Electron Interactions with Disulfide Bridges

Because of its electronic properties, sulfur plays a major role in a variety of metabolic processes and, more in general, in the chemistry of life. In particular, S-S bridges between cysteines are present in the amino acid backbone of proteins. Protein disulfur radical anions may decay following different paths through competing intra and intermolecular routes, including bond cleavage, disproportionation, protein-protein cross linking, and electron transfer. Indeed, mass spectrometry ECD (electron capture dissociation massspectroscopy) studies have shown that capture of low-energy (<0.2 eV) electrons by multiply protonated proteins is followed by dissociation of S-S bonds holding two peptide chains together. In view of the importance of organic sulfur chemistry, we report on electron interactions with disulphide bridges. To study these interactions we used as prototypes the molecules dimethyl sulfide [(CH3)2S] and dimethyl disulfide [(H3C)S2(CH3)]. We seek to better understand the electron-induced cleavage of the disulfide bond. To explore dissociative processes we performed electron scattering calculations with the Schwinger Multichannel Method with pseudopotentials (SMCPP), recently parallelized with OpenMP directives and optimized with subroutines for linear algebra (BLAS) and LAPACK routines. Elastic cross sections obtained for different S-S bond lengths indicate stabilization of the anion formed by electron attachment to a σ*SS antibonding orbital, such that dissociation would be expected.

Magnetic Properties of γ - Fe2O3 Nanoparticles at the Verge of Nucleation Process.

A low-energy new method based in a one-step synthesis at room temperature produces very small maghemite nanopar ticles. The fast neutralization reaction (co-precipitation) of a ferric solution (FeCl3 aqueous) in a basic medium (NH4OH concentrated) produces an intermediate phase, presumably two-line ferrihydrite, that in oxidizing conditions is transformed to maghemite nanopar ticles. That “primordial soup” is characterized by small atom arrangements that are the base for maghemite tiny crystals. The final product of the reaction was characterized by X-ray diffraction, high-resolution transmission electron microscopy, X-ray absorption fine structure, Mössbauer spectroscopy, and magnetometry.

Modeling the cosmological co-evolution of supermassive black holes and galaxies

In this Thesis, we investigate the cosmological co-evolution of supermassive black holes (BHs), Active Galactic Nuclei (AGN) and their hosting dark matter (DM) halos and galaxies, within the standard CDM scenario. We analyze both analytic, semi-analytic and hybrid techniques and use the most recent observational data available to constrain the assumptions underlying our models. First, we focus on very simple analytic models where the assembly of BHs is directly related to the merger history of DM haloes. For this purpose, we implement the two original analytic models of Wyithe & Loeb 2002 and Wyithe & Loeb 2003, compare their predictions to the AGN luminosity function and clustering data, and discuss possible modifications to the models that improve the match to the observation. Then we study more sophisticated semi-analytic models in which however the baryonic physics is neglected as well. Finally we improve the hybrid simulation of De Lucia & Blaizot 2007, adding new semi-analytical prescriptions to describe the BH mass accretion rate during each merger event and its conversion into radiation, and compare the derived BH scaling relations, fundamental plane and mass function, and the AGN luminosity function with observations. All our results support the following scenario: • The cosmological co-evolution of BHs, AGN and galaxies can be well described within the CDM model. • At redshifts z & 1, the evolution history of DM halo fully determines the overall properties of the BH and AGN populations. The AGN emission is triggered mainly by DM halo major mergers and, on average, AGN shine at their Eddington luminosity. • At redshifts z . 1, BH growth decouples from halo growth. Galaxy major mergers cannot constitute the only trigger to accretion episodes in this phase. • When a static hot halo has formed around a galaxy, a fraction of the hot gas continuously accretes onto the central BH, causing a low-energy “radio” activity at the galactic centre, which prevents significant gas cooling and thus limiting the mass of the central galaxies and quenching the star formation at late time. • The cold gas fraction accreted by BHs at high redshifts seems to be larger than at low redshifts.

