@phdthesis{Moigno2001, author = {Moigno, Damien}, title = {Study of the ligand effects on the metal-ligand bond in some new organometallic complexes using FT-Raman and -IR spectroscopy, isotopic substitution and density functional theory techniques}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-3101}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {The present studies which have been performed in the work-group C-2 (Prof. W. Kiefer) within the program of the Sonderforschungsbereichs 347, deal with the FT-Raman and -IR spectroscopy on new organometallic complexes, synthesized in the work-groups B-2 (Prof. W. Malisch), B-3 (Prof. W. A. Schenk), D-1 (Prof. H. Werner) and D-4 (Prof. D. Stalke). The FT-Raman spectra recorded at 1064 nm led to very useful and interesting information. Furthermore, the DFT calculations which are known to offer promise of obtaining accurate vibrational wavenumbers, were successfully used for the assignment of the vibrational spectra. For the first time it has been possible to ascribe exactly the n(RhC) stretching mode in the vinylidene rhodium(I) complex trans-[RhF(=C=CH2)(PiPr3)2] by using isotopic substitution, in conjunction with theoretical calculations. This is also true for the complexes trans-[RhF(CO)(PiPr3)2], trans-[RhF(C2H4)(PiPr3)2], trans-[RhX(=C=CHPh)(PiPr3)2] (X = F, Cl, Br, I, Me, PhCºC) and trans-[RhX(CN-2,6-xylyl)(PiPr3)2] (X = F, Cl, Br, I, CºCPh). In addition, the comparison between the n(RhC) wavenumbers of the complexes trans-[RhF(=13C=13CH2)(PiPr3)2] and trans-[RhF(CO)(PiPr3)2], containing the isoelectronic ligands 13C=13CH2 and CO, which have the same reduced mass, indicated that the Rh-C bond is stronger in the carbonyl than in the vinylidene complex. Besides, the n(RhF) stretching mode, which has been observed at higher wavenumbers in the FT-Raman and -IR spectra of trans-[RhF(CO)(PiPr3)2], showed that the carbonyl ligand is a better p-acceptor and a less effective s-donor than the vinylidene one. Moreover, the comparison of the n(CºC) and n(Rh-C) modes from the FT-Raman spectrum of the complexes trans-[Rh(CºCPh)(L)(PiPr3)2] (L = C=CHPh, CO, CN-2,6-xylyl) point out that the p-acceptor ability of the ligand trans to CºCPh should rise in the order C=CH2 < CO < CN-2,6-xylyl \pounds C=CHPh. The investigated sensitivity of the n(RhC), n(CC), n(CO) and n(CN) vibrational modes to the electronic modifications occuring in the vinylidene, carbonyl, ethylene and isonitrile complexes, should allow in the future the examination of the p-acceptor or p-donor properties of further ligands. Likewise, we were able to characterize the influence of various X ligands on the RhC bond by using the n(RhC) stretching mode as a probe for the weakening of this. The calculated wavenumbers of the n(RhC) for the vinylidene complexes trans-[RhX(=C=CHR)(PiPr3)2], where R = H or Ph, suggested that the strength of the Rh=C bond increases along the sequence X = CºCPh < CH3 < I < Br < Cl < F. For the series of carbonyl compounds trans-[RhX(CO)(PiPr3)2], where X = F, Cl, Br and I, analogous results have been obtained and confirmed from the model compounds trans-[RhX(CO)(PMe3)2]. Since, the calculated vibrational modes for the ethylene complex trans-[RhF(C2H4)(PiPr3)2] were in good agreement with the experimental results and supported the description of this complex as a metallacyclopropane, we were interested in getting more information upon this class of compounds. In this context, we have recorded the FT-Raman and -IR spectra of the thioaldehyde complexes mer-[W(CO)3(dmpe)(h2-S=CH2)] and mer-[W(CO)3(dmpe)(h2-S=CD2)] which have been synthezised by B-3. The positions of the different WL vibrational modes anticipated by the DFT calculations, were consistent with the experimental results. Indeed, the analysis of the band shifts in the FT-Raman and -IR spectra of the isotopomer mer-[W(CO)3(dmpe)(h2-S=CD2)] confirmed our assignment. The different stereoisomers of complex mer-[W(CO)3(dmpe)(h2-S=CH2)] were investigated too, since RMN and IR-data have shown that complex mer-[W(CO)3(dmpe)(h2-S=CH2)] lead in solution to an equilibrium. Since the information on the vibrational spectra of the molybdenum and tungsten complexes Cp(CO)2M-PR2-X (M = Mo, W; R = Me, tBu, Ph; X = S, Se) is very scarce, we extended our research work to this class of compounds. We have tried to elucidate the bonding properties in these chalcogenoheterocycle complexes by taking advantage of the mass effect on the different metal atoms (W vs. Mo). Thus, the observed band shifts allowed to assign most of the ML fundamental modes of these complexes. This project and the following one were a cooperation within the work-group B-2. The Raman and IR spectra of the matrix isolated photoproducts expected by the UV irradiation of the iron silyl complex Cp(CO)2FeSiH2CH3 have been already reported by Claudia Fickert and Volker Nagel in their PhD-thesis. Since no exact assignment was feasible for these spectra, we were interested in the study of the reaction products created by irradiation of the carbonyl iron silyl complex Cp(CO)2FeCH2SiH3. Although the calculated characteristic vibrational modes of the metal ligand unit for the various photoproducts are significantly different in constitution, they are very similar in wavenumbers, which did not simplify their identification. However, the theoretical results have been found to be consistent with the earlier experimental results. Finally, the last part of this thesis has been devoted to the (2-Py)2E- anions which exhibit a high selectivity toward metal-coordination. All di(2-pyridyl) amides and -phosphides which were synthesized by D-4, coordinate the R2Al+ fragment via both ring nitrogen atoms. This already suggests that the charge density in the anions is coupled into the rings and accumulated at the ring nitrogen atoms, but the Lewis basicity of the central nitrogen atom in Et2Al(2-Py)2N is still high enough to coordinate a second equivalent AlEt3 to form the Lewis acid base adduct Et2Al(2-Py)2NAlEt3. Due to the higher electronegativity of the central nitrogen atom in Me2Al(2-Py)2N, Et2Al(2-Py)2N and Et2Al(2-Py)2NAlEt3, compared to the bridging two coordinated phosphorus atom in Me2Al(2-Py)2P and Et2Al(2-Py)2P, the di(2-pyridyl)amide is the hardest Lewis base. In the phosphides merely all charge density couples into the rings leaving the central phosphorus atom only attractive for soft metals. These results were confirmed by using DFT and MP2 calculations. Moreover, a similar behaviour has been observed and described for the benzothiazolyl complex [Me2Al{Py(Bth)P}], where complementary investigations are to be continued. The DFT calculations carried out on the model compounds analysed in these studies supply very accurate wavenumbers and molecular geometries, these being in excellent agreement with the experimental results obtained from the corresponding isolated complexes.}, subject = {{\"U}bergangsmetallkomplexe}, language = {en} } @phdthesis{Siefritz2002, author = {Siefritz, Franka}, title = {Expression and Function of the Nicotiana tabacum Aquaporin NtAQP1}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-3053}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2002}, abstract = {Die vorliegende Arbeit zeigt die Korrelation zwischen r{\"a}umlichem und zeitlichem Expressionsmuster von dem Aquaporin NtAQP1 und seiner Funktion im Wasserhaushalt in planta. Immunologische in situ-Studien deuteten auf eine NtAQP1-Protein-Akkumulation in der Wurzelexodermis und -endodermis, im Cortex, in der N{\"a}he der Leitb{\"u}ndel, im Xylemparenchym und in Zellen der Atemh{\"o}hle hin. Das Aquaporin wurde auch in longitudinalen Zellreihen der Petiolen in erh{\"o}hten Mengen gefunden. Expressionsstudien mit transgenen Pflanzen (Ntaqp1-Promotor::gus oder ::luc) best{\"a}tigten die NtAQP1-Akkumulation in der Wurzel, dem Spross und den Petiolen, lokalisierten dessen Expression aber auch in Pollen, Adventivwurzel und Blatthaaren. Die Ntaqp1-Expression wurde w{\"a}hrend Wachstumsprozessen wie Sprossorientierung nach Gravistimulation oder Photostimulation, Samenkeimung, aber auch w{\"a}hrend der vergleichsweise schnellen circadianen Blattbewegung induziert. Die Expression wurde weiterhin durch Phytohormone, im Speziellen durch Gibberellins{\"a}ure (GA) und osmotischen Stress stimuliert. Weitere Analysen hoben eine diurnale und sogar circadiane Expression von Ntaqp1 in Wurzeln und Petiolen hervor. Die funktionelle Analyse des Aquaporins wurde mittels reverser Genetik und biophysikalischen Studien durchgef{\"u}hrt. Die Antisense-Technik wurde benutzt, um die NtAQP1-Expression in Tabakpflanzen zu reduzieren. Die Antisense (AS)-Pflanzen zeigten eine starke Verringerung der Ntaqp1-mRNA, eine weniger ausgepr{\"a}gte Verminderung der hoch homologen NtPIP1a-mRNA und keinen Effekt auf die Expression anderer Aquaporin-Genfamilien (PIP2, TIP). Die Funktion von NtAQP1 auf zellul{\"a}rer Ebene wurde mit einer hierf{\"u}r neuentwickelten Apparatur untersucht. Der experimentelle Aufbau erm{\"o}glichte die Aufzeichnung der osmotisch induzierten Protoplasten-Volumenzunahme. Die Reduktion von NtAQP1 durch die Antisense-Expression verminderte die zellul{\"a}re Wasserpermeabilit{\"a}t um mehr als 50 \%. Die Funktion von NtAQP1 in der Gesamtpflanze wurde z.B. durch die "High-pressure flow meter" Methode bestimmt. Diese Messungen ergaben eine Reduktion der hydraulischen Wurzelleitf{\"a}higkeit pro Wurzeloberfl{\"a}cheneinheit (KRA) der Wurzeln der AS-Linien um mehr als 50 \%. Die KRA wies eine starke diurnale und circadiane Schwankung auf, mit einem Maximum in der Mitte der Lichtperiode, {\"a}hnlich