Synthese und Photochemie von Dendrimeren mit stilbenoiden Chromophoren

Dendrimere spielen als strukturtreue Nanopartikel eine herausragende Rolle. Ziel dieser Arbeit war, Dendrimere mit einer hohen Dichte an photoaktiven Chromophoren herzu-stellen und zu untersuchen. Dazu wurden die terminalen Aminogruppen von Poly(propylenimin)dendrimeren 1. und 2. Generation, Astramol DAB-Am-4R und DAB-Am-8R, mit Stilbenen und Styrylstilbenen als Chromophor verknüpft. Mittels Wittig-Horner- und Heck-Reaktion wurden (E)-Stilbene aufgebaut, die auf der einen Seite drei Propoxygruppen zur Verbesserung der Löslichkeit und auf der anderen Seite eine passende Funktionalität zur Verknüpfung mit dem dendritischen Core tragen. Als Verknüpfungsmethoden wurden die Verknüpfung als Amid (PSDA), Schiffsche Base (PSDS) und Harnstoff (PSDH) getestet. Die Schiffschen Basen wurden außerdem zur Erhöhung der Hydrolysestabilität zum sekundären Amin reduziert (PSDR und PQDR). Durch die Verknüpfung mit dem Core werden die stilbenoiden Chromophore sehr stark photoaktiviert. Das beruht auf einem Singulett-Energietransfer (Förster-Mechanismus) von Chromophor zu Chromophor. Dieser Prozeß konkurriert zu den Deaktivierungsprozessen, verlängert die mittlere S1-Lebensdauer und erhöht somit die Chancen der Photochemie. Der Styrylstilben-Chromophor hat darüber hinaus einen erheblichen Teil seiner UV-Absorbtion bereits im Tageslicht und photopolymerisiert daher bereits im Tageslicht. Vor allem bei den Dendrimeren 2. Generation stellte sich die Frage nach der vollständigen, d.h. achtfachen Umsetzung; das Core sollte als Knäuel vorliegen, die Arme zum Teil nach innen gefaltet und somit dem Reaktand nur bedingt zugänglich. Auch dort konnten unter optimierten Reaktionsbedingungen alle Aminogruppen umgesetzt werden. Die vollständige Umsetzung der Dendrimere wurde mittels NMR und massenspektroskopischen Methoden untersucht. Bei den Absorptionsspektren der Dendrimere 1. Generation ändert sich die Lage der Maxima je nach Art der Verknüpfung der Chromophore mit dem Core. Die Verlängerung des Chromophors um eine Styryleinheit bedingt eine beträchtliche Rotverschiebung. Die Lage der Emissionsmaxima differiert stärker als die Lage der Absorptionsmaxima. Den geringsten Stokes-Shift weist der Harnstoff auf, dann folgt das sekundäre Amin, dann die Schiffsche Base. Dies weist auf unterschiedlich relaxierte S1-Geometrien hin. Die Verbindungen PSDS1, PSDR1 und PSDH1 aus 3,4,5-Tripropoxystilbeneinheit und Astramol-Core 1. Generation DAB-Am-4 wurden in einer Konzentration von 10-5 mol/L belichtet. Der vollständige Photoabbau durch Belichtung in Chloroform mit einer Xenon-Lampe erfolgte ohne jeglichen Filter innerhalb von zehn Minuten (PSDH1), 20 Minuten (PSDR1) und einer Stunde (PSDS1). Allen drei Verbindungen gemeinsam ist das Entstehen eines intermediären neuen Maximums geringer Intensität, das um etwa 100 nm bathochrom verschoben ist. Das Harnstoffsystem weist außerdem ein weiteres intermediäres Maximum bei 614 nm auf. Diese Maxima können (laut früherer Untersuchungen) durch Oxidation entstandenen chinoiden Strukturen zugeordnet werden, deren Lebensdauer (im Sekundenbereich) zu kurz für eine NMR-Charakterisierung ist. PSDR1 wurde außerdem bei höheren Konzentrationen (10-4 und 10-3 mol/L) mit einer Quecksilberlampe mit Pyrex-Filter (lambda > 300 nm) belichtet. Dabei wird, wie erwartet, eine Verbreiterung der NMR-Signale beobachtet. Es bildet sich zunächst cis-Stilben. Außerdem läßt sich bei 4.3 ppm ein Signal beobachten, das von inter- oder intramolekular gebildeten Methinprotonen herrührt. Auch wenn laut MOPAC- und Kraftfeldrechnung die Doppelbindungen ungünstig für eine [pi2s + pi2s]-Cyclodimerisierung zueinander stehen, kann im photochemisch angeregten Zustand eine Geometrie vorherrschen, die die intramolekulare Kopf-Kopf-Cyclobutanbildung ermöglicht. Die massenspektrometrischen Untersuchungen der Belichtungsprodukte (FD, ESI, MALDI-TOF) zeigen als höchste Masse lediglich das Monomer. Allerdings kann dadurch nicht auf eine rein intramolekulare Reaktion geschlossen werden. Die fortschreitende statistische CC-Verknüpfung kann schnell zu vernetzten Nanopartikeln führen, die im Massenspektrometer nicht fliegen. Die NMR-Spektren der mit zunehmender Vernetzung immer schlechter löslich werdenden Teilchen belegen die Oligomerisierung.