Metrologia dei campi di radiazioni di bassa energia

The conversion coefficients from air kerma to ICRU operational dose equivalent quantities for ENEA’s realization of the X-radiation qualities L10-L35 of the ISO “Low Air Kerma rate” series (L), N10-N40 of the ISO “Narrow spectrum” series (N) and H10-H60 of the ISO “High Air-kerma rate” (H) series and two beams at 5 kV and 7.5 kV were determined by utilising X-ray spectrum measurements. The pulse-height spectra were measured using a planar high-purity germanium spectrometer (HPGe) and unfolded to fluence spectra using a stripping procedure then validate with using Monte Carlo generated data of the spectrometer response. HPGe portable detector has a diameter of 8.5 mm and a thickness of 5 mm. The entrance window of the crystal is collimated by a 0.5 mm thick Aluminum ring to an open diameter of 6.5 mm. The crystal is mounted at a distance of 5 mm from the Berillium window (thickness 25.4 micron). The Monte Carlo method (MCNP-4C) was used to calculate the efficiency, escape and Compton curves of a planar high-purity germanium detector (HPGe) in the 5-60 keV energy. These curves were used for the determination of photon spectra produced by the X-ray machine SEIFERT ISOVOLT 160 kV in order to allow a precise characterization of photon beams in the low energy range, according to the ISO 4037. The detector was modelled with the MCNP computer code and validated with experimental data. To verify the measuring and the stripping procedure, the first and the second half-value layers and the air kerma rate were calculated from the counts spectra and compared with the values measured using an a free-air ionization chamber. For each radiation quality, the spectrum was characterized by the parameters given in ISO 4037-1. The conversion coefficients from the air kerma to the ICRU operational quantities Hp(10), Hp(0.07), H’(0.07) and H*(10) were calculated using monoenergetic conversion coefficients. The results are discussed with respect to ISO 4037-4, and compared with published results for low-energy X-ray spectra. The main motivation for this work was the lack of a treatment of the low photon energy region (from a few keV up to about 60 keV).

Progetto di reti Sensori Wireless e tecniche di Fusione Sensoriale

Ambient Intelligence (AmI) envisions a world where smart, electronic environments are aware and responsive to their context. People moving into these settings engage many computational devices and systems simultaneously even if they are not aware of their presence. AmI stems from the convergence of three key technologies: ubiquitous computing, ubiquitous communication and natural interfaces. The dependence on a large amount of fixed and mobile sensors embedded into the environment makes of Wireless Sensor Networks one of the most relevant enabling technologies for AmI. WSN are complex systems made up of a number of sensor nodes, simple devices that typically embed a low power computational unit (microcontrollers, FPGAs etc.), a wireless communication unit, one or more sensors and a some form of energy supply (either batteries or energy scavenger modules). Low-cost, low-computational power, low energy consumption and small size are characteristics that must be taken into consideration when designing and dealing with WSNs. In order to handle the large amount of data generated by a WSN several multi sensor data fusion techniques have been developed. The aim of multisensor data fusion is to combine data to achieve better accuracy and inferences than could be achieved by the use of a single sensor alone. In this dissertation we present our results in building several AmI applications suitable for a WSN implementation. The work can be divided into two main areas: Multimodal Surveillance and Activity Recognition. Novel techniques to handle data from a network of low-cost, low-power Pyroelectric InfraRed (PIR) sensors are presented. Such techniques allow the detection of the number of people moving in the environment, their direction of movement and their position. We discuss how a mesh of PIR sensors can be integrated with a video surveillance system to increase its performance in people tracking. Furthermore we embed a PIR sensor within the design of a Wireless Video Sensor Node (WVSN) to extend its lifetime. Activity recognition is a fundamental block in natural interfaces. A challenging objective is to design an activity recognition system that is able to exploit a redundant but unreliable WSN. We present our activity in building a novel activity recognition architecture for such a dynamic system. The architecture has a hierarchical structure where simple nodes performs gesture classification and a high level meta classifiers fuses a changing number of classifier outputs. We demonstrate the benefit of such architecture in terms of increased recognition performance, and fault and noise robustness. Furthermore we show how we can extend network lifetime by performing a performance-power trade-off. Smart objects can enhance user experience within smart environments. We present our work in extending the capabilities of the Smart Micrel Cube (SMCube), a smart object used as tangible interface within a tangible computing framework, through the development of a gesture recognition algorithm suitable for this limited computational power device. Finally the development of activity recognition techniques can greatly benefit from the availability of shared dataset. We report our experience in building a dataset for activity recognition. Such dataset is freely available to the scientific community for research purposes and can be used as a testbench for developing, testing and comparing different activity recognition techniques.