dem Verlauf des Expressionsmusters von Ntaqp1 in Wurzeln. Unter gut gew{\"a}sserten Bedingungen ergaben Gaswechsel-, Spross- (Ystem) und Blatt- Wasserpotenial (Yleaf)-Messungen unterschiedliche Werte in AS- und Kontrollpflanzen. In wasserlimitierender Umgebung zeigten AS-Pflanzen jedoch ein st{\"a}rker negativeres Y als Kontrollpflanzen, obwohl eine weitere Abnahme der Transpiration in AS-Pflanzen beobachtet werden konnte. Quantitative Analysen belegten eine st{\"a}rker ausgepr{\"a}gte Welkreaktion in den AS- als in den Kontrollpflanzen. Quantitative Studien der Blattbewegung von AS- verglichen mit Kontrollpflanzen hoben eine drastische Reduktion in Geschwindigkeit und Ausmaß der Reaktion hervor. Folgende Schlussfolgerungen konnten gezogen werden. NtAQP1 wurde an Orten mit erwartet hohem Wasserfluss von und zum Apoplasten oder Symplasten exprimiert. Außerdem deuteten das spezifische Verteilungsmuster und die zeitliche Expression von NtAQP1 in Petiolen und dem sich biegenden Spross auf eine Beteiligung in der transzellul{\"a}ren Wasserbewegung hin. Die Reduktion von NtAQP1 durch die Antisense-Expression verringerte die zellul{\"a}re Pos. Die NtAQP1-Funktion erh{\"o}ht also eindeutig die Membranwasserpermeabilit{\"a}t von Tabak-Wurzelprotoplasten. Die Abnahme der spezifischen hydraulischen Wurzelleitf{\"a}higkeit (KRA) befand sich in der gleichen Gr{\"o}ßenordnung wie die Verringerung der mittleren zellul{\"a}ren Wasserpermeabilit{\"a}t. Dies weist darauf hin, dass die Aquaporin-Expression essentiell f{\"u}r die Aufrechterhaltung der nat{\"u}rlichen Wurzelleitf{\"a}higkeit ist. Die Verringerung von KRA in AS -Pflanzen k{\"o}nnte der erste sichere Beweis daf{\"u}r sein, dass der Weg der Wasseraufnahme von der Wurzeloberfl{\"a}che in das Xylem den {\"U}bergang {\"u}ber Membranen einschließt. Die Reduktion von NtAQP1 resultierte in einem Wasserstresssignal, das ein Schließen der Stomata zur Folge hatte. NtAQP1 scheint an der Vermeidung von Wasserstress in Tabak beteiligt zu sein. NtAQP1 spielt eine essentielle Rolle bei schnellen Pflanzenbewegungen und der transzellul{\"a}ren Wasserverschiebung.}, subject = {Tabak}, language = {en} } @phdthesis{Wirth2001, author = {Wirth, Hans-Christoph}, title = {Multicriteria Approximation of Network Design and Network Upgrade Problems}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2845}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {Network planning has come to great importance during the past decades. Today's telecommunication, traffic systems, and logistics would not have been evolved to the current state without careful analysis of the underlying network problems and precise implementation of the results obtained from those examinations. Graphs with node and arc attributes are a very useful tool to model realistic applications, while on the other hand they are well understood in theory. We investigate network design problems which are motivated particularly from applications in communication networks and logistics. Those problems include the search for homogeneous subgraphs in edge labeled graphs where either the total number of labels or the reload cost are subject to optimize. Further, we investigate some variants of the dial a ride problem. On the other hand, we use node and edge upgrade models to deal with the fact that in many cases one prefers to change existing networks rather than implementing a newly computed solution from scratch. We investigate the construction of bottleneck constrained forests under a node upgrade model, as well as several flow cost problems under a edge based upgrade model. All problems are examined within a framework of multi-criteria optimization. Many of the problems can be shown to be NP-hard, with the consequence that, under the widely accepted assumption that P is not equal to NP, there cannot exist efficient algorithms for solving the problems. This motivates the development of approximation algorithms which compute near-optimal solutions with provable performance guarantee in polynomial time.}, subject = {Netzplantechnik}, language = {en} } @phdthesis{Schmitz2000, author = {Schmitz, Heinz}, title = {The Forbidden Pattern Approach to Concatenation Hierarchies}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2832}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2000}, abstract = {The thesis looks at the question asking for the computability of the dot-depth of star-free regular languages. Here one has to determine for a given star-free regular language the minimal number of alternations between concatenation on one hand, and intersection, union, complement on the other hand. This question was first raised in 1971 (Brzozowski/Cohen) and besides the extended star-heights problem usually refered to as one of the most difficult open questions on regular languages. The dot-depth problem can be captured formally by hierarchies of classes of star-free regular languages B(0), B(1/2), B(1), B(3/2),... and L(0), L(1/2), L(1), L(3/2),.... which are defined via alternating the closure under concatenation and Boolean operations, beginning with single alphabet letters. Now the question of dot-depth is the question whether these hierarchy classes have decidable membership problems. The thesis makes progress on this question using the so-called forbidden pattern approach: Classes of regular languages are characterized in terms of patterns in finite automata (subgraphs in the transition graph) that are not allowed. Such a characterization immediately implies the decidability of the respective class, since the absence of a certain pattern in a given automaton can be effectively verified. Before this work, the decidability of B(0), B(1/2), B(1) and L(0), L(1/2), L(1), L(3/2) were known. Here a detailed study of these classes with help of forbidden patterns is given which leads to new insights into their inner structure. Furthermore, the decidability of B(3/2) is proven. Based on these results a theory of pattern iteration is developed which leads to the introduction of two new hierarchies of star-free regular languages. These hierarchies are decidable on one hand, on the other hand they are in close connection to the classes B(n) and L(n). It remains an open question here whether they may in fact coincide. Some evidence is given in favour of this conjecture which opens a new way to attack the dot-depth problem. Moreover, it is shown that the class L(5/2) is decidable in the restricted case of a two-letter alphabet.}, subject = {Sternfreie Sprache}, language = {en} } @phdthesis{Nahler2001, author = {Nahler, Michael}, title = {Isomorphism classes of almost completely decomposable groups}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2817}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {In this thesis we investigate near-isomorphism classes and isomorphism classes of almost completely decomposable groups. In Chapter 2 we introduce the concept of almost completely decomposable groups and sum up their most important facts. A local group is an almost completely decomposable group with a primary regulator quotient. A uniform group is a rigid local group with a homocyclic regulator quotient. In Chapter 3 a weakening of isomorphism, called type-isomorphism, appears. It is shown that type-isomorphism agrees with Lady's near-isomorphism. By the Main Decomposition Theorem and the Primary Reduction Theorem we are allowed to restrict ourselves on clipped local groups, namely groups without a direct rank-one summand. In Chapter 4 we collect facts of matrices over commutative rings with an identity element. Matrices over the local ring (Z / p^e Z) of residue classes of the rational integers modulo a prime power play an important role. In Chapter 5 we introduce representing matrices of finite essential extensions. Here a normal form for local groups is found by the Gauß algorithm. Uniform groups have representing matrices in Hermite normal form. The classification problems for almost completely decomposable groups up to isomorphism and up to near-isomorphism can be rephrased as equivalence problems for the representing matrices. In Chapter 6 we derive a criterion for the representing matrices of local groups in Gauß normal form. In Chapter 7 we formulate the matrix criterion for uniform groups. Two representing matrices in Hermite normal form describe isomorphic groups if and only if the rest blocks of the representing matrices are T-diagonally equivalent. Starting from a fixed near-isomorphism class in Chapter 8 we investigate isomorphism classes of uniform groups. We count groups and isomorphism classes. In Chapter 9 we specialize on uniform groups of rank 2r with a regulator quotient of rank r such that the rest block of the representing matrix is invertible and normed.