MetaVaccinology: a new vaccine discovery tool

In the last decade, the reverse vaccinology approach shifted the paradigm of vaccine discovery from conventional culture-based methods to high-throughput genome-based approaches for the development of recombinant protein-based vaccines against pathogenic bacteria. Besides reaching its main goal of identifying new vaccine candidates, this new procedure produced also a huge amount of molecular knowledge related to them. In the present work, we explored this knowledge in a species-independent way and we performed a systematic in silico molecular analysis of more than 100 protective antigens, looking at their sequence similarity, domain composition and protein architecture in order to identify possible common molecular features. This meta-analysis revealed that, beside a low sequence similarity, most of the known bacterial protective antigens shared structural/functional Pfam domains as well as specific protein architectures. Based on this, we formulated the hypothesis that the occurrence of these molecular signatures can be predictive of possible protective properties of other proteins in different bacterial species. We tested this hypothesis in Streptococcus agalactiae and identified four new protective antigens. Moreover, in order to provide a second proof of the concept for our approach, we used Staphyloccus aureus as a second pathogen and identified five new protective antigens. This new knowledge-driven selection process, named MetaVaccinology, represents the first in silico vaccine discovery tool based on conserved and predictive molecular and structural features of bacterial protective antigens and not dependent upon the prediction of their sub-cellular localization.

Molekulare Reaktionsmuster in dendritischen Zellen nach Allergenexposition

Allergische Erkrankungen, wie zum Beispiel die allergische Rhinitis oder das allergische Asthma haben im Verlauf der letzten vier Jahrzehnte stark zugenommen. So leidet heute jeder vierte bis fünfte Mensch an einer Allergie. Ausgelöst wird diese IgE-vermittelte Hypersensibilitätsreaktion des Typs I (Allergie vom Soforttyp) von Allergenen und beruht auf der Aktivierung von Mastzellen durch die Interaktion eines Antigens mit dem an eine Mastzelle über die Fc-Rezeptoren gebundenen IgE-Moleküls. Die degranulierende Mastzelle sezerniert Mediatoren, was zu einem Auftreten von allergischen Symptomen führt. Die Bildung von IgE wird durch das von TH2-Zellen produzierte Zytokin IL-4 induziert. Das von TH1-Zellen produzierte Zytokin IFN- ist in der Lage die Sekretion von IL-4 zu inhibieren, wie auch IL-4 hemmend auf die Produktion von IFN- wirkt. Dieses TH1-/ TH2-Gleichgewicht ist bei allergischen Erkrankungen in Richtung TH2 verschoben. Allergene werden von antigenpräsentierenden Zellen aufgenommen, prozessiert und auf der Zelloberfläche präsentiert. Die potentesten antigenpräsentierenden Zellen sind die dendritischen Zellen, die nach Kontakt mit einem Allergen in die benachbarten Lymphknoten wandern, ausreifen und kostimulatorische Moleküle exprimieren. Sie sind so in der Lage T-Zellen zu aktivieren und entweder in TH1- oder in TH2-Zellen differenzieren zu lassen. Die zytokinabhängige TH1- beziehungsweise TH2-Differenzierung führt zur Aktivierung der Januskinasen. Im aktiven Zustand phosphorylieren sie STAT-Moleküle, die dimerisieren und in den Zellkern translozieren, wo sie unter anderem als Transkriptionsfaktoren für Zytokingene dienen. Unreife humane dendritische Zellen von Allergikern zeigen nach Stimulation mit Proteinallergenen eine schnelle Phosphorylierung des mit der TH2-Entwicklung assoziierten STAT6. Dahingegen sind TH1-Antwort hervorrufende Kontaktallergene nicht in der Lage STAT6 oder andere STAT-Moleküle in dendritischen Zellen zu induzieren. Die Transkriptionsfaktoren T-bet und GATA3 sind ebenfalls von Bedeutung für die TH1-/TH2-Entwicklung, da T-bet ausschließlich in TH1-Zellen, GATA3 nur in TH2-Zellen exprimiert wird. Die Regulation des JAK/STAT-Weg unterliegt den Molekülen der intrazellulär vorkommenden Familie der SOCS-Proteine. SOCS3 ist in TH2-Zellen höher exprimiert als SOCS1, wohingegen SOCS1 in TH1-Zellen eine erhöhte Expression gegenüber SOCS3 aufweist. In der vorliegenden Arbeit wurde der Einfluss von Proteinallergenen auf humane dendritische Zellen untersucht. Zunächst konnte eine morphologische Veränderung der unreifen dendritischen Zellen nach Kontakt mit dem Allergenextrakt beobachtet werden. Die beginnende Ausreifung der Zellen konnte mittels Durchflußzytometrie anhand der kostimulatorischen Moleküle CD80 und CD86, insbesondere aber über den Marker für reife dendritische Zellen CD83, nachgewiesen werden. Die zu beobachtende beginnende Ausreifung scheint ein Effekt des bakteriellen Lipopolysaccharids (LPS) zu sein, das in dem Allergenextrakt vorkommt, da sich durch Zugabe des kationischen Antibiotikums Polymyxin B die beginnende Reifung verhindern ließ. Auf RNA-Ebene war es im Rahmen dieser Arbeit möglich, den Einfluss verschiedener Allergene auf unreifen humanen dendritischen Zellen näher zu charakterisieren. So weisen unreife humane dendritische Zellen nach Kontakt mit Proteinallergenextrakt ein TH2-assoziiertes Genexpressionprofil auf, was sich durch eine erhöhte relative Expression der Gene SOCS3 und GATA3 auszeichnet. Im Gegensatz hierzu zeigen unreife humane dendritische Zellen nach Inkubation mit dem Kontaktallergen MCI/MI eine erhöhte relative Expression des Gens T-bet, was mit einer TH1-Antwort assoziiert ist. Nach Zugabe des „TH1-/ TH2-neutralen“ Tetanustoxoids konnten erhöhte relative Expressionen der Gene GATA3, T-bet und SOCS3 gemessen werden. Die Ergebnisse in dem in dieser Arbeit benutzten humanen in vitro System geben Anlass zur Hypothese, dass die Art der Immunantwort (TH1 versus TH2) sich bereits auf Ebene der dendritischen Zellen anbahnt. GeneChip-Analysen mittels High Density Micro Arrays von unreifen humanen dendritischen Zellen, die entweder mit Proteinallergenextrakt oder mit LPS in Berührung kamen, zeigten statistisch signifikant regulierte Gene, die allerdings keine Gemeinsamkeiten aufwiesen. Es konnten für die mit Alllergenextrakt gepulsten dendritischen Zellen insgesamt 10 Gene identifiziert werden, jedoch gelang es nicht, diese näher zu deuten oder in einen Zusammenhang mit der allergischen Erkrankung oder der dendritischen Zelle zu bringen. Für die mit LPS, dem stärkeren Stimulus, gepulsten dendritischen Zellen konnten 40 Gene identifiziert werden, die unter anderem für die Maturierung der dendritischen Zelle verantwortlich sind. Zudem war es möglich, die Daten der Arrays auf Proteinebene exemplarisch anhand des Chemokins CXCL2 (Gro-β) zu verifizieren.

