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Geoarchaeological and chronometrical evidence of early human occupation on Lanzarote (Canary Islands) (2003)

Ludwig Zöller Hans von Suchodoletz Nils Küster

Two desert loess–paleosol sequences in sediment traps were investigated using (pedo-) stratigraphy, sedimentology, soil mineralogy and IRSL dating. So far we cannot recognise significant IRSL age-underestimates from the polymineral fine-grain fraction of our samples. We establish a first palaeoclimatic sequence spanning the past ca 200 ka which can be compared to data from other Canary Islands and surrounding areas, including terrestrial and deep sea records. More humid phases on Lanzarote are apparently triggered by Milankovich forcing, but the climate remained semi-arid to arid all over the past 200 ka. The onset of human occupation of the island during a slightly moister period is bracketed between 5 and 10 ka, based on the occurrence of archaeosediments containing bones of ovicaprid. This is the first proof of much earlier occupation than witnessed so far from archaeological records. The early subsidiary economy had a strong impact on soil stability and landscape shaping of the island.

Dynamics of vortices in the two-dimensional anisotropic Heisenberg model with magnetic fields. (2003)

Juan Pablo Zagorodny

The subject of this work is the dynamics of a vortex in a classical 2-dimensional spin system with anisotropic exchange interaction under the combined action of magnetic fields and damping. Static as well as dynamic magnetic fields were employed (as dynamical field we used a homogeneous field which is rotating in the XY-plane). The most important goal of this work was to demonstrate that there is a coupling between the inner and translational freedom degrees of the vortex, coupling which is responsible for at least 2 phenomena that we study in detail in this Thesis: 1. the switching or flipping of the vortex polarization (for negative field frequency), and 2. the formation of stable orbits of the vortex center around the center of the system driven by the rotating field (for positive frequency). It was known to us that the polarization can change abruptly its sign under the action of a field rotating in the XY-plane, for p omega < 0 and appropriate field amplitudes. In the Chapter 4 we have investigated the possible underlying mechanisms for this phenomenon. Our main results can be summarized as follows: a) The flipping times do not depend essentially on the size of the system, provided that the lattice is large enough (radius L >~ 36 lattice constants). In other words, the switching of the vortex polarization is not much affected by the presence of boundaries. b) In our numerical simulations we observed a clear correlation between the core magnetization dynamics (the oscillations of the core spins in the out-of-plane direction) and the velocity of the vortex center in the plane of the lattice. c) A diagram of flipping events as a function of the field parameters, from extensive numerical simulations with an OP vortex in a rotating magnetic field, was presented. We found out that in the (omega, h) parameters space there is no well-defined curve which separates the regime where the flips do not occur from the regime where they do. We found intervals ("windows'') of intermittent flip and non-flip events. d) The switching of the vortex polarization can be achieved also by applying a static magnetic field with both in-plane (IP) and out-of-plane (OP) components. The IP component of the field sets the vortex into translational movement in the XY-plane, while the OP component breaks the vertical symmetry favoring one of the two possible orientations. e) The switching dynamics may be described in terms of a core model which takes into account a coupling between the vortex polarization dynamics and the motion of the vortex center. We showed that a reduced core model, which is valid near the threshold of the IP-OP vortex instability (lambda ~ lambda c), can be mapped to a generalized Thiele equation with an inertial term. f) It is plausible that the phenomenon of switching we described will not be essentially affected by the inclusion of a dipole-dipole interaction. The experimental works on nanodisks mentioned in the Introduction of this Thesis reported the observation of vortices in either of two polarization states, and the switching between them was forced by means of static fields perpendicular to the plane of the disks. Rotating magnetic fields might be used as well static fields with both IP and OP components to make this switching more favorable. In the Chapter 5 we turned to the study of the movement of the vortex in the XY plane, in the presence of the IP rotating field. Attention was directed to the existence of stable orbits, where the vortex stays inside the system in a stationary movement, forming circular limit cycles. We discussed then the failure of the conventional Thiele approach to describe this phenomenon, and this motivated us to formulate an extended collective coordinate Theory, which leads to a qualitative agreement with the results of the simulations. A diagram of the different types of trajectories, as a function of the field parameters, showed the presence of non-monotonous effects and "windows'', like in the case of the switching diagram. We are led to conclude that for some regions of the field parameters space, the system exhibits chaos -which is typical for many-body systems-, though no particular tool of the chaos theory was used to study our discrete and collective coordinate models, from this viewpoint. Our theoretical work qualitatively suggests that it would be interesting to apply in the experiments weak rotating fields like those used here, to control both the mean position of a vortex in larger magnetic dots (where the vortex center could show dynamics) and at the same time the sign of the out-of-plane core magnetization. Future directions of this work may include the use of inhomogeneous fields, particularly with a gaussian localization in a small region of the lattice or "spot'', as a model of the field of a laser beam.