}, subject = {Fast vollst{\"a}ndig zerlegbare Gruppe}, language = {en} } @phdthesis{Kosub2001, author = {Kosub, Sven}, title = {Complexity and Partitions}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2808}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {Computational complexity theory usually investigates the complexity of sets, i.e., the complexity of partitions into two parts. But often it is more appropriate to represent natural problems by partitions into more than two parts. A particularly interesting class of such problems consists of classification problems for relations. For instance, a binary relation R typically defines a partitioning of the set of all pairs (x,y) into four parts, classifiable according to the cases where R(x,y) and R(y,x) hold, only R(x,y) or only R(y,x) holds or even neither R(x,y) nor R(y,x) is true. By means of concrete classification problems such as Graph Embedding or Entailment (for propositional logic), this thesis systematically develops tools, in shape of the boolean hierarchy of NP-partitions and its refinements, for the qualitative analysis of the complexity of partitions generated by NP-relations. The Boolean hierarchy of NP-partitions is introduced as a generalization of the well-known and well-studied Boolean hierarchy (of sets) over NP. Whereas the latter hierarchy has a very simple structure, the situation is much more complicated for the case of partitions into at least three parts. To get an idea of this hierarchy, alternative descriptions of the partition classes are given in terms of finite, labeled lattices. Based on these characterizations the Embedding Conjecture is established providing the complete information on the structure of the hierarchy. This conjecture is supported by several results. A natural extension of the Boolean hierarchy of NP-partitions emerges from the lattice-characterization of its classes by considering partition classes generated by finite, labeled posets. It turns out that all significant ideas translate from the case of lattices. The induced refined Boolean hierarchy of NP-partitions enables us more accuratly capturing the complexity of certain relations (such as Graph Embedding) and a description of projectively closed partition classes.}, subject = {Partition }, language = {en} } @phdthesis{Glasser2001, author = {Glaßer, Christian}, title = {Forbidden-Patterns and Word Extensions for Concatenation Hierarchies}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-1179153}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {Starfree regular languages can be build up from alphabet letters by using only Boolean operations and concatenation. The complexity of these languages can be measured with the so-called dot-depth. This measure leads to concatenation hierarchies like the dot-depth hierarchy (DDH) and the closely related Straubing-Th{\´e}rien hierarchy (STH). The question whether the single levels of these hierarchies are decidable is still open and is known as the dot-depth problem. In this thesis we prove/reprove the decidability of some lower levels of both hierarchies. More precisely, we characterize these levels in terms of patterns in finite automata (subgraphs in the transition graph) that are not allowed. Therefore, such characterizations are called forbidden-pattern characterizations. The main results of the thesis are as follows: forbidden-pattern characterization for level 3/2 of the DDH (this implies the decidability of this level) decidability of the Boolean hierarchy over level 1/2 of the DDH definition of decidable hierarchies having close relations to the DDH and STH Moreover, we prove/reprove the decidability of the levels 1/2 and 3/2 of both hierarchies in terms of forbidden-pattern characterizations. We show the decidability of the Boolean hierarchies over level 1/2 of the DDH and over level 1/2 of the STH. A technique which uses word extensions plays the central role in the proofs of these results. With this technique it is possible to treat the levels 1/2 and 3/2 of both hierarchies in a uniform way. Furthermore, it can be used to prove the decidability of the mentioned Boolean hierarchies. Among other things we provide a combinatorial tool that allows to partition words of arbitrary length into factors of bounded length such that every second factor u leads to a loop with label u in a given finite automaton.}, subject = {Automatentheorie}, language = {en} } @phdthesis{Dittmann2001, author = {Dittmann, Ulrich}, title = {Coset Types and Tight Subgroups of Almost Completely Decomposable Groups}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2762}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {A completely decomposable group is a direct sum of subgroups of the rationals. An almost completely decomposable group is a torsion free abelian group that contains a completely decomposable group as subgroup of finite index. Tight subgroups are maximal subgroups (with respect to set inclusion) among the completely decomposable subgroups of an almost completely decomposable group. In this dissertation we show an extended version of the theorem of Bezout, give a new criterion for the tightness of a completely decomposable subgroup, derive some conditions under which a tight subgroup is regulating and generalize a theorem of Campagna. We give an example of an almost completely decomposable group, all of whose regulating subgroups do not have a quotient with minimal exponent. We show that among the types of elements of a coset modulo a completely decomposable group there exists a unique maximal type and define this type to be -the- coset type. We give criteria for tightness and regulating in term of coset types as well as a representation of the type subgroups using coset types. We introduce the notion of reducible cosets and show their key role for transitions from one completely decomposable subgroup up to another one containing the first one as a proper subgroup. We give an example of a tight, but not regulating subgroup which contains the regulator. We develop the notion of a fully single covered subset of a lattice, show that V-free implies fully single covered, but not necessarily vice versa, and we define an equivalence relation on the set of all finite subsets of a given lattice. We develop some extension of ordinary Hasse diagrams, and apply the lattice theoretic results on the lattice of types and almost completely decomposable groups.}, subject = {Torsionsfreie Abelsche Gruppe}, language = {en} } @phdthesis{Walfort2001, author = {Walfort, Bernhard}, title = {Novel dianionic sulfur ylides and related compounds}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-1181274}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {Priority task of the thesis was to replace oxygen atoms in sulfur oxoanions SOnm- or imido groups in sulfur polyimido anions S(NR)nm- isoelectronically by R2C-methylene groups. This would open a wide avenue to new target molecules containing a formally double bonded carbon next to formally double bonded nitrogen atoms in highly charged sulfur-centred anions like S(CR2)x(NR)ym-. They clearly are reminiscent to sulfur ylides. Both, alkylendiimidosulfites and alkylentriimidosulfates are accessible via deprotonaton of the corresponding alkyldiimidosulfinates and alkyltriimidosulfonates with methyllithium. The reactivity of the novel compounds is dominated by the carbanionic centre. Addition reactions to another SN formal doubble bond are feasible and are leading to the yet unknown imidoanalogues compounds alkyl-bis-(diimidosulfinates) and alkyl-bis-(triimidosulfonates).}, subject = {Schwefelylide}, language = {en} } @phdthesis{Wong2001, author = {Wong, Amanda}, title = {Implications of Advanced Glycation Endproducts in Oxidative Stress and Neurodegenerative Disorders}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2537}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {The reactions of reducing sugars with primary amino groups are the most common nonenzymatic modifications of proteins. Subsequent rearrangements, oxidations, and dehydrations yield a heterogeneous group of mostly colored and fluorescent compounds, termed "Maillard products" or advanced glycation end products (AGEs). AGE formation has been observed on long-lived proteins such as collagen, eye lens crystalline, and in pathological protein deposits in Alzheimer's (AD) and Parkinson's disease (PD) and dialysis-related amyloidosis. AGE-modified proteins are also involved in the complications of diabetes. AGEs accumulate in the the ß-amyloid plaques and neurofibrillary tangles (NFT) associated with AD and in the Lewy bodies characteristic of PD. Increasing evidence supports a role for oxidative stress in neurodegenerative disorders such as AD and PD. AGEs have been shown to contribute towards oxidative damage and chronic inflammation, whereby activated microglia secrete cytokines and free radicals, including nitric oxide (NO). Roles proposed for NO in the pathophysiology of the central nervous system are increasingly diverse and range from intercellular signaling, through necrosis of cells and invading pathogens, to the involvement of NO in apoptosis. Using in vitro experiments, it was shown that AGE-modified bovine serum albumin (BSA-AGE) and AGE-modified ß-amyloid, but not their unmodified proteins, induce NO production in N-11 murine microglia cells. This was mediated by the receptor for AGEs (RAGE) and upregulation of the inducible nitric oxide synthase (iNOS). AGE-induced enzyme activation and NO production could be blocked by intracellular-acting antioxidants: Ginkgo biloba special extract EGb 761, the estrogen derivative, 17ß-estradiol, R-(+)-thioctic acid, and a nitrone-based free radical trap, N-tert.