Photoproduktion neutraler Pionen am Proton mit linear polarisierten Photonen im Bereich der Schwelle

Diese Arbeit beschreibt ein Experiment zur Photoproduktionneutraler Pionen am Proton im Schwellenbereich. DurchVerwendung linear polarisierter Photonen konnte neben dentotalen und differentiellen Wirkungsquerschnitten zum erstenMal die Photonasymmetrie nahe der Schwelle gemessen werden.Besonderes Interesse galt dem aus diesen physikalischenObservablen bestimmbaren s-Wellen-Multipol E0+ sowie der erstmaligen Bestimmung aller drei p-Wellen-KombinationenP1, P2 und P3 im Bereich der Schwelle.Das Experiment wurde 1995/1996 am ElektronenbeschleunigerMAMI (Mainzer Mikrotron) der Universität Mainz durchgeführt.Durch Verwendung eines Diamanten als Bremsstrahltarget fürdie Elektronen wurden über den Prozeß der kohärentenBremsstrahlung linear polarisierte Photonen erzeugt. DieEnergie der Photonen wurde über die Messung der Energie der gestreuten Elektronen in der MainzerPhotonenmarkierungsanlage bestimmt. Der Detektor TAPS, eineAnordnung aus 504 BaF2-Modulen, war um einFlüssigwasserstofftarget aufgebaut. In den Modulen wurdendie im Target produzierten neutralen Pionen über ihrenZerfall in zwei Photonen nachgewiesen.Die totalen und differentiellen Wirkungsquerschnitte wurdenim Energiebereich zwischen der Schwelle von 144.7 MeV und168 MeV gemessen. Die erstmals gemessene Photonasymmetriefür 159.5 MeV ist positiv und hat einen Wert von+0.217+/-0.046 für einen Polarwinkel von 90 Grad. Der Multipol E0+ und die drei p-Wellen-Kombinationen wurden andie physikalischen Observablen über zwei unterschiedlicheMethoden angepaßt, die übereinstimmende Ergebnisselieferten. Die Vorhersagen der Niederenergietheoreme derchiralen Störungstheorie für P1 und P2 stimmen beiEinbeziehung der statistischen und systematischen Fehler mitden experimentellen Werten überein.