Expression profiling in developing peach seed and mesocarp as affected by growth regulators

Jasmonates (JAs) and spermidine (Sd) influence fruit (and seed) development and ripening. In order to unravel their effects in peach fruit, at molecular level, field applications of methyl jasmonate (MJ) and propyl dihydrojasmonate (PDJ), and Sd were performed at an early developmental stage (late S1). At commercial harvest, JA-treated fruit were less ripe than controls. Realtime RT-PCR analyses confirmed a down-regulation of ethylene biosynthetic, perception and signaling genes, and flesh softening-related genes. The expression of cell wall-related genes, of a sugar-transporter and hormone-related transcript levels was also affected by JAs. Seeds from JA-treated fruit showed a shift in the expression of developmental marker genes suggesting that the developmental program was probably slowed down, in agreement with the contention that JAs divert resources from growth to defense. JAs also affected phenolic content and biosynthetic gene expression in the mesocarp. Levels of hydroxycinnamic acids, as well as those of flavan-3-ols, were enhanced, mainly by MJ, in S2. Transcript levels of phenylpropanoid pathway genes were up-regulated by MJ, in agreement with phenolic content. Sd-treated fruits at harvest showed reduced ethylene production and flesh softening. Sd induced a short-term and long-term response patterns in endogenous polyamines. At ripening the up-regulation of the ethylene biosynthetic genes was dramatically counteracted by Sd, leading to a down-regulation of softening-related genes. Hormone-related gene expression was also altered both in the short- and long-term. Gene expression analyses suggest that Sd interfered with fruit development/ripening by interacting with multiple hormonal pathways and that fruit developmental marker gene expression was shifted ahead in accord with a developmental slowing down. 24-Epibrassinolide was applied to Flaminia peaches under field conditions early (S1) or later (S3) during development. Preliminary results showed that, at harvest, treated fruit tended to be larger and less mature though quality parameters did not change relative to controls.