-butyl-*-phenylnitrone (PBN). Methylglyoxal (MG) and 3-deoxyglucosone (3-DG), common precursors in the Maillard reaction, were also tested for their ability to induce the production of NO in N-11 microglia. However, no significant changes in nitrite levels were detected in the cell culture medium. The significance of these findings was supported by in vivo immunostaining of AD brains. Single and double immunostaining of cryostat sections of normal aged and AD brains was performed with polyclonal antibodies to AGEs and iNOS and monoclonal antibodies to Aß and PHF-1 (marker for NFT) and reactive microglia. In aged normal individuals as well as early stage AD brains (i.e. no pathological findings in isocortical areas), a few astrocytes showed co-localisation of AGE and iNOS in the upper neuronal layers of the temporal (Area 22) and entorhinal (Area 28, 34) cortices compared with no astrocytes detected in young controls. In late AD brains, there was a much denser accumulation of astrocytes co-localised with AGE and iNOS in the deeper and particularly upper neuronal layers. Also, numerous neurons with diffuse AGE but not iNOS reactivity and some AGE and iNOS-positive microglia were demonstrated, compared with only a few AGE-reactive neurons and no microglia in controls. Finally, astrocytes co-localised with AGE and iNOS as well as AGE and ß-amyloid were found surrounding mature but not diffuse ß-amyloid plaques in the AD brain. Parts of NFT were AGE-immunoreactive. Immunohistochemical staining of cryostat sections of normal aged and PD brains was performed with polyclonal antibodies to AGEs. The sections were counterstained with monoclonal antibodies to neurofilament components and a-synuclein. AGEs and a-synuclein were colocalized in very early Lewy bodies in the substantia nigra of cases with incidental Lewy body disease. These results support an AGE-induced oxidative damage due to the action of free radicals, such as NO, occurring in the AD and PD brains. Furthermore, the involvement of astrocytes and microglia in this pathological process was confirmed immunohistochemically in the AD brain. It is suggested that oxidative stress and AGEs participate in the very early steps of Lewy body formation and resulting cell death in PD. Since the iNOS gene can be regulated by redox-sensitive transcription factors, the use of membrane permeable antioxidants could be a promising strategy for the treatment and prevention of chronic inflammation in neurodegenerative disorders.}, subject = {Maillard-Reaktion}, language = {en} } @phdthesis{Klock2001, author = {Klock, Heike}, title = {Hydrogeology of the Kalahari in north-eastern Namibia}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-1181287}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {This study has focused on hydrogeological and hydrochemical settings of the Northern Namibian Kalahari Catchment which is the Namibian part of the Makgadikgadi-Kalahari-Catchment. Recharge has been the subject of process-understanding, quantification and regionalisation. Within the semiarid study area a bimodal surface constitution is prominent: hardrocks areas allow for fast infiltration along karsts and joints, whereas areas covered by unconsolidated sediments receive minor diffuse recharge and locally some preferred flow path recharge develops along shrinkage cracks and rootlets. Five substratum classes have been soil physically studied: Pans and vleis, brown to red soils, dune sand, soil with an aeolian influence, and calcrete. Aeolian sands are most promising for the development of direct diffuse recharge. Recharge by preferred flow might occur in all soil classes either due to joints in calcrete or structures and rootlets in soils. All soil classes contribute to indirect recharge because even the dune sand allows, albeit very locally, the generation of runoff. The occurrences of recharge through the unconsolidated soil and the hardrocks have been confirmed by hydrograph interpretation and by a study of hydrochemical data which identified groundwater of flood water and flood water after soil passage composition. Other prominent hydrochemical processes in the Kalahari are associated with the carbonate-equilibrium-system, mixing with highly mineralised water that is either sulphate (central area) or chloride dominated (fringe area) and development of sodium hydrogencarbonate water types. The latter is mostly generated by feldspar weathering. Variations of the hydrochemical compositions were observed for shallow groundwaters. They do not only reflect the recharge amount but also the recharge conditions, e.g. a wetter year is allowing more vegetation which increases the hydrogencarbonate content. Inverse determination of recharge by the chloride mass balance method gives recharge amounts between 0.2 and locally more than 100 mm/a. The least favoured recharge conditions are found for Kalahari covered areas, the largest amount occurs in the Otavi area. The distribution of recharge areas within the catchment is rather complex and regionalisation of recharge for the entire catchment was done by a forward approach using satellite images and by an inverse approach using hydrochemical data. From the inverse hydrochemical approach a basin-wide balanced recharge amount of 1.39 mm/a is achieved. The forward approach gave a basin-wide figure of 0.88 (minimum assumption) to 4.53 mm/a (maximum assumption). A simplistic groundwater flow model confirmed the results from the minimum recharge regionalisation by satellite images and the result from the hydrochemical approach. Altogether a mutually verified basin-wide recharge figure of ca. 1 mm/a turns out.}, subject = {Kalahari}, language = {en} } @phdthesis{Weidenmueller2001, author = {Weidenm{\"u}ller, Anja}, title = {From individual behavior to collective structure}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2448}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {The social organization of insect colonies has long fascinated naturalists. One of the main features of colony organization is division of labor, whereby each member of the colony specializes in a subset of all tasks required for successful group functioning. The most striking aspect of division of labor is its plasticity: workers switch between tasks in response to external challenges and internal perturbations. The mechanisms underlying flexible division of labor are far from being understood. In order to comprehend how the behavior of individuals gives rise to flexible collective behavior, several questions need to be addressed: We need to know how individuals acquire information about their colony's current demand situation; how they then adjust their behavior according; and which mechanisms integrate dozens or thousands of insect into a higher-order unit. With these questions in mind I have examined two examples of collective and flexible behavior in social bees. First, I addressed the question how a honey bee colony controls its pollen collection. Pollen foraging in honey bees is precisely organized and carefully regulated according to the colony's needs. How this is achieved is unclear. I investigated how foragers acquire information about their colony's pollen need and how they then adjust their behavior. A detailed documentation of pollen foragers in the hive under different pollen need conditions revealed that individual foragers modulate their in-hive working tempo according to the actual pollen need of the colony: Pollen foragers slowed down and stayed in the hive longer when pollen need was low and spent less time in the hive between foraging trips when pollen need of their colony was high. The number of cells inspected before foragers unloaded their pollen load did not change and thus presumably did not serve as cue to pollen need. In contrast, the trophallactic experience of pollen foragers changed with pollen need conditions: trophallactic contacts were shorter when pollen need was high and the number and probability of having short trophallactic contacts increased when pollen need increased. Thus, my results have provided support for the hypothesis that trophallactic experience is one of the various information pathways used by pollen foragers to assess their colony's pollen need. The second example of collective behavior I have examined in this thesis is the control of nest climate in bumble bee colonies, a system differing from pollen collection in honey bees in that information about task need (nest climate parameters) is directly available to all workers. I have shown that an increase in CO2 concentration and temperature level elicits a fanning response whereas an increase in relative humidity does not. The fanning response to temperature and CO2 was graded; the number of fanning bees increased with stimulus intensity. Thus, my study has evidenced flexible colony level control of temperature and CO2. Further, I have shown that the proportion of total work force a colony invests into nest ventilation does not change with colony size. However, the dynamic of the colony response changes: larger colonies show a faster response to perturbations of their colony environment than smaller colonies. Thus, my study has revealed a size-dependent change in the flexible colony behavior underlying homeostasis. I have shown that the colony response to perturbations in nest climate is constituted by workers who differ in responsiveness. Following a brief review of current ideas and models of self-organization and response thresholds in insect colonies, I have presented the first detailed investigation of interindividual variability in the responsiveness of all workers involved in a collective behavior. My study has revealed that bumble bee workers evidence consistent responses to certain stimulus levels and differ in their response thresholds. Some consistently respond to low stimulus intensities, others consistently respond to high stimulus intensities. Workers are stimulus specialists rather than task specialists. Further, I have demonstrated that workers of a colony differ in two other parameters of responsiveness: response probability and fanning activity. Response threshold, response probability and fanning activity are independent parameters of individual behavior. Besides demonstrating and quantifying interindividual variability, my study has provided empirical support for the idea of specialization through reinforcement. Response thresholds of fanning bees decreased over successive trials. I have discussed the importance of interindividual variability for specialization and the collective control of nest climate and present a general discussion of self-organization and selection. This study contributes to our understanding of individual behavior and collective structure in social insects. A fascinating picture of social organization is beginning to emerge. In place of centralized systems of communication and information transmission, insect societies frequently employ mechanisms based upon self-organization. Self-organization promises to be an important and unifying principle in physical, chemical and biological systems.