Mesonic chiral perturbation theory - odd intrinsic parity sector

In der vorliegenden Dissertation werden zwei verschiedene Aspekte des Sektors ungerader innerer Parität der mesonischen chiralen Störungstheorie (mesonische ChPT) untersucht. Als erstes wird die Ein-Schleifen-Renormierung des führenden Terms, der sog. Wess-Zumino-Witten-Wirkung, durchgeführt. Dazu muß zunächst der gesamte Ein-Schleifen-Anteil der Theorie mittels Sattelpunkt-Methode extrahiert werden. Im Anschluß isoliert man alle singulären Ein-Schleifen-Strukturen im Rahmen der Heat-Kernel-Technik. Zu guter Letzt müssen diese divergenten Anteile absorbiert werden. Dazu benötigt man eine allgemeinste anomale Lagrange-Dichte der Ordnung O(p^6), welche systematisch entwickelt wird. Erweitert man die chirale Gruppe SU(n)_L x SU(n)_R auf SU(n)_L x SU(n)_R x U(1)_V, so kommen zusätzliche Monome ins Spiel. Die renormierten Koeffizienten dieser Lagrange-Dichte, die Niederenergiekonstanten (LECs), sind zunächst freie Parameter der Theorie, die individuell fixiert werden müssen. Unter Betrachtung eines komplementären vektormesonischen Modells können die Amplituden geeigneter Prozesse bestimmt und durch Vergleich mit den Ergebnissen der mesonischen ChPT eine numerische Abschätzung einiger LECs vorgenommen werden. Im zweiten Teil wird eine konsistente Ein-Schleifen-Rechnung für den anomalen Prozeß (virtuelles) Photon + geladenes Kaon -> geladenes Kaon + neutrales Pion durchgeführt. Zur Kontrolle unserer Resultate wird eine bereits vorhandene Rechnung zur Reaktion (virtuelles) Photon + geladenes Pion -> geladenes Pion + neutrales Pion reproduziert. Unter Einbeziehung der abgeschätzten Werte der jeweiligen LECs können die zugehörigen hadronischen Strukturfunktionen numerisch bestimmt und diskutiert werden.

Optische Eigenschaften von Pi-konjugierten Modellsystemen

Der erste Teil der vorliegenden Arbeit beschäftigt sich mit der Modifikation der spontanen Emission im Strong Coupling Regime. Hierzu wurden geeignete optische, organische 'Halbleiter'-Mikroresonatoren präpariert.Zunächst wurde das verwendete optisch aktive Material, das J-Aggregat PIC, spektroskopisch charakterisiert. In Transmissionsmessungen an den Mikroresonatoren wurden Vakuum-Rabi-Splitting-Energien zwischen 26 und 52 meV bestimmt. Es wurde die Abhängigkeit der Vakuum-Rabi-Splitting-Energie von der räumlichen Position der optisch aktiven Schicht innerhalb des Mikroresonators untersucht. Durch eine Simulation konnte nachgewiesen werden, daß der Grund für die Asymmetrie des Rabi-Splittings bei einer Verstimmung von 0 meV durch die Asymmetrie des Absorptionsspektrums des optisch aktiven Materials gegeben ist. Weiterhin wurde die Photolumineszenz der Mikroresonatoren untersucht. Es konnte in temperaturabhängigen Messungen gezeigt werden, daß die hochenergetische Bande gegenüber der niederenergetischen Bande bei steigender Temperatur entsprechend einer Boltzmann-Verteilung stärker besetzt wird.Im zweiten Teil der Arbeit wurden die optischen Eigenschaften von dünnen Filmen N´N´Bis (2,6-xylyl)perylene-3,4:9,10-bis(dicarboximide) (DPP-PTCDI) abhängig von der Schichtdicke untersucht. Die Photolumineszenzspektren der dünnen Filme wurden mit zunehmender Dicke durch eine neue Bande bei kleineren Energien bestimmt. Diese Bande kann mit der Emission aus Fallenzuständen erklärt werden. Durch Photolumineszenz-Anregungsspektroskopie konnte gezeigt werden, daß die Fallenzustände auch im Grundzustand existieren. Exzimere können daher als Ursache ausgeschlossen werden.

Hybrid Methods for Resource Allocation and Scheduling Problems in Deterministic and Stochastic Environments