Poly(p-phenylen)-Derivate für die Anwendung in Leuchtdioden

Zusammenfassung Das 2,7-Polyfluoren (2,7-PF) wurde in neuer Zeit sowohl wegen seiner einfachen Synthese und hohen Fluoreszenzquantenausbeuten als auch seiner chemischen und thermischen Stabilität intensiv untersucht. Leider liegt das Emissionsmaximum von 2,7-PF in einem Bereich, bei dem das menschliche Auge nicht genügend Sensitivität aufweist. Das Leiter-Poly(p-phenylen) (LPPP) besitzt die optimale Wellenlänge. Jedoch zeigt das LPPP wegen seines steifen Rückgrates große Aggregationstendenz im Film auf, wodurch die Emissionsfarbe bathochrom verschoben und die Photolumineszenzquantenausbeute verringert wird. Es ist deshalb wünschenswert, Polymere zu synthetisieren, die eine längerwellige Emissionsbande als 2,7-PF und eine geringere Aggregationstendenz als LPPP 20 besitzen. Eine Reihe neuer blau emittierender Polymere auf der Basis von Indenofluoren- und Fluoren-Bausteinen mit geringer Aggregationstendenz, hoher thermischer und chemischer Stabilität sowie guter Verarbeitbarkeit wurden dargestellt. Die Polymere weisen eine hohe thermische Stabilität auf (Zersetzung ca.: 310 °C) und sind sehr gut löslich in organischen Lösungsmitteln. Das Absorptionsmaximum des 2,8-Polyindenofluoren (2,8-PIF) in Chloroform liegt bei 416 nm, das Emissionsmaximun bei 432 nm. Die Phasenumwandlungstemperatur beim PIF liegt ca. bei 260 °C. Leider zeigen 2,8-PIF Aggregationstendenzen im Film. Um die Aggregation komplett zu unterbinden, wurden Polyphenylene als Seitenketten an das Dibromfluoren angebracht. Anschließend wurde nach Yamamoto polymerisiert. Das dendritnische PF (DPF) weist die gleiche thermische Stabilität wie die PIFs 28 auf (Zersetzung: 340 °C). Das Polymer 62a ist sehr gut löslich in Toluol, Xylol und chlorierten organischen Lösungsmitteln. Die Absorptions- und Emissionsmaxima des DPFs in Lösung (Chloroform) weisen keine Veränderung gegenüber PF auf. Die Emissionsmaxima des DPFs im Film und nach dem Tempern (100 °C, 24 h) zeigen lediglich eine Verschiebung um 8 nm. Eine Aggregatenbande entsteht jedoch nicht. Dies unterstreicht die abschirmende Eigenschaft der dendritischen Substituenten. Durch Copolymerisation lassen sich die Eigenschaften von Polymeren variieren. Um die Aggregationstendenz der PIF-Derivate zu verringern, wurden die entsprechenden Monomere in verschiedenen Verhältnissen copolymerisiert. Durch die Copolymerisation wurde die PL-Quantenausbeute auf 50 % erhöht. Weiterhin wurden Copolymere von Indenofluoren und 9,10-Dibromanthracen, und erschiedenen Perylenen hergestellt, um zu blau, rot und grün emittierenden Polymeren zu gelangen. Alle blau emittierenden Polymeren wurden in Leuchtdioden untersucht. Das DPF und das Copolymer aus Indenofluoren und Anthracene wiesen die besten Eigenschaften hierfür auf.

Photovoltaics from discotic liquid crystalline HBCs & poly(2,7-carbazole)s

In this study, the use of the discotic liquid crystalline HBCs and conjugated polymers based on 2,7-carbazole were investigated in detail as donor materials in organic bulk-heterojunction solar cells. It has been shown that they perform efficiently in photovoltaic devices in combination with suitable acceptors. The efficiency was found to depend strongly dependent on the morphology of the film. By investigation of a series of donor materials with similar molecular structures based on both discotic molecules and conjugated polymers, a structure-performance relation was established, which is not only instructive for these materials but also serves as a guideline for improved molecular design. For the series of HBCs used in this study, it is found that the device efficiency decreases with increasing length of the alkyl substituents in the HBC. Thus, the derivative with the smallest alkyl mantle, being more crystalline compared to the HBCs with longer alkyl chains, gave the highest EQE of 12%. A large interfacial separation was found in the blend of HBC-C6,2 and PDI, since the crystallization of the acceptor occurred in a solid matrix of HBC. This led to small dispersed organized domains and benefited the charge transport. In contrast, blends of HBC-C10,6/PDI or HBC-C14,10/PDI revealed a rather homogeneous film limiting the percolation pathways due to a mixed phase. For the first time, poly(2,7-carbazole) was incorporated as a donor material in solar cells using PDI as an electron acceptor. The good fit in orbital energy levels and absorption spectra led to high efficiency. This result indicates that conjugated polymers with high band-gap can also be applied as materials to build efficient solar cells if appropriate electron acceptors are chosen. In order to enhance the light absorption ability, new ladder-type polymers based on pentaphenylene and hexaphenylene with one and three nitrogen bridges per repeat unit have been synthesized and characterized. The polymer 2 with three nitrogen bridges showed more red-shifted absorbance and emission and better packing in the solid-state than the analogous polymer 3 with only one nitrogen bridge per monomer unit. An overall efficiency as high as 1.3% under solar light was obtained for the device based on 1 and PDI, compared with 0.7% for the PCz based device. Therefore, the device performance correlates to a large extent with the solar light absorption ability and the lateral distance between conjugated polymer chains. Since the lateral distance is determined by the length and number of attached alkyl side chains, it is possible to assume that these substituents insulate the charge carrier pathways and decrease the device performance. As an additional consequence, the active semiconductor is diluted in the insulating matrix leading to a lower light absorption. This work suggests ways to improve device performance by molecular design, viz. maintaining the HOMO level while bathochromically shifting the absorption by adopting a more rigid ladder-type structure. Also, a high ratio of nitrogen bridges with small alkyl substituents was a desirable feature both in terms of adjusting the absorption and maintaining a low lateral inter-chain separation, which was necessary for obtaining high current and efficiency values.

