöglichkeiten für die Schwamm-Phasen aber sehr eingeschränkt. Durch verzweigte Cotenside ist es gelungen, den Existenzbereich der Schwamm-Phase enorm zu vergrößern, ohne dabei ihre grundlegend positiven Eigenschaften zu verlieren. Diese neue Phase weist all die für eine klassische Schwamm-Phase typischen Eigenschaften auf: die Potenzab-hängigkeiten charakteristischer Größen in Verdünnungsreihen (vgl. Elektrodoppelbrechung), Fließdoppelbrechung, eine niedrige Viskosität und das typische Verhalten bei Neutronenstreu- und NMR- Experimenten, das durch den hohen Unordnugsgrad der isotropen Schwamm-Phase verursacht wird. Den Ähnlichkeiten mit der klassischen Schwamm-Phase stehen, abgesehen vom extrem großen Cotensid/Tensid Existenzbereich, auch eine Reihe von markanten Unterschieden gegenüber. Einer davon ist zum Beispiel die sehr viel höhere Leitfähigkeit der Schwamm-Phase. Diese hängt stark von der Struktur des vermessenen Systems ab. An den FF-TEM-Aufnahmen erkennt man, daß die neue Phase sehr ungeordnete Strukturelemente besitzt. Sie ist geprägt durch Passagen und Brücken, die zwischen den Membranen der Doppelschicht liegen. Die idealerweise getrennten Hälften des bikontinuierlichen Systems sind auf diese Weise für Ionen durchlässig geworden. Auch die Tatsache, daß die neuartige Schwamm-Phase in ionischen Tensiden mit zweiwertigen Gegenionen existiert, ist außergewöhnlich. Bemerkenswert ist in diesem Zusammenhang, daß mit stark verzweigten Cotensiden wie EHG oder PPA die Ausbildung komplexer Strukturen trotz ionischer Ladungsträger möglich ist, und das sogar besser, als in Systemen ohne Ladungsträger. Im System DDMAO/EHG/Wasser wurde dies sowohl durch Zugabe des ionischen Tensids Mg(DS)2, als auch durch Zugabe von Salz nachgewiesen. Interessant aus thermodynamischer Sicht ist der Phasenübergang zwischen der Lamellaren-Phase und der Schwamm-Phase im System 50 mM Ca(C14-alpha-MES)2/EHG/Wasser, in dem anscheinend kein Zweiphasengebiet zwischen den strukturell so unterschiedlichen Phasen vorhanden ist. Ein wichtiger Punkt bei der Untersuchung der neuartigen Schwamm-Phase war auch die Erforschung eines eventuellen Übergangszustands zwischen der klassischen und der neuen Schwamm-Phase. im System Mg(DS)2/DDMAO/EHG/n-Hexanol/Wasser. In dieser Arbeit wurden mit Hilfe des Leitfähigkeitsverlaufs die Phasenschemata dieses Fünfstoff-Systems bei unterschiedlichen Zusammensetzungen untersucht. Der beobachtete Übergang zwischen neuer und klassischer Phase erfolgt kontinuierlich.

Importance of floral scent compounds for the interaction between Silene latifolia (Caryophyllaceae) and the nursery pollinator Hadena bicruris (Lepidoptera: Noctuidae) (2004)

Stefan Dötterl

In the present study, the role of floral volatiles for the interaction between the nocturnal Caryophyllaceae Silene latifolia, and the noctuid moth Hadena bicruris was determined. This insect-plant relationship is one of the known nursery pollination systems, where pollinators reproduce within the flowers they pollinate. Silene latifolia is a dioecious weed, native to Europe and formerly introduced to North America. It is the main larval host plant of H. bicruris, which is distributed in Europe and North Africa. Especially night-active moths, among them H. bicruris, which are attracted by the flower scent, pollinate S. latifolia. However, until now, nothing was known about the role of single flower scent compounds for the attraction of the moths. This thesis describes the chemical composition and the geographical variability in the flower scent of S. latifolia. Furthermore, electrophysiological and behavioural tests with floral scent extracts and single authentic standard compounds were carried out in H. bicruris to identify the attractive compounds of the complex floral scent. To get an insight into the role of floral scent in guiding potential pollinators on flowers, the spatial fragrance pattern within the flowers of S. latifolia was determined, additionally. The variability in floral scent was very high, especially between different populations, and different chemotypes were characterised.Typical compounds in floral scent of S. latifolia were lilac aldehyde isomers, trans-beta-ocimene, benzaldehyde, phenyl acetaldehyde, or veratrole. Some of these compounds are known to attract nocturnal Lepidoptera species. To characterise antennal and behavioural responses of H. bicruris to various floral scent chemotypes of S. latifolia, and to S. vulgaris (which is rarely also used as host plant), different S. latifolia extracts, and a S. vulgaris extract were analysed using GC-MS methods. These extracts were further used in GC-FID/EAG and GC-MS/EAG detections, respectively. Main compounds in the tested extracts often elicited main signals in the antennae (e.g. lilac aldehydes, phenyl acetaldehyde). Some compounds elicited main signals in the antennae, though they were only minor components in the extracts (e.g. 3-methyl-butyl-aldoxime, benzaldehyde). Other compounds elicited only weak signals in the antennae, though they were abundant in the extracts (e.g. myrcene, methyl benzoate). The compounds of the most common chemotypes of S. latifolia were very sensitively detected by Hadena bicruris, whereas compounds of less abundant chemotypes were less sensitively detected. Floral scent blends that were dominated by lilac aldehydes or phenyl acetaldehyde effectively attracted moths. Hadena bicruris can electrophysiologically and behaviourally distinguish between its main host plant, S. latifolia, and the similarly scented S. vulgaris, another rarely used larval host plant, only by their floral scent. To identify floral scent compounds of S. latifolia that are important for the attraction of H. bicruris, the GC-FID/EAD or the GC-MS/EAD method was used in a first step to identify compounds that elicit signals in the antennae of the moth. Electrophysiologically very active compounds were tested in wind tunnel bioassays, and the attractivity of these compounds was compared to the attractivity of the natural scent of whole flowers of S. latifolia. The antennae of H. bicruris detected substances of several compound classes such as monoterpenoids, benzenoids, fatty acid derivatives, and nitrogen-bearing compounds. Lilac aldehydes were the most attractive compounds in wind tunnel bioassays, and attracted 90% of the tested moths, as did the scent of single flowers. Some compounds did not attract any moth, though they elicited significant signals in the antennae. To determine the parts of the female and male flowers responsible for scent emission, volatiles from attached intact flowers were sampled and then single flower parts were progressively removed. After each preparation step, volatiles were collected from the remaining “flower”. Especially the petals and the anthophore emitted the typical flower volatiles of S. latifolia; and compounds emitted from the petals differed from the compounds emitted by the anthophore. The anthophore emitted only lilac aldehydes and alcohols. Lilac aldehydes are known to be behaviourally very attractive for noctuid Lepidoptera such as Autographa gamma and Hadena bicruris, and they may serve as nectar guides in S. latifolia.

Refine

Author

Year of publication

Document Type

Language

Keywords

Institute

69 search hits