Maximum Entropy Method in Superspace Crystallography (2003)

Lukas Palatinus

This thesis discusses several aspects of the combination of the Maximum Entropy Method (MEM) for the reconstructions of the electron density with the superspace approach to the description of structures of aperiodic crystals. It is shown that the MEM in superspace provides a parameter-free reconstruction of the modulation functions with sufficient accuracy. The MEM in superspace has been applied to diffraction data of several compounds. The computer program BayMEM was developed for this purpose. BayMEM allows electron densities of the ordinary 3D structures and the superspace electron densities of the aperiodic structures to be reconstructed using the same general principles. The program has been extended by adding features improving its versatility and accuracy of the results. The improvements include attaching of the set of subroutines MemSys5 to BayMEM, implementation of the method of the Generalized F-constraints and the static weighting, implementation of the G-constraints, of the Prior-derived F-constraints and of the two-channel entropy. The second major computer program EDMA is a software tool for analysis of the electron densities in arbitrary dimension. The program analyzes the MEM electron density and extracts quantitative information about the atoms according to Bader's formalism “Atoms in molecules“. Two new variants of the constraints in the MEM have been developed in order to solve the problems with artifacts in the MEM reconstructions. The two methods are the Generalized F-constraints and the Prior-derived F-constraints. The concept of the Generalized F-constraints is based in the observation, that the standard F-constraint is not sufficiently strong to constrain the histogram of the normalized residuals of the structure factors to the expected Gaussian shape. Higher moments of the distribution of the normalized residuals were therefore used as the constraint in the MEM calculations. With these constraints significantly improved histograms were obtained. The source of some artifacts in the MEM electron densities was identified to be the tendency of the MEM to estimate incorrectly those structure factors, that are not included in the experimental dataset. It is shown that the missing structure factors can successfully be replaced by the structure factors derived from the procrystal electron density. If the structure factors derived from the procrystal prior electron density (the Prior-derived F-constraints) are used as additional constraints in the MEM calculation, the result is free of sharp artifacts and the quality of the reconstruction of the electron density is comparable with the results of multipole refinements. To test the accuracy of the MEM in superspace, the method was applied to the dataset of the misfit-layer composite structure of (LaS)1.14NbS2. It has been shown, that the MEM on the model structure factors reproduces the model modulation functions with accuracy better that 10% of the pixel size of the grid, on which the electron density was sampled. The structure of the high-pressure phase III of Bi provided a prominent example illustrating the advantages of the MEM in superspace over the standard structure refinements. The MEM in superspace was applied to the diffraction data of Bi-III to extract more information about the modulation than obtained from the standard structure refinement. The modulation functions extracted from the MEM electron density revealed a block-wave-like shape of the modulation function of the Bi atom of the host structure that indicates shifts of the atom between two stable environments rather than smooth harmonic variation of the position indicated by the modulation function from the standard refinement. Secondly, the MEM modulation function of the Bi atoms in channels allowed to better understand the nature of the most prominent feature of the modulated structure - the occurrence of the pairs of Bi atoms along the channels. The incommensurately modulated structure of ammonium tetrafluoroberyllate (NH4)2BeF4, stable between 175K and 182K, was solved and refined in superspace. The known two-fold low-temperature superstructure of (NH4)2BeF4, that is stable below 175K has been described in superspace as a commensurately modulated structure. With aid of this description the close relationship between the two structures has been found. The MEM was applied to the incommensurate structure to test the appropriateness of the refined harmonic structure model. The MEM has shown that the harmonic model is very accurate. The MEM in superspace was established in this thesis as a reliable tool for the structure solutions of the modulated structure. The individual chapters together form a framework that allows to use the MEM in superspace to extract novel information from the diffraction data of both the periodic and aperiodic structures, that cannot be obtained from the structure refinements.