Physiological and Biochemical Aspects of Iron Nutrition in Grapevine

The objective of this thesis was to study the response mechanisms of grapevine to Fe-deficiency and to potential Fe chlorosis prevention strategies. The results show that the presence of bicarbonate in the nutrient solution shifted the activity of PEPC and TCA cycle enzymes and the accumulation/translocation of organic acids in roots of Fe-deprived plants. The rootstock 140 Ruggeri displayed a typical behavior of calcicole plants under bicarbonate stress. The Fe chlorosis susceptible rootstock 101-14 reacted to a prolonged Fe-deficiency reducing the root activity of PEPC and MDH. Noteworthy, it accumulates high levels of citric acid in roots, indicating a low capacity to utilizing, transporting and/or exudating organic acids into the rhizosfere. In contrast, 110 Richter rootstock is capable to maintain an active metabolism of organic acids in roots, accumulating them to a lesser extent than 101-14. Similarly to 101-14, SO4 genotype displays a strong decrease of mechanisms associated to Fe chlorosis tolerance (PEPC and MDH enzymes). Nevertheless it is able to avoid excessive accumulation of citric acid in roots, similar as 110 Richter rootstock. Intercropping with Festuca rubra increased leaf chlorophyll content and net photosynthesis. In addition, intercropping reduces the activity of PEPC in roots, similary to Fe-chelate supply. Applications of NH4+ with nitrification inhibitor prevents efficiently Fe-deficiency, increases chlorophyll content, and induces similar root biochemical responses as Fe-EDDHA. Without the addition of nitrification inhibitors, the effectiveness of NH4+ supply on Fe chlorosis prevention resulted significantly lower. The aspects intertwined in this investigation highlight the complexity of Fe physiology and the fine metabolic tuning of grapevine genotypes to Fe availability and soil-related environmental factors. The experimental evidences reveal the need to carry out future researches on Fe nutrition maintaining a continous flow of knowledge between theoretical and agronomical perspectives for fully supporting the efforts devoted to convert science into practice.

Evolutionary tendencies in flowers of Marantaceae with special reference to the style movement mechanism

One of the quickest plant movements ever known is made by the ´explosive´ style in Marantaceae in the service of secondary pollen presentation – herewith showing a striking apomorphy to the sister Cannaceae that might be of high evolutionary consequence. Though known already since the beginning of the 19th century the underlying mechanism of the movement has hitherto not been clarified. The present study reports about the biomechanics of the style-staminode complex and the hydraulic principles of the movement. For the first time it is shown by experiment that in Maranta noctiflora through longitudinal growth of the maturing style in the ´straitjacket´ of the hooded staminode both the hold of the style prior to its release and its tensioning for the movement are brought about. The longer the style grows in relation to the enclosing hooded staminode the more does its capacity for curling up for pollen transfer increase. Hereby I distinguish between the ´basic tension´ that a growing style builds up anyway, even when the hooded staminode is removed beforehand, and the ´induced tension´ which comes about only under the pressure of a ´too short´ hooded staminode and which enables the movement. The results of these investigations are discussed in view of previous interpretations ranging from possible biomechanical to electrophysiological mechanisms. To understand furthermore by which means the style gives way to the strong bending movement without suffering outwardly visible damage I examined its anatomical structure in several genera for its mechanical and hydraulic properties and for the determination of the entire curvature after release. The actual bending part contains tubulate cells whose walls are extraordinarily porous and large longitudinal intercellular spaces. SEM indicates the starting points of cell-wall loosening in primary walls and lysis of middle lamellae - probably through an intense pectinase activity in the maturing style. Fluorescence pictures of macerated and living style-tissue confirm cell-wall perforations that do apparently connect neighbouring cells, which leads to an extremely permeable parenchyma. The ´water-body´ can be shifted from central to dorsal cell layers to support the bending. The geometrical form of the curvature is determined by the vascular bundles. I conclude that the style in Marantaceae contains no ´antagonistic´ motile tissues as in Mimosa or Dionaea. Instead, through self-maceration it develops to a ´hydraulic tissue´ which carries out an irreversible movement through a sudden reshaping. To ascertain the evolutionary consequence of this apomorphic pollination mechanism the diversity and systematic value of hooded staminodes are examined. For this hooded staminodes of 24 genera are sorted according to a minimalistic selection of shape characters and eight morphological types are abstracted from the resulting groups. These types are mapped onto an already available maximally parsimonious tree comprising five major clades. An amazing correspondence is found between the morphological types and the clades; several sister-relationships are confirmed and in cases of uncertain position possible evolutionary pathways, such as convergence, dispersal or re-migration, are discussed, as well as the great evolutionary tendencies for the entire family in which – at least as regards the shape of hooded staminodes – there is obviously a tendency from complicated to strongly simplified forms. It suggests itself that such simplifying derivations may very likely have taken place as adaptations to pollinating animals about which at present too little is known. The value of morphological characters in relation to modern phylogenetic analysis is discussed and conditions for the selection of morphological characters valuable for a systematic grouping are proposed. Altogether, in view of the evolutionary success of Marantaceae compared with Cannaceae the movement mechanism of the style-staminode complex can safely be considered a key innovation within the order Zingiberales.