}, subject = {Hummeln}, language = {en} } @phdthesis{Gehring2001, author = {Gehring, Iris}, title = {Volcanostratigraphy using geophysical methods on La Fossa di Vulcano (S-Italy)}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-1181941}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {For many active volcanoes all over the world a civil protection program, normally combined with hazard maps, exists. Optimising of hazard maps and the associated hazard assessment implies a detailed knowledge of the volcanostratigraphy, because the deposits provoke information on the potential behaviour during a new activity cycle. Pyroclastic deposits, however, may vary widely in thickness and distribution over very short lateral distances. High resolution characterisation of single strata often cannot be archived, if solely sedimentological and geochemical methods are used. Gamma-ray measurements taken in the field combined with grain-size depended magnetic susceptibility measurements made in the laboratory are used in this work to optimise the resolution of volcanostratigraphic investigations. The island of Vulcano is part of the Aeolian Archipelago sited of the northern coast of Sicily. La Fossa cone is the active centre of Vulcano, where fumarolic and seismic activity can be observed. The cone was built up during the last 6,000 years, whereby the last eruption period is dated to historic times (1888-1890). For the tuff cone La Fossa the most likely volcanic hazards are the emplacement of pyroclastic deposits as well as gas hazards (especially SOx and CO2), due to this the detailed knowledge of the stratigraphy is mandatory. Most of the population resides in Vulcano Porto and the nearby sited peninsula of Vulcanello, which are highly endangered locations for a future eruption scenario. Measurements, made in standard outcrops, allow a characterisation of the successions Punte Nere, Tufi Varicolori, Palizzi, Commenda, and Cratere Attuale. A discrimination of all successions by solely one of the methods is rarely possible. In some cases, however, the combination of the methods leads to clear results. It can also be noticed that the exposition as well as the sedimentation type (wet-surge or dry-surge deposits) affect the measurements. In general it can be assumed that the higher the magma is evolved the higher the g -ray values and the lower the susceptibility values. Measurements from the Wingertsberg (Laacher See deposits, Eifel, W-Germany) show clearly that a higher degree of magma evolution correlates with lower susceptibility and higher gamma-ray values. Variations of the values can be observed not only by the change of the degree of magmatic evolution but also by the inhomogeneous deposition conditions. Particularly the gamma-ray measurements show lower values for the wet-surge deposits than for the dry-surge deposits, even though the erupted material has the same geochemical composition. This can be explained especially by reactions inside of the moist eruption cloud and short-time after deposition, when easily soluble elements like K, U, and Th can be leached by these aggressive fluids. Even extended exposition and high water content can provoke depletion of various elements within the complete or parts of the outcrop, too. If the deposits are affected by a fumarolic activity especially the susceptibility values show significant variations, whereas in general extreme low values are observed. Contamination of deposits also can occur, if they are overlain by weathered deposits of higher concentration of K, U, and Th. Weathering and mobilisation within the upper deposits can generate an element enrichment within the lower deposits. In general the element ratios of the barried underlying deposits are less affected than the exposed ones. After gauging the values of the well defined succession for standard outcrops undefined outcrops were measured. These outcrops are not clearly classified by sedimentological and geochemical methods, thus a correlation with the combined geophysical methods is useful. In general the combination of the methods allows a correlation, although in some cases more than one interpretation is possible. But in connection with time marker horizons as well as sedimentological features an interpretation is feasible. These situations show that a classification solely based on geophysical methods is possible for many cases but, if the volcanic system is more complex, a combination with sedimentological and geochemical methods may be needed. The investigations on Vulcano, documented in this work, recommend a re-interpretation of the dispersial of some successions of La Fossa cone, especially the presumption that Tufi Varicolori only exist inside of the Caldera of La Fossa. As a consequence the eruption and energy model especially for Tufi Varicolori have to be reviewed.}, subject = {Vulcano}, language = {en} } @phdthesis{AlFarajat2001, author = {Al-Farajat, Mohammad}, title = {Hydrogeo-Eco-Systems in Aquaba/Jordan - Coasts and Region}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-1182066}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {The coast of Aqaba and the Aqaba region (Jordan) were investigated on their hydrogeo-ecosystem. The results of the research were translated into digits to build a geo-spatial data base. The fillings of the graben aquifer receive indirect type of recharge through the side wadis which drain the highlands. Surface water balance was modeled for a period of 20 years of daily climate records using MODBIL program which attributes direct recharge to wet years only. The hydrodynamic fresh water/seawater interface in the coastal zones was investigated by applying vertical geoelectric surveys and models of several methods to confirm its coincidence with the aquifer's flow amounts, where human impacts in terms of over-pumping allowed more encroachment of seawater into land, and unintended recharge which led to seaward interface migration. A groundwater balance and solute transport were approached by developing a flow model from the hydrogeological and hydrochemical data. The nature of soil cover and aquifer whose physical properties enhance human impacts indicated the vulnerability of groundwater to pollution. This certainly threatens the marine ecology which forms the sink where the in-excess flow ends. The constructed digital background was exported into GIS to sub-zone the study area in terms of the aquifer's vulnerability to pollution risks using DRASTIC index. However, it was unable to meet all geo-spatial factors that proved to have significant impacts on the vulnerability. Consequently, a comprehensive index -SALUFT- was developed. This suggests the suitable land use units for each zone in the light of vulnerability grades aiming at protecting the available groundwater resources.}, subject = {Golf von Akaba}, language = {en} } @phdthesis{Stuntz2001, author = {Stuntz, Sabine}, title = {The influence of epiphytes on arthropods in the tropical forest canopy}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-1179126}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {The understanding of the mechanisms underlying the establishment and maintenance of the extraordinary biodiversity in tropical forests is a major challenge for modern biology. In this context, epiphytes are presumed to play an important role. To investigate the biological reality of this persistent yet insufficiently investigated notion, I conducted the present study. The main questions I intended to clarify were: (1) do epiphytes affect arthropod abundance and diversity in tropical tree crowns? and (2) what might be the driving forces behind this potential influence? I studied the arthropod fauna of 25 tree crowns bearing different epiphyte assemblages, and the resident fauna of 90 individual epiphytes. I also quantified the mitigating influence of epiphytes on the microclimate in tree crowns. In total, more than 277,000 arthropods were collected and about 700 morphospecies determined. Epiphytes had a significant moderating influence on canopy microclimate (Chapter 3), both at various microsites within a tree crown and among tree crowns with different epiphyte growth. On hot dry season days, they provided microsites with lower temperatures and reduced evaporative water loss compared to epiphyte-free spaces within the same tree crown. Quantitative sampling of the arthropods inhabiting three different epiphyte species provided compelling evidence for the specificity of epiphyte-associated faunas (Chapter 4). Epiphytes proved to be microhabitats for a diverse and numerous arthropod fauna, and different epiphyte species fostered both taxonomically and ecologically very distinct arthropod assemblages: among epiphyte hosts, the inhabitant faunas showed remarkably little species overlap, and guild composition