Instabilities in layered liquids induced by external fields (2003)

Günter Auernhammer

In this thesis, we have shown that the inclusion of a nematic degree of freedom in the macroscopic hydrodynamic description of smectic-A-like liquids leads to a number of interesting results. While the director and the layer normal are coupled such that they are parallel in equilibrium, in non-equilibrium situations, the director needs not be parallel to the smectic layer normal. This is in contrast to standard smectic-A hydrodynamics. Using irreversible thermodynamics and symmetry arguments, we derived a complete set of macroscopic hydrodynamic equations for the director variables, the layer displacement, the velocity field, and the moduli of the nematic and smectic order parameters. Recent experiments find that the parallel orientation of smectic-A- like liquids is destabilized by an applied shear. After destabilization, two typical scenarios are observed in a steady state situation: i) The layers are oriented perpendicular to the vorticity direction of the flow, i.e., they lie in the plane spanned by the velocity and the gradient direction (`perpendicular' orientation). ii) Closed multi-lamellar vesicles (`onions') form. A number of experiments indicate that the onset of this reorientation is controlled by the applied shear rate. In contrast to standard smectic-A hydrodynamics where shear in the parallel orientation has no effect on the layers, this destabilizing effect comes out naturally from our extended smectic-A hydrodynamics. The argumentation goes along the following lines. The shear field exerts a torque on the director that must be balanced by the coupling to the layer normal. In the limit of small angles, balancing these torques leads, in the steady state, to a shear-induced director tilt proportional to the shear rate. The preferred thickness of a smectic layer is directly connected to the projection of the averaged molecular axes on the layer normal, or, in terms of our model, the thickness is proportional to the projection of the director on the layer normal. If the director is tilted, this projection is shorter. This decrease of the projection is equivalent to an effective dilation, because the actual layer thickness is larger than the preferred layer thickness. Similar to the case of low molecular weight smectic-A liquid crystals under a dilative strain, this effective dilation leads to an undulation instability. To investigate the stability of the parallel alignment, we performed a linear and weakly non-linear analysis of the governing equations. The initial state is the above described spatially homogeneous director tilt with the smectic layers in the parallel orientation. The linear stability analysis showed an undulation instability which sets in above a critical tilt angle (or equivalently, a critical shear rate). This critical tilt angle turned out to depend strongly on the material parameters. For a typical low molecular weight thermotropic liquid crystal, we estimated the critical tilt angle to be on the order of a few degrees. The linear stability analysis also revealed that the nematic and smectic order is modulated close to the boundaries. Since the probability for the formation of defects is larger in regions with a decreased modulus of the order parameter, these variations in the modulus of the order parameter open the way for a destabilization of the layered structure. We note that a detailed investigation of this point is beyond the scope of the present work. Finally, we could exclude an oscillatory instability for all physically reasonable regions in parameter space. The weakly non-linear analysis shows that the bifurcation is supercritical for most physically relevant regions in the parameter space. A detailed comparison to an independent approach was undertaken in a collaboration with simulation physicists from the Max-Planck- Institute for Polymer Research in Mainz. In a molecular dynamics simulation, a model layered liquid consisting of chains of four particles (AABB) was considered. The interaction potential of particles not connected by springs is attractive for like particles and repulsive for particles of a different nature. The simulation demonstrated the two main predictions of our analytic theory: The director tilts in the flow direction and, above a critical shear rate, the layers show stationary undulations with a wave vector in the vorticity direction. Besides this good qualitative agreement, a reasonable quantitative agreement for the critical shear rate was found.