Finite-element discretization of 3D energy-transport equations for semiconductors

In this thesis a mathematical model was derived that describes the charge and energy transport in semiconductor devices like transistors. Moreover, numerical simulations of these physical processes are performed. In order to accomplish this, methods of theoretical physics, functional analysis, numerical mathematics and computer programming are applied. After an introduction to the status quo of semiconductor device simulation methods and a brief review of historical facts up to now, the attention is shifted to the construction of a model, which serves as the basis of the subsequent derivations in the thesis. Thereby the starting point is an important equation of the theory of dilute gases. From this equation the model equations are derived and specified by means of a series expansion method. This is done in a multi-stage derivation process, which is mainly taken from a scientific paper and which does not constitute the focus of this thesis. In the following phase we specify the mathematical setting and make precise the model assumptions. Thereby we make use of methods of functional analysis. Since the equations we deal with are coupled, we are concerned with a nonstandard problem. In contrary, the theory of scalar elliptic equations is established meanwhile. Subsequently, we are preoccupied with the numerical discretization of the equations. A special finite-element method is used for the discretization. This special approach has to be done in order to make the numerical results appropriate for practical application. By a series of transformations from the discrete model we derive a system of algebraic equations that are eligible for numerical evaluation. Using self-made computer programs we solve the equations to get approximate solutions. These programs are based on new and specialized iteration procedures that are developed and thoroughly tested within the frame of this research work. Due to their importance and their novel status, they are explained and demonstrated in detail. We compare these new iterations with a standard method that is complemented by a feature to fit in the current context. A further innovation is the computation of solutions in three-dimensional domains, which are still rare. Special attention is paid to applicability of the 3D simulation tools. The programs are designed to have justifiable working complexity. The simulation results of some models of contemporary semiconductor devices are shown and detailed comments on the results are given. Eventually, we make a prospect on future development and enhancements of the models and of the algorithms that we used.

Il corpo e l'individuo tra proprietà ed autodeterminazione. Con particolare riferimento al fenomeno delle biobanche

La bioetica è il luogo ideale per cercare risposte ai grandi interrogativi concernenti la vita, la morte e la cura dell'essere umano. I recenti dibattiti sull'uso, ed il temuto abuso, del corpo umano in medicina hanno messo in evidenza la necessità di una discussione approfondita sul potere di scelta che l'individuo può esercitare sulla propria mente e sul proprio corpo. Spinta dal desidero di indagare l'estensione di tale potere di scelta ho voluto analizzare le tematiche riguardanti “il corpo”, “l'individuo”, “la proprietà” e “l'autodeterminazione”. L'analisi è stata condotta individuando alcuni dei differenti significati che questi termini assumono nei diversi ambiti che la bioetica lambisce e mostrando, in particolare, la visione di tale realtà attraverso le lenti del giurista. A chi appartiene il corpo? Chi ha il potere di decidere su di esso? Il potere di scelta valica gli antichi i confini legati al corpo del paziente e coinvolge tessuti, organi e cellule staccati dal corpo umano, parti che un tempo erano considerati scarti operatori sono oggi divenuti tesori inestimabili per la ricerca. L'importanza assunta dai campioni biologici ha portato alla creazione di biobanche nelle quali sono raccolti, catalogati e il DNA studiato in campioni biologici Le biobanche riflettono le tensioni della bioetica e del biodititto. Lo studio delle biobanche riguarda, tra l'altro, la riceca dell'equilibrio tra le diverse esigenze meritevoli di tutela: in primo luogo il diritto alla privacy, diritto a che le “proprie informazioni” non vengano divulgate ed il diritto a non essere discriminato ed in secondo luogo le necessità dettate dalla ricerca e dalla scienza medica. Nel 2009 la rivista Times messo biobanche tra le 10 idee in grado di cambiare il mondo anche in considarazione della medicina personalizzata e del fatto che costituiscono una la speranza per la ricerca contro le malattie attuali e future.

Mixtures of colloidal rods and spheres in bulk and in confinement

When non-adsorbing polymers are added to an isotropic suspension of rod-like colloids, the colloids effectively attract each other via depletion forces. Monte Carlo simulations were performed to study the phase diagram of such rod-polymer mixtures. The colloidal rods were modelled as hard spherocylinders; the polymers were described as spheres of the same diameter as the rods. The polymers may overlap with no energy cost, while overlap of polymers and rods is forbidden. In this thesis the emphasis was on the depletion effects caused by the addition of spheres on the isotropic phase of rod-like particles. Although most of the present experimental studies consider systems close to or beyond the isotropic-nematic transition, the isotropic phase with depletion interactions turns out to be a not less interesting topic. First, the percolation problem was studied in canonical simulations of a system of hard rods and soft spheres, where the amount of depletant was kept low to prevent phase separation of the mixture. The lowering of the percolation threshold seen in experiment is confirmed to be due to the depletion interactions. The local changes in the structure of the fluid of rods, which were measured in the simulations, indicated that the depletion forces enhance local alignment and aggregation of the rods. Then, the phase diagram of isotropic-isotropic demixing of short spherocylinders was calculated using grand canonical ensemble simulations with successive umbrella sampling. Finite size scaling analysis allowed to estimate the location of the critical point. Also, estimates for the interfacial tension between the coexisting isotropic phases and analyses of its power-law behaviour on approach of the critical point are presented. The obtained phase diagram was compared to the predictions of the free volume theory. After an analysis of the bulk, the phase behaviour in confinement was studied. The critical point of gas-liquid demixing is shifted to higher concentrations of rods and smaller concentrations of spheres due to the formation of an orientationally ordered surface film. If the separation between the walls becomes very small, the critical point is shifted back to smaller concentrations of rods because the surface film breaks up. A method to calculate the contact angle of the liquid-gas interface with the wall is introduced and the wetting behaviour on the approach to the critical point is analysed.