differed strongly. In the subsequent chapters I investigated if this pronounced effect scaled up to the level of entire tree crowns. Arthropods were captured with three different trap types to obtain an ample spectrum of the canopy fauna (Chapter 2). Four tree categories were classified, three of which were dominated by a different species of epiphyte, and an epiphyte-free control group. On a higher taxonomic level, there were no detectable effects of epiphytes on the fauna: the ordinal composition was similar among tree categories and indifferent of the amount of epiphytes in a tree crown (Chapter 5). I examined three focal groups (ants, beetles and spiders) on species level. The diversity and abundance of ants was not influenced by the epiphyte load of the study trees (Chapter 6). Although many species readily used the epiphytes as nesting site and shelter, they seemed to be highly opportunistic with respect to their host plants. Likewise, the species richness and abundance of beetles, as well as their guild composition were entirely unaffected by the presence of epiphytes in the study trees (Chapter 7). Focusing on herbivorous beetles did not alter these results. Spiders, however, were strongly influenced by the epiphyte assemblages of the host trees (Chapter 8). Overall spider abundance and species richness did not differ among trees, but particular families and guilds exhibited marked differences in abundance between the tree categories. Most remarkable were the substantial differences in spider species composition across trees with different epiphyte assemblages. Conclusion Thus, the prevalent notion that epiphytes positively influence arthropod diversity in tropical canopies seems justified, but not without reservation. Whether an influence of epiphytes on the fauna was discernible depended greatly on (1) the scale of the investigated system: clear faunal distinctions at the microhabitat level were absent or much more subtle at the level of tree crowns. (2) the focal taxa: different arthropod orders allowed for completely different statements concerning the importance of epiphytes for canopy fauna. I therefore recommend a multitaxon approach for the investigation of large-scale ecological questions. In conclusion, I resume that epiphytes are associated with a species-specific inhabiting fauna,and that epiphytes impose an influence on certain, but not all, taxa even at the level of entire tree crowns. Although I could only hypothesize about the potential causes for this influence, this study provided the first comprehensive investigation of the role of epiphytes in determining arthropod abundance and diversity in tropical tree crowns.}, subject = {Tropischer Regenwald}, language = {en} } @phdthesis{Spohn1999, author = {Spohn, Gunther}, title = {The transcriptional control of virulence gene expression in Helicobacter pylori}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2334}, school = {Universit{\"a}t W{\"u}rzburg}, year = {1999}, abstract = {The Gram-negative, spiral-shaped, microaerophilic bacterium Helicobacter pylori is the causative agent of various disorders of the upper gastrointestinal tract, such as chronic superficial gastritis, chronic active gastritis, peptic ulceration and adenocarcinoma. Although many of the bacterial factors associated with disease development have been analysed in some detail in the recent years, very few studies have focused so far on the mechanisms that regulate expression of these factors at the molecular level. In an attempt to obtain an overview of the basic mechanisms of virulence gene expression in H. pylori, three important virulence factors of this pathogen, representative of different pathogenic mechanisms and different phases of the infectious process, are investigated in detail in the present thesis regarding their transcriptional regulation. As an essential factor for the early phase of infection, including the colonisation of the gastric mucosa, the flagella are analysed; the chaperones including the putative adhesion factors GroEL and DnaK are investigated as representatives of the phase of adherence to the gastric epithelium and persistence in the mucus layer; and finally the cytotoxin associated antigen CagA is analysed as representative of the cag pathogenicity island, which is supposed to account for the phenomena of chronic inflammation and tissue damage observed in the later phases of infection. RNA analyses and in vitro transcription demonstrate that a single promoter regulates expression of cagA, while two promoters are responsible for expression of the upstream divergently transcribed cagB gene. All three promoters are shown to be recognised by RNA polymerase containing the vegetative sigma factor sigma 80. Promoter deletion analyses establish that full activation of the cagA promoter requires sequences up to -70 and binding of the C-terminal portion of the alpha subunit of RNA polymerase to an UP-like element located between -40 and -60, while full activation of the major cagB promoter requires sequences upstream of -96 which overlap with the cagA promoter. These data suggest that the promoters of the pathogenicity island represent a class of minimum promoters, that ensure a basic level of transcription, while full activation requires regulatory elements or structural DNA binding proteins that provide a suitable DNA context. Regarding flagellar biosynthesis, a master transcriptional factor is identified that regulates expression of a series of flagellar basal body and hook genes in concert with the alternative sigma factor sigma 54. Evidence is provided that this regulator, designated FlgR (for flagellar regulatory protein), is necessary for motility and transcription of five promoters for seven basal body and hook genes. In addition, FlgR is shown to act as a repressor of transcription of the sigma 28-regulated promoter of the flaA gene, while changes in DNA topology are shown to affect transcription of the sigma 54-regulated flaB promoter. These data indicate that the regulatory network that governs flagellar gene expression in H. pylori shows similarities to the systems of both Salmonella spp. and Caulobacter crescentus. In contrast to the flagellar genes which are regulated by three different sigma factors, the three operons encoding the major chaperones of H. pylori are shown to be transcribed by RNA polymerase containing the vegetative sigma factor sigma 80. Expression of these operons is shown to be regulated negatively by the transcriptional repressor HspR, a homologue of a repressor protein of Streptomyces spp., known to be involved in negative regulation of heat shock genes. In vitro studies with purified recombinant HspR establish that the protein represses transcription by binding to large DNA regions centered around the transcription initiation site in the case of one promoter, and around -85 and -120 in the case of the the other two promoters. In contrast to the situation in Streptomyces, where transcription of HspR-regulated genes is induced in response to heat shock, transcription of the HspR-dependent genes in H. pylori is not inducible with thermal stimuli. Transcription of two of the three chaperone encoding operons is induced by osmotic shock, while transcription of the third operon, although HspR-dependent, is not affected by salt treatment. Taken together, the analyses carried out indicate that H. pylori has reduced its repertoire of specific regulatory proteins to a basic level that may ensure coordinate regulation of those factors that are necessary during the initial phase of infection including the passage through the gastric lumen and the colonisation of the gastric mucosa. The importance of DNA topology and/or context for transcription of many virulence gene promoters may on the other hand indicate, that a sophisticated global regulatory network is present in H. pylori, which influences transcription of specific subsets of virulence genes in response to changes in the microenvironment.}, subject = {Helicobacter-pylori-Infektion}, language = {en} } @phdthesis{Spaethe2001, author = {Spaethe, Johannes}, title = {Sensory Ecology of Foraging in Bumblebees}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-1179692}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {Pollinating insects exhibit a complex behavior while foraging for nectar and pollen. Many studies have focused on ultimate mechanisms of this behavior, however, the sensory-perceptual processes that constrain such behavior have rarely been considered. In the present study I used bumblebees (Bombus terrestris), an important pollinating insect, to investigate possible sensory constraints on foraging behavior. Additionally, I survey inter-individual variation in the sensory capabilities and behavior of bumblebees caused by the pronounced size polymorphism among members of a single colony. In the first chapter I have focused on the sensory-perceptual processes that constrain the search for flowers. I measured search time for artificial flowers of various sizes and colors, a key variable defining the value of a prey type in optimal foraging theory. When flowers were large, search times correlate well with the color contrast of the targets with their green foliage-type background, as predicted by a model of color opponent coding using inputs from the bee's UV, blue, and green receptors. Targets which made poor color contrast with their backdrop, such as white, UV-reflecting ones, or red flowers, take longest to detect, even though brightness contrast with the background is pronounced. When searching for small targets, bumblebees change