This work presents exact, hybrid algorithms for mixed resource Allocation and Scheduling problems; in general terms, those consist into assigning over time finite capacity resources to a set of precedence connected activities. The proposed methods have broad applicability, but are mainly motivated by applications in the field of Embedded System Design. In particular, high-performance embedded computing recently witnessed the shift from single CPU platforms with application-specific accelerators to programmable Multi Processor Systems-on-Chip (MPSoCs). Those allow higher flexibility, real time performance and low energy consumption, but the programmer must be able to effectively exploit the platform parallelism. This raises interest in the development of algorithmic techniques to be embedded in CAD tools; in particular, given a specific application and platform, the objective if to perform optimal allocation of hardware resources and to compute an execution schedule. On this regard, since embedded systems tend to run the same set of applications for their entire lifetime, off-line, exact optimization approaches are particularly appealing. Quite surprisingly, the use of exact algorithms has not been well investigated so far; this is in part motivated by the complexity of integrated allocation and scheduling, setting tough challenges for ``pure'' combinatorial methods. The use of hybrid CP/OR approaches presents the opportunity to exploit mutual advantages of different methods, while compensating for their weaknesses. In this work, we consider in first instance an Allocation and Scheduling problem over the Cell BE processor by Sony, IBM and Toshiba; we propose three different solution methods, leveraging decomposition, cut generation and heuristic guided search. Next, we face Allocation and Scheduling of so-called Conditional Task Graphs, explicitly accounting for branches with outcome not known at design time; we extend the CP scheduling framework to effectively deal with the introduced stochastic elements. Finally, we address Allocation and Scheduling with uncertain, bounded execution times, via conflict based tree search; we introduce a simple and flexible time model to take into account duration variability and provide an efficient conflict detection method. The proposed approaches achieve good results on practical size problem, thus demonstrating the use of exact approaches for system design is feasible. Furthermore, the developed techniques bring significant contributions to combinatorial optimization methods.

Sistemi riconfigurabili a basso consumo per applicazioni di monitoraggio distribuito