THE REDEEMED CHRISTIAN CHURCH OF GOD (RCCG), NIGERIA. LOCAL IDENTITIES AND GLOBAL PROCESSES IN AFRICAN PENTECOSTALISM (2003)

Asonzeh Franklin-Kennedy Ukah

This study documents the history and growth of the Redeemed Christian Church of God (RCCG). The RCCG is a pentecostal church in Nigeria, established in 1952, but was little known until the 1990s when it came into national prominence. It was founded by Josiah Akindayomi who was converted form Yoruba religion into the Church Missionary Society (CMS). He left the CMS to join the Cherubim and Seraphim (C&S), one of the emerging African Independent Churches (AICs). From here, he founded his own independent church which in subsequent years developed into a pentecostal church. The RCCG is one of many pentecostal churches existing in Nigeria. Although some research exists on Nigerian Pentecostalism, there is almost nothing on the RCCG. The present study presents a case study which deals with Pentecostalism in Nigeria and tries to relate it to globalisation discourse. It is the first such study from Africa. Its contribution is in providing a case study on a religious group that also relates to contemporary processes which, some scholars have argued, have side-stepped Africa (Brouwer et al. 1996; Gifford 1998; 2001; Cooper 2001). It builds on, and follows the scholarly tradition of Peel (1968; 2000); Hackett (1987; 1989); Marshall-Fratani (1998). These scholars have worked on the Nigerian religious sphere by combining History of Religions and social scientific approaches. The study is made up of three parts. Part one is composed of the historical section comprising chapters 2 and 3 which includes the biographies of the founder of RCCG and his successor. Part two is the descriptive section which is made up of chapters 4, 5 and 6. This section focuses on organisational structure, institutions, doctrines and rituals of the RCCG. Chapter 4 presents the organisational structure of the church at the present period. It also discusses some of the para-church groups, schools, media use, finance and the place of women in the church. Chapter 5 examines the belief system while chapter 6 presents the ritual activities of the church. Part 3, which consists of chapter 7, is the theoretical reflection on our case study. While the RCCG has grown by reinterpreting its doctrines in line with local social, economic, political and cultural situation, part of its appeal to a broad spectrum of people, groups and organisations is its marketing strategies as well as its relationship with global economic players such as Coca-Cola company, Procter and Gamble, a wide range of manufacturing companies, banks and other financial institutions which provide scarce human and economic resources for the church’s social, religious, economic and political mobilisation in Nigeria.

How availability and quality of nectar and honeydew shape an Australian rainforest ant community (2003)