their strategy in several ways. They fly significantly slower and closer to the ground, so increasing the minimum detectable area subtended by an object on the ground. In addition they use a different neuronal channel for flower detection: instead of color contrast, they now employ only the green receptor signal for detection. I related these findings to temporal and spatial limitations of different neuronal channels involved in stimulus detection and recognition. Bumblebees do not only possess species-specific sensory capacities but they also exhibit inter-individual differences due to size. Therefore, in the next two chapters I have examined size-related effects on the visual and olfactory system of Bombus terrestris. Chapter two deals with the effect of scaling on eye architecture and spatial resolving power of workers. Foraging efficiency in bees is strongly affected by proficiency of detecting flowers. Both floral display size and bee spatial vision limit flower detection. In chapter one I have shown that search times for flowers strongly increases with decreasing floral display size. The second factor, bee spatial vision, is mainly limited by two properties of compound eyes: (a) the interommatidial angle {\c{C}}{\aa} and (b) the ommatidial acceptance angle {\c{C}}{\´a}. When a pollinator strives to increase the resolving power of its eyes, it is forced to increase both features simultaneously. Bumblebees show a large variation in body size. I found that larger workers with larger eyes possess more ommatidia and larger facet diameters. Large workers with twice the size of small workers (thorax width) have about 50 per cent more ommatidia, and a 1.5 fold enlarged facet diameter. In a behavioral test, large and small workers were trained to detect the presence of a colored stimulus in a Y-maze apparatus. The stimulus was associated with a sucrose reward and was presented in one arm, the other arm contained neither stimulus nor reward. The minimum visual angle a bee is able to detect was estimated by testing the bee at different stimuli sizes subtending angles between 30° and 3° on the bee's eye. Minimum visual detection angles range from 3.4° to 7.0° among tested workers. Larger bumblebees are able to detect objects subtending smaller visual angles, i.e. they are able to detect smaller objects than their small conspecifics. Thus morphological and behavioral findings indicate an improved visual system in larger bees. Beside vision, olfaction is the most important sensory modality while foraging in bees. Bumblebees utilize species-specific odors for detecting and identifying nectar and pollen rich flowers. In chapter three I have investigated the olfactory system of Bombus terrestris and the effect of scaling on antennal olfactory sensilla and the first olfactory neuropil in the bumblebee brain, the antennal lobes. I found that the pronounced size polymorphism exhibited by bumblebees also effects their olfactory system. Sensilla number (I measured the most common olfactory sensilla type, s. placodea), sensilla density, volume of antennal lobe neuropil and volume of single identified glomeruli correlate significantly with worker's size. The enlarged volume of the first olfactory neuropil in large individuals is caused by an increase in glomeruli volume and coarse neuropil volume. Additionally, beside an overall increase of brain volume with scaling I found that the olfactory neuropil increases disproportionately compared to a higher order neuropil, the central body. The data predict a higher odor sensitivity in larger bumblebee workers. In the last chapter I have addressed the question if scaling alters foraging behavior and rate in freely foraging bumblebees. I observed two freely foraging B. terrestris colonies and measured i) trip number, ii) trip time, iii) proportion of nectar trips, and iv) nectar foraging rate of different sized foragers. In all observation periods large foragers exhibit a significantly higher foraging rate than small foragers. None of the other three foraging parameters is affected by workers' size. Thus, large foragers contribute disproportionately more to the current nectar influx of their colony. To summarize, this study shows that understanding the mechanisms of visual information processing and additionally comprising inter-individual differences of sensory capabilities is crucial to interpret foraging behavior of bees.}, subject = {Hummeln}, language = {en} } @phdthesis{SoutoCarneiro2000, author = {Souto-Carneiro, Maria Margarida}, title = {Molecular and functional analyses of human synovial B-lymphocytes in rheumatoid arthritis}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2308}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2000}, abstract = {B-cells of the rheumatoid synovial tissue are a constant part of and, in some histopathological subtypes, the dominant population of the inflammatory infiltrate, located in the region of tissue destruction. The pattern of B-cell distribution and the relationship to the corresponding antigen-presenting cells (follicular dendritic reticulum cells: FDCs) show a great variety. B-cells may exhibit (i) a follicular organization forming secondary follicles; (ii) follicle-like patterns with irregularly formed FDC networks, and (iii) a diffuse pattern of isolated FDCs. Molecular analysis of immunoglobulin VH and VL genes from human synovial B-cell hybridomas and synovial tissue demonstrates somatic mutations due to antigen activation. The FDC formations in the synovial tissue may therefore serve as an environment for B-cell maturation, which is involved in the generation of autoantibodies. An autoantibody is defined as "pathogenic" if it fulfills the Witebsky-Rose-Koch criteria for classical autoimmune diseases: definition of the autoantibody; induction of the disease by transfer of the autoantibody; and isolation of the autoantibody from the disease-specific lesion. B-cells from rheumatoid synovial tissue show specificity for FcIgG, type II collagen, COMP, sDNA, tetanus toxoid, mitochondrial antigens (M2), filaggrin and bacterial HSPs. The contributions of these antigens to the pathogenesis of RA are still hypothetical. A possible contribution could derive from crossreactivity and epitope mimicry: due to crossreaction, an antibody directed originally against a foreign infectious agent could react with epitopes from articular tissues, perpetuating the local inflammatory process. The characteristic distribution pattern, the localisation within the area of tissue destruction, the hypermutated IgVH and IgVL genes, and their exclusive function to recognize conformation-dependent antigens suggest a central role for B-cells in the inflammatory process of rheumatoid arthritis. Therefore, the analysis of synovial B-cell hybridomas and experimental expression of synovial IgVH and IgVL genes will help to characterise the antigens responsible for the pathogenesis of rheumatoid arthritis. In the present study 55 IgVH genes amplified from 3 different anatomical regions of a RA patient were analysed adding further information on synovial B-cell maturation and recirculation in RA. This analysis demonstrated somatically mutated IgVh genes in all different regions with amino acid deletions and mixed IgVh molecules, suggesting the existence of a novel pathway to generate (auto)antibody specificities. The comparison of amino acid sequences of amplified genes belonging to the VH1 family (with predominantly the same germline counterpart) exhibited a strong homology, indicating an apparently conserved mutational pattern. This suggests that the number of antigens activating B-cells in the different locations is restricted. The most striking result was the finding of clonally related sequences in different anatomical regions indicating a recirculation of activated B-cells between the different affected joints. Also in the present study a synovial B-cell hybridoma was analyzed for its specific recognition of cartilage antigens. A heptameric peptide of cartilage oligomeric protein (COMP) could be defined as the target structure. The IgVH-gene (IgHV4-59*01) of the IgG2l hybridoma has somatically mutated genes with high R/S values in the CDR regions (9:2). Thus, indicating that this hybridoma originates from a synovial B-cell which has been antigen activated/selected for its affinity. To analyse the presence of the clonotypic IgHV4-59*01 sequences in other cases of RA and osteoarthritis (OA) synovitis, primers specific for the CDR3 rearrangement of this hybridoma were used. The clonotypic and clone related sequences (98 per cent ± 1 per cent homology) could only be detected in synovitis of RA cases but not in OA cases indicating that this B-cell is specific to RA synovitis. The identified heptameric peptide of COMP was used in a peptide ELISA to analyse whether there is a specific binding in RA serum samples. Serum samples (IgG) from RA patients (n=22) showed a significant higher efficiency to the COMP heptamer than the OA sera (n=24) and the age matched healthy controls (n=20) (for both p<1x10-4, Students t-test). The specificity of this B-cell hybridoma may therefore be defined as RA specific. Since COMP is restricted to cartilage and tendons which are organs specifically affected in RA this COMP specific autoantibody represents the first organ specific autoantibody in RA. The IgG2 COMP specific autoantibody with somatically mutated IgVH genes is different from germline encoded, antigen clearing IgM autoantibodies and may therefore be directly involved as an "arthritogenic autoantibody" in cartilage and tendons destruction by complement activation.