The collapse of linear polyelectrolyte chains in a poor solvent: When does a collapsing polyelectrolyte collect its counter ions?

The collapse of linear polyelectrolyte chains in a poor solvent: When does a collapsing polyelectrolyte collect its counter ions? The collapse of polyions in a poor solvent is a complex system and is an active research subject in the theoretical polyelectrolyte community. The complexity is due to the subtle interplay between hydrophobic effects, electrostatic interactions, entropy elasticity, intrinsic excluded volume as well as specific counter-ion and co-ion properties. Long range Coulomb forces can obscure single molecule properties. The here presented approach is to use just a small amount of screening salt in combination with a very high sample dilution in order to screen intermolecular interaction whereas keeping intramolecular interaction as much as possible (polyelectrolyte concentration cp ≤ 12 mg/L, salt concentration; Cs = 10^-5 mol/L). This is so far not described in literature. During collapse, the polyion is subject to a drastic change in size along with strong reduction of free counterions in solution. Therefore light scattering was utilized to obtain the size of the polyion whereas a conductivity setup was developed to monitor the proceeding of counterion collection by the polyion. Partially quaternized PVP’s below and above the Manning limit were investigated and compared to the collapse of their uncharged precursor. The collapses were induced by an isorefractive solvent/non-solvent mixture consisting of 1-propanol and 2-pentanone, with nearly constant dielectric constant. The solvent quality for the uncharged polyion could be quantified which, for the first time, allowed the experimental investigation of the effect of electrostatic interaction prior and during polyion collapse. Given that the Manning parameter M for QPVP4.3 is as low as lB / c = 0.6 (lB the Bjerrum length and c the mean contour distance between two charges), no counterion binding should occur. However the Walden product reduces with first addition of non solvent and accelerates when the structural collapse sets in. Since the dielectric constant of the solvent remains virtually constant during the chain collapse, the counterion binding is entirely caused by the reduction in the polyion chain dimension. The collapse is shifted to lower wns with higher degrees of quaternization as the samples QPVP20 and QPVP35 show (M = 2.8 respectively 4.9). The combination of light scattering and conductivity measurement revealed for the first time that polyion chains already collect their counter ions well above the theta-dimension when the dimensions start to shrink. Due to only small amounts of screening salt, strong electrostatic interactions bias dynamic as well as static light scattering measurements. An extended Zimm formula was derived to account for this interaction and to obtain the real chain dimensions. The effective degree of dissociation g could be obtained semi quantitatively using this extrapolated static in combination with conductivity measurements. One can conclude the expansion factor a and the effective degree of ionization of the polyion to be mutually dependent. In the good solvent regime g of QPVP4.3, QPVP20 and QPVP35 exhibited a decreasing value in the order 1 > g4.3 > g20 > g35. The low values of g for QPVP20 and QPVP35 are assumed to be responsible for the prior collapse of the higher quaternized samples. Collapse theory predicts dipole-dipole attraction to increase accordingly and even predicts a collapse in the good solvent regime. This could be exactly observed for the QPVP35 sample. The experimental results were compared to a newly developed theory of uniform spherical collapse induced by concomitant counterion binding developed by M. Muthukumar and A. Kundagrami. The theory agrees qualitatively with the location of the phase boundary as well as the trend of an increasing expansion with an increase of the degree of quaternization. However experimental determined g for the samples QPVP4.3, QPVP20 and QPVP35 decreases linearly with the degree of quaternization whereas this theory predicts an almost constant value.

Ultra-low power WSNs: distributed signal processing and dynamic resource management

This thesis presents several data processing and compression techniques capable of addressing the strict requirements of wireless sensor networks. After introducing a general overview of sensor networks, the energy problem is introduced, dividing the different energy reduction approaches according to the different subsystem they try to optimize. To manage the complexity brought by these techniques, a quick overview of the most common middlewares for WSNs is given, describing in detail SPINE2, a framework for data processing in the node environment. The focus is then shifted on the in-network aggregation techniques, used to reduce data sent by the network nodes trying to prolong the network lifetime as long as possible. Among the several techniques, the most promising approach is the Compressive Sensing (CS). To investigate this technique, a practical implementation of the algorithm is compared against a simpler aggregation scheme, deriving a mixed algorithm able to successfully reduce the power consumption. The analysis moves from compression implemented on single nodes to CS for signal ensembles, trying to exploit the correlations among sensors and nodes to improve compression and reconstruction quality. The two main techniques for signal ensembles, Distributed CS (DCS) and Kronecker CS (KCS), are introduced and compared against a common set of data gathered by real deployments. The best trade-off between reconstruction quality and power consumption is then investigated. The usage of CS is also addressed when the signal of interest is sampled at a Sub-Nyquist rate, evaluating the reconstruction performance. Finally the group sparsity CS (GS-CS) is compared to another well-known technique for reconstruction of signals from an highly sub-sampled version. These two frameworks are compared again against a real data-set and an insightful analysis of the trade-off between reconstruction quality and lifetime is given.