Nico Blüthgen

Ant communities visiting nectar and honeydew sources were studied in a tropical lowland rainforest in North Queensland, Australia. The study focused on the hypothesis whether the distribution and composition of nectar and honeydew diets influence resource partitioning and competition in the ant community, and thus regulate community composition. Ants were the most common consumers on all extrafloral nectaries, while they constituted only a minority of floral visitors. In total, 43 ant species were observed to consume nectar from extrafloral nectaries (34 plant species) or from flowers (14 plant species), and wound sap exudates (three plant species). Six nectar-foraging ant species attended trophobionts (including at least 12 species of homopterans and two species of lycaenid caterpillars) for honeydew. Ant species showed a significant compartmentalisation of nectar use across plant species, although most ant species visited a broad spectrum of plants that strongly overlapped between different ants. Trophobioses were much more specialised at the study site, and some ant species attended certain trophobionts exclusively. On each plant individual, only a single ant colony was observed attending trophobionts. In contrast, simultaneous co-occurrences between different ant species foraging for nectar on the same plant individuals were common (observed in 23% of the surveys), although these proportions varied strongly across plant and ant species. The two most dominant ant species (Oecophylla smaragdina and Anonychomyrma gilberti) had mutually exclusive territories, and they were each associated with a significantly different assemblage of other ant species on nectar plants. This community pattern corresponds with the concept of ant mosaics that is based on dominance hierarchies. Honeydew and nectar sources varied substantially in carbohydrate and amino acid concentration and composition (HPLC analyses). There was a strong relationship between the composition of these resources and their use by ants, in particular by the dominant O. smaragdina. Among all 32 nectar and honeydew sources analysed, resources actually consumed by this ant were characterised by relatively similar amino acid profiles and higher total sugar concentration. The most common diets of O. smaragdina included two honeydew sources (Sextius ‘kurandae’ membracids on Entada phaseoloides and Caesalpinia traceyi legume lianas) and two extrafloral nectars (Flagellaria indica and Smilax cf. australis) that had the broadest spectrum of amino acids. Furthermore, these trophobioses on lianas showed a significantly higher per capita recruitment of this ant species (number of workers per individual homopteran) compared to trees. F. indica and S. cf. australis extrafloral nectaries were also commonly monopolised by O. smaragdina in a similar way as trophobioses; co-occurrences were significantly rarer than at other nectar sources. Field experiments on nectar preferences were performed using artificial sugar and amino acid solutions in pairwise comparisons. Preferences among sugars were largely concordant between ant species. For most ant species, sucrose was more attractive than any other sugar, and attractiveness increased with sugar concentration. Most ant species also preferred sugar solutions containing mixtures of amino acids over pure sugar solutions. However, choices between different single amino acids in sugar solutions varied substantially and significantly between species. Preferences between solutions were significantly reduced in the presence of competing ant species. Thus the experiments show that both variability in gustatory preferences, especially for amino acids, and conditional effects of competition may be important for resource selection and partitioning in nectar feeding ant communities. Stable carbon and nitrogen isotope composition was analysed for 50 ant species, and additionally for associated plants, homopterans and other arthropods from the study site. Nitrogen isotope ratios (d15N) of ants were not correlated with those of plant foliage from which the ants were collected. Instead, d15N may represent a