The term Ambient Intelligence (AmI) refers to a vision on the future of the information society where smart, electronic environment are sensitive and responsive to the presence of people and their activities (Context awareness). In an ambient intelligence world, devices work in concert to support people in carrying out their everyday life activities, tasks and rituals in an easy, natural way using information and intelligence that is hidden in the network connecting these devices. This promotes the creation of pervasive environments improving the quality of life of the occupants and enhancing the human experience. AmI stems from the convergence of three key technologies: ubiquitous computing, ubiquitous communication and natural interfaces. Ambient intelligent systems are heterogeneous and require an excellent cooperation between several hardware/software technologies and disciplines, including signal processing, networking and protocols, embedded systems, information management, and distributed algorithms. Since a large amount of fixed and mobile sensors embedded is deployed into the environment, the Wireless Sensor Networks is one of the most relevant enabling technologies for AmI. WSN are complex systems made up of a number of sensor nodes which can be deployed in a target area to sense physical phenomena and communicate with other nodes and base stations. These simple devices typically embed a low power computational unit (microcontrollers, FPGAs etc.), a wireless communication unit, one or more sensors and a some form of energy supply (either batteries or energy scavenger modules). WNS promises of revolutionizing the interactions between the real physical worlds and human beings. Low-cost, low-computational power, low energy consumption and small size are characteristics that must be taken into consideration when designing and dealing with WSNs. To fully exploit the potential of distributed sensing approaches, a set of challengesmust be addressed. Sensor nodes are inherently resource-constrained systems with very low power consumption and small size requirements which enables than to reduce the interference on the physical phenomena sensed and to allow easy and low-cost deployment. They have limited processing speed,storage capacity and communication bandwidth that must be efficiently used to increase the degree of local ”understanding” of the observed phenomena. A particular case of sensor nodes are video sensors. This topic holds strong interest for a wide range of contexts such as military, security, robotics and most recently consumer applications. Vision sensors are extremely effective for medium to long-range sensing because vision provides rich information to human operators. However, image sensors generate a huge amount of data, whichmust be heavily processed before it is transmitted due to the scarce bandwidth capability of radio interfaces. In particular, in video-surveillance, it has been shown that source-side compression is mandatory due to limited bandwidth and delay constraints. Moreover, there is an ample opportunity for performing higher-level processing functions, such as object recognition that has the potential to drastically reduce the required bandwidth (e.g. by transmitting compressed images only when something ‘interesting‘ is detected). The energy cost of image processing must however be carefully minimized. Imaging could play and plays an important role in sensing devices for ambient intelligence. Computer vision can for instance be used for recognising persons and objects and recognising behaviour such as illness and rioting. Having a wireless camera as a camera mote opens the way for distributed scene analysis. More eyes see more than one and a camera system that can observe a scene from multiple directions would be able to overcome occlusion problems and could describe objects in their true 3D appearance. In real-time, these approaches are a recently opened field of research. In this thesis we pay attention to the realities of hardware/software technologies and the design needed to realize systems for distributed monitoring, attempting to propose solutions on open issues and filling the gap between AmI scenarios and hardware reality. The physical implementation of an individual wireless node is constrained by three important metrics which are outlined below. Despite that the design of the sensor network and its sensor nodes is strictly application dependent, a number of constraints should almost always be considered. Among them: • Small form factor to reduce nodes intrusiveness. • Low power consumption to reduce battery size and to extend nodes lifetime. • Low cost for a widespread diffusion. These limitations typically result in the adoption of low power, low cost devices such as low powermicrocontrollers with few kilobytes of RAMand tenth of kilobytes of program memory with whomonly simple data processing algorithms can be implemented. However the overall computational power of the WNS can be very large since the network presents a high degree of parallelism that can be exploited through the adoption of ad-hoc techniques. Furthermore through the fusion of information from the dense mesh of sensors even complex phenomena can be monitored. In this dissertation we present our results in building several AmI applications suitable for a WSN implementation. The work can be divided into two main areas:Low Power Video Sensor Node and Video Processing Alghoritm and Multimodal Surveillance . Low Power Video Sensor Nodes and Video Processing Alghoritms In comparison to scalar sensors, such as temperature, pressure, humidity, velocity, and acceleration sensors, vision sensors generate much higher bandwidth data due to the two-dimensional nature of their pixel array. We have tackled all the constraints listed above and have proposed solutions to overcome the current WSNlimits for Video sensor node. We have designed and developed wireless video sensor nodes focusing on the small size and the flexibility of reuse in different applications. The video nodes target a different design point: the portability (on-board power supply, wireless communication), a scanty power budget (500mW),while still providing a prominent level of intelligence, namely sophisticated classification algorithmand high level of reconfigurability. We developed two different video sensor node: The device architecture of the first one is based on a low-cost low-power FPGA+microcontroller system-on-chip. The second one is based on ARM9 processor. Both systems designed within the above mentioned power envelope could operate in a continuous fashion with Li-Polymer battery pack and solar panel. Novel low power low cost video sensor nodes which, in contrast to sensors that just watch the world, are capable of comprehending the perceived information in order to interpret it locally, are presented. Featuring such intelligence, these nodes would be able to cope with such tasks as recognition of unattended bags in airports, persons carrying potentially dangerous objects, etc.,which normally require a human operator. Vision algorithms for object detection, acquisition like human detection with Support Vector Machine (SVM) classification and abandoned/removed object detection are implemented, described and illustrated on real world data. Multimodal surveillance: In several setup the use of wired video cameras may not be possible. For this reason building an energy efficient wireless vision network for monitoring and surveillance is one of the major efforts in the sensor network community. Energy efficiency for wireless smart camera networks is one of the major efforts in distributed monitoring and surveillance community. For this reason, building an energy efficient wireless vision network for monitoring and surveillance is one of the major efforts in the sensor network community. The Pyroelectric Infra-Red (PIR) sensors have been used to extend the lifetime of a solar-powered video sensor node by providing an energy level dependent trigger to the video camera and the wireless module. Such approach has shown to be able to extend node lifetime and possibly result in continuous operation of the node.Being low-cost, passive (thus low-power) and presenting a limited form factor, PIR sensors are well suited for WSN applications. Moreover techniques to have aggressive power management policies are essential for achieving long-termoperating on standalone distributed cameras needed to improve the power consumption. We have used an adaptive controller like Model Predictive Control (MPC) to help the system to improve the performances outperforming naive power management policies.