Chemical, biochemical and microbiological indicators to assess soil quality in temperate agro-ecosystems

Soil is a critically important component of the earth’s biosphere. Developing agricultural production systems able to conserve soil quality is essential to guarantee the current and future capacity of soil to provide goods and services. This study investigates the potential of microbial and biochemical parameters to be used as early and sensitive soil quality indicators. Their ability to differentiate plots under contrasting fertilization regimes is evaluated based also on their sensitivity to seasonal fluctuations of environmental conditions and on their relationship with soil chemical parameters. Further, the study addresses some of the critical methodological aspects of microplate-based fluorimetric enzyme assays, in order to optimize assay conditions and evaluate their suitability to be used as a toll to asses soil quality. The study was based on a long-term field experiment established in 1966 in the Po valley (Italy). The soil was cropped with maize (Z. mays L.) and winter wheat (T. aestivum L.) and received no organic fertilization, crop residue or manure, in combination with increasing levels of mineral N fertilizer. The soil microbiota responded to manure amendment increasing it biomass and activity and changing its community composition. Crop residue effect was much more limited. Mineral N fertilization stimulated crop residue mineralization, shifted microbial community composition and influenced N and P cycling enzyme activities. Seasonal fluctuations of environmental factors affected the soil microbiota. However microbial and biochemical parameters seasonality did not hamper the identification of fertilization-induced effects. Soil microbial community abundance, function and composition appeared to be strongly related to soil organic matter content and composition, confirming the close link existing between these soil quality indicators. Microplate-based fluorimetric enzyme assays showed potential to be used as fast and throughput toll to asses soil quality, but required proper optimization of the assay conditions for a precise estimation of enzymes maximum potential activity.

Simulations of charge transport in organic compounds

To aid the design of organic semiconductors, we study the charge transport properties of organic liquid crystals, i.e. hexabenzocoronene and carbazole macrocycle, and single crystals, i.e. rubrene, indolocarbazole and benzothiophene derivatives (BTBT, BBBT). The aim is to find structure-property relationships linking the chemical structure as well as the morphology with the bulk charge carrier mobility of the compounds. To this end, molecular dynamics (MD) simulations are performed yielding realistic equilibrated morphologies. Partial charges and molecular orbitals are calculated based on single molecules in vacuum using quantum chemical methods. The molecular orbitals are then mapped onto the molecular positions and orientations, which allows calculation of the transfer integrals between nearest neighbors using the molecular orbital overlap method. Thus we obtain realistic transfer integral distributions and their autocorrelations. In case of organic crystals the differences between two descriptions of charge transport, namely semi-classical dynamics (SCD) in the small polaron limit and kinetic Monte Carlo (KMC) based on Marcus rates, are studied. The liquid crystals are investigated solely in the hopping limit. To simulate the charge dynamics using KMC, the centers of mass of the molecules are mapped onto lattice sites and the transfer integrals are used to compute the hopping rates. In the small polaron limit, where the electronic wave function is spread over a limited number of neighboring molecules, the Schroedinger equation is solved numerically using a semi-classical approach. The results are compared for the different compounds and methods and, where available, with experimental data. The carbazole macrocycles form columnar structures arranged on a hexagonal lattice with side chains facing inwards, so columns can closely approach each other allowing inter-columnar and thus three-dimensional transport. When taking only intra-columnar transport into account, the mobility is orders of magnitude lower than in the three-dimensional case. BTBT is a promising material for solution-processed organic field-effect transistors. We are able to show that, on the time-scales of charge transport, static disorder due to slow side chain motions is the main factor determining the mobility. The resulting broad transfer integral distributions modify the connectivity of the system but sufficiently many fast percolation paths remain for the charges. Rubrene, indolocarbazole and BBBT are examples of crystals without significant static disorder. The high mobility of rubrene is explained by two main features: first, the shifted cofacial alignment of its molecules, and second, the high center of mass vibrational frequency. In comparsion to SCD, only KMC based on Marcus rates is capable of describing neighbors with low coupling and of taking static disorder into account three-dimensionally. Thus it is the method of choice for crystalline systems dominated by static disorder. However, it is inappropriate for the case of strong coupling and underestimates the mobility of well-ordered crystals. SCD, despite its one-dimensionality, is valuable for crystals with strong coupling and little disorder. It also allows correct treatment of dynamical effects, such as intermolecular vibrations of the molecules. Rate equations are incapable of this, because simulations are performed on static snapshots. We have thus shown strengths and weaknesses of two state of the art models used to study charge transport in organic compounds, partially developed a program to compute and visualize transfer integral distributions and other charge transport properties, and found structure-mobility relations for several promising organic semiconductors.