powerful indicator of trophic position of omnivorous ants like in other foodweb studies, suggesting that members of the ant community spread out in a continuum between largely herbivorous species, feeding on nectar or honeydew, and predatory taxa. Variability between colonies of the same species was also pronounced. d15N values of O. smaragdina colonies from mature forests, where most of their nectar and honeydew sources are found, indicate lower trophic levels than isotope signatures of colonies from open secondary vegetation. This study demonstrates that the distribution and quality of honeydew and nectar sources have a strong structuring impact in diverse tropical ant communities. Amino acids were found to play a key role for ant species preferences and competition, and for nitrogen fluxes to colonies of the arboreal ant fauna.

QUANTIFYING THE DISTRIBUTION OF FOREST FUNCTIONAL TYPES AND FOREST LEAF AREA INDEX IN THE ALPS (2003)

Albena Bobeva

Land cover change is an important element of global environmental change processes. Most ecosystem processes strongly depend on land cover and its attributes. Mapping land cover, especially in mountain terrain is a difficult and challenging task. Remote sensing is an attractive source of thematic maps, such as those depicting land cover. Thematic mapping from remote sensing data is typically based on image classification. The image classification procedure synthesizes satellite data with field data and other ancillary data derived from a Geographic Information System (GIS - ArcInfo) coverage. The present study combines GIS and remote sensing data to produce a land cover map for the National Park Berchtesgaden and to build an extrapolation for other test areas in the Alps (Stubai and Ötz Valleys). Although a vast GIS data set had been assembled for the National Park, remote sensing was not previously used as a tool for land cover mapping and forest ecosystem analysis. For supervised classification, the maximum likelihood algorithm was used to sort and group data into discrete classes, which can be uniquely identified. Comparison and accuracy assessment with „ground truth“ data was carried out. An overall accuracy of 86% and 87% of the classification results in the National Park Berchtesgaden and in Stubai Valley, respectively, was achieved. Another important parameter determining gas exchange (water loss and carbon gain) of alpine forests is Leaf Area Index (LAI). Remote sensing provides a means to estimate LAI over large areas. To map LAI in mountain regions, Landsat TM NDVI index and SR index were examined together with forest inventory data of the Berchtesgaden National Park. “Ground truth” point grid maps for LAI were obtained through the use of allometric relationships (relating tree size and leaf area) as derived from tree harvests and together with the forest inventory database. On the basis of the forest mask derived from land classification and the Landsat vegetation indices, homogeneous forest polygons were identified. They were used for polygon by polygon correlation between LAI and vegetation indices. Mean forest polygon values were used to determine the relationships. With the derived equations, LAI was mapped at 30m resolution (Landsat data). Using the digital elevation model, the distribution of the vegetation types and LAI along elevation gradients was investigated. The results in National Park Berchtesgaden were further used in an extrapolation to classify land cover in Stubai and Ötz Valleys. Except to detect the distribution of land cover classes, supervised classification was used as a part of the algorithm for predicting forest leaf area index at the investigated sites. The digital LAI map of Stubai Valley was compared with LAI map derived from allometric relationships in Neustift (part of Stubai Valley). A correlation between NDVI and LAI in Neustift was derived. The validation results derived for coniferous forest in Neustift (Stubai Valley) show good correspondence to the results derived in Berchtesgaden. For both investigated sites, leaf area index can successfully be described with simple and reasonable correlation with NDVI.