Dispersion approach to real and virtual Compton scattering

In recent years, new precision experiments have become possible withthe high luminosity accelerator facilities at MAMIand JLab, supplyingphysicists with precision data sets for different hadronic reactions inthe intermediate energy region, such as pion photo- andelectroproduction and real and virtual Compton scattering.By means of the low energy theorem (LET), the global properties of thenucleon (its mass, charge, and magnetic moment) can be separated fromthe effects of the internal structure of the nucleon, which areeffectively described by polarizabilities. Thepolarizabilities quantify the deformation of the charge andmagnetization densities inside the nucleon in an applied quasistaticelectromagnetic field. The present work is dedicated to develop atool for theextraction of the polarizabilities from these precise Compton data withminimum model dependence, making use of the detailed knowledge of pionphotoproduction by means of dispersion relations (DR). Due to thepresence of t-channel poles, the dispersion integrals for two ofthe six Compton amplitudes diverge. Therefore, we have suggested to subtract the s-channel dispersion integrals at zero photon energy($nu=0$). The subtraction functions at $nu=0$ are calculated through DRin the momentum transfer t at fixed $nu=0$, subtracted at t=0. For this calculation, we use the information about the t-channel process, $gammagammatopipito Nbar{N}$. In this way, four of thepolarizabilities can be predicted using the unsubtracted DR in the $s$-channel. The other two, $alpha-beta$ and $gamma_pi$, are free parameters in ourformalism and can be obtained from a fit to the Compton data.We present the results for unpolarized and polarized RCS observables,%in the kinematics of the most recent experiments, and indicate anenhanced sensitivity to the nucleon polarizabilities in theenergy range between pion production threshold and the $Delta(1232)$-resonance.newlineindentFurthermore,we extend the DR formalism to virtual Compton scattering (radiativeelectron scattering off the nucleon), in which the concept of thepolarizabilities is generalized to the case of avirtual initial photon by introducing six generalizedpolarizabilities (GPs). Our formalism provides predictions for the fourspin GPs, while the two scalar GPs $alpha(Q^2)$ and $beta(Q^2)$ have to befitted to the experimental data at each value of $Q^2$.We show that at energies betweenpion threshold and the $Delta(1232)$-resonance position, thesensitivity to the GPs can be increased significantly, as compared tolow energies, where the LEX is applicable. Our DR formalism can be used for analysing VCS experiments over a widerange of energy and virtuality $Q^2$, which allows one to extract theGPs from VCS data in different kinematics with a minimum of model dependence.