}, subject = {Rheumatoide Arthritis}, language = {en} } @phdthesis{Bluem2001, author = {Bl{\"u}m, Martina}, title = {Reaktivation and stabilization phases of eolian deposits under climatic and anthropogenic influences in the Rolling Plains of Texas, U.S.A.}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-1179360}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2001}, abstract = {There are ample sand dune and sand sheets in the Texas Rolling Plains, U.S.A. Their varied location, morphology and paleosol content pointed to differnces in their historical develpment throughout the Holocene. Younger dunes, so called fence line dunes have been identified as remnants of unsound agricultural practices which just recently formed at the beginning of this century. Correspondingly soils were eroded, in parts, down to the C-horizon in some of these areas. More mature sand were dated with the radiocarbon method and identified having formed during the Altithermal warming period. This study identifies major eolian anthropogenic and climatic reactivation and stabilisation phases in the Rolling Plains of Texas during the Holocene, but also ties them into the existing Southern High Plains and Great Plains climatic record. This study also researched the reasons for the regional and local sand reactivation phases and contributes to the eolian history in the Great Plains region. The outline of this dissertation is oriented towards a comprehensive regional approach in cultural and physical geography. Chapter 1 covers the physiographic setting of the Rolling Plains region including geology, geomorphology, climate and vegetation. Here the prerequisites for eolian activity in the area are explained, followed by the criteria for the selection of the individual study sites. In chapter 2 selected dune fields and sand sheets are introduced. Chapter 3 outlines the methodology as a combination of field research, laboratory analysis and remote sensing techniques, along with a brief interpretation of their application and success rate. Chapter 4 investigates interactive processes between the cultural development and the physical landscape of the region. The next 4 chapters are focusing on research results and interpretation. Chapter 5 interprets the youngest eolian episodes resulting from the cultural de-velopment of the area, including a description and definition of so called "fenceline dunes" and "shinnery motts". Other dunes with very young buried horizons are also described in this chapter, and a comparison with outcrops in the Nebraska Sand Hills is performed. Chapter 6 interprets short-term, cyclic, drought related sand reactivations several hundred years ago by means of a Post Oak (Quercus stellata) tree ring record as established by STAHLE and CLEAVELAND (1988). In chapter 7 older Holocene reactivation cycles are introduced, investigating the idea of the existence of a warmer period, previously named the Altithermal, which so far has only been identified in the Southern High Plains. The last chapter (8) includes a brief statement of the study's purpose along with the summary and discussion of results presented. This chapter will end with further implications of this research.}, subject = {Texas }, language = {en} } @phdthesis{Siebert2002, author = {Siebert, Torsten Uwe}, title = {Four-Wave Mixing Techniques Applied to the Investigation of Non-Adiabatic Dynamics in Polyatomic Molecules}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-2456}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2002}, abstract = {In the experiments presented in this work, third-order, time-resolved spectroscopy was applied to the disentanglement of nuclear and electronic degrees of freedom in polyatomic molecules. The motivation for approaching this problem was given by the decisive role that the coupling of nuclear and electronic dynamics plays in the mechanism of photochemical reactions and photobiological processes. In order to approach this complex problem, different strategies within the framework of time-resolved, four-wave mixing spectroscopy were developed that allowed for the dynamic as well as the energetic aspects of vibronic coupling in non-radiative transitions of polyatomic molecules to be addressed. This was achieved by utilizing the influence of optical as well as Raman resonances on four-wave mixing processes. These resonance effects on third-order, optical processes allow for a high selectivity to be attained with respect to the interrogation of specific aspects of molecular dynamics. The development of different strategies within the framework of time-resolved, four-wave mixing spectroscopy for addressing the problem of vibronic coupling began with the experiments on gaseous iodine. This simple, well investigated molecular system was chosen in order to unambiguously characterize the effect of Raman resonances on four-wave mixing processes. A time-resolved degenerative four-wave mixing (DFWM) experiment was carried out on gaseous iodine that allowed for the dynamics of coherent Stokes Raman scattering (CSRS) as well as a coherent anti-Stokes Raman scattering (CARS) to be observed parallel to the dynamics of a DFWM process at different spectral positions of the FWM signal. Here, the state-selectivity of these different FWM processes manifests itself in the vibrational wave packet dynamics on different electronic potentials of iodine. It could be shown that Raman resonances determine the selectivity with which these FWM processes prepare and interrogate nuclear dynamics in different electronic states. With the insight gained into the relevance of Raman resonant processes in FWM spectroscopy, an experimental scheme was devised that utilizes this effect to selectively interrogate the dynamics of a specific vibrational mode within a polyatomic molecule during a radiationless electronic transition. Here, a CARS process was employed to selectively probe specific vibrational modes of a molecular system by variably tuning the energy difference between the lasers involved in the CARS process to be in Raman resonance with the vibrational energy spacing of a particular vibrational mode. Using this aspect of a tunable resonance enhancement within a CARS scheme, this optical process was incorporated in a time-resolved pump-probe experiment as a mode-selective probe mechanism. This type of experimental configuration, that employs four pulsed laser fields, was classified as a pump-CARS scheme. Here, a laser pulse independent of the CARS process initiates the molecular dynamics that are interrogated selectively with respect to the vibrational mode of the system through the simultaneous interaction of the three pulsed fields involved in the CARS process. Time-resolution on a femtosecond timescale is achieved by introducing a time delay between the independent pump laser and the laser pulses of the CARS process. The experimental configuration of a pump-CARS scheme was applied to the study of the nuclear dynamics involved in the radiationless electronic transition between the first excited singlet state (S1) and the electronic ground state (S0) of all-trans-b-carotene. The mode-selective CARS probe allowed for the characteristic timescale with which specific vibrational modes are repopulated in the S0 state to be determined. From the varying repopulation times of specific vibrational modes, a mechanism with which the full set of vibrational states of the S0 potential are repopulated subsequent to the internal conversion process could be postulated. Most importantly, the form of nuclear motion that primarily funnels the population between the two electronic states could be identified as the C=C symmetric symmetric stretch mode in the polyene backbone of b-carotene. With this, the reaction coordinate of this radiationless electronic transition could be identified. The experiment shows, that the CARS probe is capable of determining the nuclear motion coupled to a radiationless electronic transition in complex polyatomic systems. The S1/S0 internal conversion process in b-carotene was further investigated with time-resolved transient gratings. Here, the energetic aspects of a non-adiabatic transition was addressed by determining the influence of the vibrational energy on the rate of this internal conversion. In order to compare the rate of internal conversion taking place out of vibrational ground state modes versus this transition initiating out of vibrationally hot modes, the strategy of shifting the probe mechanism in the transient grating scheme to spectral positions within and out of the red flank of the S1 absorption profile was pursued. The interrogation of different vibrational states was verified by determining the degree of vibrational cooling, taking place parallel to the internal conversion process. With this strategy, it could be shown that vibrationally hot states contribute to the internal conversion with a higher rate than vibrational ground state modes. In summary, different third-order, optical processes in the framework of time-resolved FWM were applied to the study of non-adiabatic dynamics in polyatomic molecules. By utilizing the effect of optical as well as Raman resonances on different FWM processes, it could be shown that third-order, time-resolved spectroscopy is a powerful tool for gaining insight into complex molecular dynamics such as vibronic coupling. The experiments presented in this work showed that the CARS process, as a mode-selective probe in time-resolved experiments, is capable of disentangling nuclear and electronic dynamics.}, subject = {Provitamin A}, language = {en} }