Phase Behavior and Structural Transitions in The Mixtures of Cationic Surfactants and Hydrophobic Counterions (2003)

Rami Abdel-Rahem

Anionic hydrophobic counterions with certain geometry adsorb onto the surface of cationic surfactant micelles and they minimize the repulsion between the headgroups, so the charge density on the surface is reduced. As a result of this, the micelle spontaneously changes its morphology due to a new packing for the head groups. The adsorption of 2-hydroxy-1-naphthoic acid 2,1 HNC and 6-hydroxy-2-naphthoic acid 6,2 HNC onto the surface of the cationic surfactant cetyltrimethylammonium hydroxide was studied. The results were compared to the published system 3-hydroxy-2-naphthoic acid 3,2 HNC/CTAOH. When an increasing amount of 2,1 HNC is introduced into a micellar solution of 100 mM CTAOH, one finds low viscous micellar solution, viscoelastic gel (consisting of rod like micelles), turbid region (two phase region), and viscoelastic liquid crystalline gel (consisting of multilamellar vesicles MLV with yield value). The complex viscosity (0.01 Hz) of 100 mM CTAOH rises by six orders of magnitude as the rodlike micelles form.It decreases then to the turbid region, and then rises again approximately six orders of magnitude. The second rising of the complex viscosity is accompained by the formation of a liquid crystalline phase which consists of multilamellar vesicles. This has been proven by DICM, FF-TEM and Cryo-TEM. The vesicles were polydisperse and ranged from 100 to 1000 nm in diameter. SANS detected the transition in the microstructure which was caused by changing the concentration of 2,1 HNC in the system. SANS calculations show results similar to that obtained by microscopic methods. Surprising rheological behavior was measured in the rodlike micelle region, at which storage modulus was about one order of magnitude higher than loss modulus and both were parallel in the frequency range 0.001-10 Hz. Such behavior usually indicates the presence of vesicles in the liquid crystal phases. It was proved that other rheological measurements can be used to distinguish the tow types, namely, amplitude sweep measurements, first normal stress difference N1 (Weissenbeg effect), the effect of adding electrolyte, and stress relaxation curves. When 6,2 HNC (new substitution of HNC) is added with an increasing amount to 100 mM CTAOH, a new phase behavior is observed. Here the structure changes from small micelle aggregates into rodlike micelles, and then a two phase region consisting of L1-phase and un-reacted 6,2 HNC is formed. No transition into MLV has been detected. In the case of 3,2 HNC and 2,1 HNC, the hydroxyl and the carboxyl group are neighboring, so they can effectively share in reducing the repulsion between the headgroups while the rings are in interaction with hydrocarbon tails. For 6,2 HNC the hydroxyl group is in position number 6 on the aromatic rings, which means that hydroxyl group is distant from the carboxyl group, thereby, less screening for the cationic charge in the micelle surface is obtained. Substitution of HNC plays a main role in controlling the microstructure and other physical properties such viscosity, Krafft point, ..etc. In the second part of this work, the hydrophobic counterion is fixed (2,1 HNC), and the length of the cationic surfactant‘s chain is changed from C16 into C14, C12, C10 and C8. For the system 2,1 HNC/ tetradecyltrimethylammonium hydroxide TTAOH similar phase behavior as 2,1 HNC/CTAOH is observed. At 2,1 HNC/TTAOH ratio r aproximately 1, formation of MLV is observed. After the neutralization addition of excess amount of 2,1 HNC is possible since the insoluble molecular form of 2,1 HNC becomes solublized in the formed MLV. Conductivity measurements prove that 2,1 HNC stays in the molecular form after the neutralization. A difference in the rheological behavior of the system 2,1 HNC/TTAOH compared to 2,1 HNC/CTAOH is seen. In the rodlike micelles region of 2,1 HNC/TTAOH, the solutions exhibit a short relaxation time compared to 2,1 HNC/CTAOH system. FF-TEM and SANS proved the formation of polydisperse MLV in this system with a maximum diameter of about 2000 nm and wall thickens of about 28 nm. As a result of this work, it is concluded that the role of the hydrophobic counterions with certain geometry could be looked upon as a co-surfactant with a shorter chain length which changes the bending rigidity, of the bilayer. They are surface active species that bind strongly on the micelle surface and change the packing parameter of the headgroups. It is suggested that the hydrophobicity of the counterion plays an important role in deciding the structure of the supramolecular assemblies such as vesicles, or micelles. As a consequence one can change the morphology of micelle species by changing the ratio of counterion /surfactant ion. These studies also suggest that by mixing cationic surfactant and hydrophobic counterion with varying cationic surfactants chain lengths, one can have a control over the supramolecular structures formed.

Novel Precursors for Polymer-Protein-Conjugate Synthesis via Reversible Addition-Fragmentation Chain Transfer Polymerization (2003)

Christine Maria Schilli

The RAFT polymerization of N-isopropylacrylamide with two different chain transfer agents, namely benzyl 1-pyrrolecarbodithioate and cumyl 1-pyrrolecarbodithioate, yielded polymers with narrow molecular weight distributions as well as Mn values that were in good agreement with the calculated ones. A comparison between the Mn values determined from gel permeation chromatography, GPC, and the values from MALDI-TOF mass spectrometry showed that the molecular weights obtained from GPC using polystyrene standards were considerably higher. A relation between log Mn,MALDI and log Mn,GPC was established, which permitted construction of a calibration curve for PNIPAAm polymers. In-situ Fourier-transform near-infrared spectroscopy was applied for the reliable determination of monomer conversions and it indicated living characteristics. Both polymerization processes showed an induction period that seems to be correlated with a retardation in rate, where the induction time is higher for the cumyl chain transfer agent as compared to the benzyl chain transfer agent of the same concentration. The induction periods decrease with decreasing transfer agent concentration and were explained in terms of the different stabilities of the respective radicals that add to monomer in the reinitiation step. The more stable cumyl radical adds slower than the benzyl radical. Both UV spectroscopy and MALDI-TOF mass spectrometry confirm the presence of the expected dithiocarbamate endgroups. MALDI-TOF characterization of the polymer samples showed the transfer agent endgroups together with some initiator-derived polymers. Endgroups that seemed to originate from disproportionation or transfer were the result of fragmentation under MALDI conditions as was shown by a post source decay analysis and MALDI-TOF characterization of the hydrolyzed polymer. With amine-reactive diacetone acrylamide, 2-vinyl-4,4-dimethyl-5-oxazolone and N-hydroxysuccinimide methacrylate, new monomers were polymerized via RAFT in a controlled manner. Poly(diacetone acrylamide) and poly(2-vinyl-4,4-dimethyl-5-oxazolone) showed low polydispersities and good control over molecular weight, where poly(N-hydroxysuccinimide methacrylate) displayed relatively high polydispersities despite the controlled polymerization evident from the monomodal GPC traces. These amine-reactive polymers were subsequently used for successful conjugation to the primary amino group of the model peptide glycine-leucine. For poly(N-isopropylacrylamide)-block-poly(acrylic acid), PNIPAAm-b-PAA, it was demonstrated that hydrogen bonding between N-isopropylacrylamide and acrylic acid units influences strongly its behavior in both the solid state and in solution. The block copolymers form micelles in aqueous solutions in dependence of pH and temperature. Cloud point measurements indicated the formation of larger aggregates at pH 4.5 and temperatures above LCST, whereas micelles formed at pH 5-7 and temperatures above LCST. At pH 5.6 and 50 °C, only micelles were found, whereas, at lower temperatures, larger aggregates and micelles coexist. Formation of larger aggregates by hydrogen bonding interactions was revealed by IR and Raman spectroscopy as well as by cryogenic transmission electron microscopy and dynamic light scattering. Differential scanning calorimetry yielded glass transition temperatures of PNIPAAm-b-PAA that were well above the transition temperatures of the homopolymers, demonstrating molecular interactions between the acrylic acid and the N-isopropylacrylamide blocks. Conjugation of sulfhydryl-terminated PNIPAAm to thiol disulfide exchange reagents and maleimides was probed for later conjugation to proteins. Evaluation of the different cross-linking systems resulted in the choice of maleimides as cross-linkers for subsequent conjugation to the protein streptavidin. Sulfhydryl-terminated PNIPAAm-b-PAA was conjugated to the streptavidin mutant S139C using a bismaleimide cross-linker and also direct conjugation via disulfide linkage. Both conjugations were successful and proceeded with more than 50 % conversion. Conjugation of PNIPAAm and PNIPAAm-b-PAA was also achieved by non-covalent attachment of the biotinylated polymers to wild-type streptavidin. Conjugates of wild-type streptavidin with biotinylated PNIPAAm-b-PAA were found to remain dissolved at temperatures above LCST even at very low pH values, which was in contrast to the observed precipitation of the unconjugated block copolymer at pH <= 4.5. Conjugates of wild-type streptavidin with biotinylated PNIPAAm of different molecular weights formed aggregates in aqueous solutions above LCST and a dependence of aggregate size on the size of the polymer was found

Analysis of alkali-inducible genes of Bacillus subtilis (2003)

Akram Atalla

Using the DNA macroarray technique, it could be shown that more than 80 genes induced after alkali shock (Wiegert et al., 2001). While most of them are under the control of the alternative sigma factor (sigmaW), the remaining genes are under the control of one or more unknown regulator(s). By their signature, two of them kipR and yvdT code for regulatory proteins, while pspA, member of the sigmaW regulon, encodes another potential regulator. In this doctoral work, the genes kipR, yvd and pspA were analyzed. The kipR and yvdT genes code for a transcriptional regulator of the IcIR and TetR/AcrR family while the pspA encode a transcriptional anti-activator in E. coli . In Northern blot analyses, it could be shown that all three genes are induced after alkali shock. The transcription start points of the kipR and yvdT genes were identified by primer extension experiments, and it appeared that the transcription is dependent on a vegetative sigma A-like promoter. To identify genes which are under the negative control of the transcriptional anti-activator PspA, a DNA macroarray experiment was carried out. It turned out that several genes are repressed by a factor of at least three under conditions of PspA overproduction. By using the Far-western blot technique, a protein which might interact with the PspA protein was identified. This protein has a molecular weight approximately 50 kDa. In addition, expression of the pst operon ( pst stay for phosphate-specific transport) was analyzed which is induced after phosphate starvation and after alkaline shock. The genes of this operon are involved in the phosphate transport into the cytoplasma. By Northern-blot experiments, it could be shown that all genes of this operon are alkali-inducible. When the transcriptional start point was determined by primer extension, it turned out to be identical to the one determined under phosphate limitation. This transcription start point is preceded by a typical sigmaA-type promoter. Furthermore, alkali-induction is dependent on the PhoP-PhoR two-component signal transduction system. Phosphate-uptake experiments revealed that the uptake of inorganic phosphate was completely abolished after increasing the external pH value.

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