Liquid crystalline oligofluorenes and their derivatives

Homo-oligofluorenes (OFn), polyfluorenes (PF2/6) and oligofluorenes with one fluorenenone group in the center (OFnK) were synthesized. They were used as model compounds to understand of the structure-property relationships of polyfluorenes and the origin of the green emission in the photoluminescence (after photooxidation of the PFs) and the electroluminescence (EL) spectra. The electronic, electrochemical properties, thermal behavior, supramolecular self-assembly, and photophysical properties of OFn, PF2/6 and OFnK were investigated. Oligofluorenes with 2-ethylhexyl side chain (OF2-OF7) from the dimer up to the heptamer were prepared by a series of stepwise transition metal mediated Suzuki and Yamamoto coupling reactions. Polyfluorene was synthesized by Yamamoto coupling of 2,7-dibromo-9,9-bis(2-ethylhexyl)fluorene. Oligofluorenes with one fluorenone group in the center (OF3K, OF5K, OF7K) were prepared by Suzuki coupling between the monoboronic fluorenyl monomer, dimer, trimer and 2, 7-dibromofluorenone. The electrochemical and electronic properties of homo-oligofluorenes (OFn) were systematically studied by several combined techniques such as cyclic voltammetry, differential pulse voltammetry, UV-vis absorption spectroscopy, steady and time-resolved fluorescence spectroscopy. It was found that the oligofluorenes behave like classical conjugated oligomers, i.e., with the increase of the chain-length, the corresponding oxidation potential, the absorption and emission maximum, ionization potential, electron affinity, band gap and the photoluminescence lifetime displayed a very good linear relation with the reciprocal number of the fluorene units (1/n). The extrapolation of these linear relations to infinite chain length predicted the electrochemical and electronic properties of the corresponding polyfluorenes. The thermal behavior, single-crystal structure and supramolecular packing, alignment properties, and molecular dynamics of the homo-oligofluorenes (OFn) up to the polymer were studied using techniques such as TGA, DSC, WAXS, POM and DS. The OFn from tetramer to heptamer show a smectic liquid crystalline phase with clearly defined isotropization temperature. The oligomers do show a glass transition which exhibits n-1 dependence and allows extrapolation to a hypothetical glass transition of the polymer at around 64 °C. A smectic packing and helix-like conformation for the oligofluorenes from tetramer to heptamer was supported by WAXS experiments, simulation, and single-crystal structure of some oligofluorene derivatives. Oligofluorenes were aligned more easily than the corresponding polymer, and the alignability increased with the molecular length from tetramer to heptamer. The molecular dynamics in a series of oligofluorenes up to the polymer was studied using dielectric spectroscopy. The photophysical properties of OFn and PF2/6 were investigated by the steady-state spectra (UV-vis absorption and fluorescence spectra) and time-resolved fluorescence spectra both in solution and thin film. The time-resolved fluorescence spectra of the oligofluorenes were measured by streak camera and gate detection technique. The lifetime of the oligofluorenes decreased with the extension of the chain-length. No green emission was observed in CW, prompt and delayed fluorescence for oligofluorenes in m-THF and film at RT and 77K. Phosphorescence was observed for oligofluorenes in frozen dilute m-THF solution at 77K and its lifetime increased with length of oligofluorenes. A linear relation was obtained for triplet energy and singlet energy as a function of the reciprocal degree of polymerization, and the singlet-triplet energy gap (S1-T1) was found to decrease with the increase of degree of polymerization. Oligofluorenes with one fluorenone unit at the center were used as model compounds to understand the origin of the low-energy (“green”) emission band in the photoluminescence and electroluminescence spectra of polyfluorenes. Their electrochemical properties were investigated by CV, and the ionization potential (Ip) and electron affinity (Ea) were calculated from the onset of oxidation and reduction of OFnK. The photophysical properties of OFnK were studied in dilute solution and thin film by steady-state spectra and time-resolved fluorescence spectra. A strong green emission accompanied with a weak blue emission were obtained in solution and only green emission was observed on film. The strong green emission of OFnK suggested that rapid energy transfer takes place from higher energy sites (fluorene segments) to lower energy sites (fluorenone unit) prior to the radiative decay of the excited species. The fluorescence spectra of OFnK also showed solvatochromism. Monoexponential decay behaviour was observed by time-resolved fluorescence measurements. In addition, the site-selective excitation and concentration dependence of the fluorescence spectra were investigated. The ratio of green and blue emission band intensities increases with the increase of the concentration. The observed strong concentration dependence of the green emission band in solution suggests that increased interchain interactions among the fluorenone-containing oligofluorene chain enhanced the emission from the fluorenone defects at higher concentration. On the other hand, the mono-exponential decay behaviour and power dependence were not influenced significantly by the concentration. We have ruled out the possibility that the green emission band originates from aggregates or excimer formation. Energy transfer was further investigated using a model system of a polyfluorene doped by OFnK. Förster-type energy transfer took place from PF2/6 to OFnK, and the energy transfer efficiency increased with increasing of the concentration of OFnK. Efficient funneling of excitation energy from the high-energy fluorene segments to the low-energy fluorenone defects results from energy migration by hopping of excitations along a single polymer chain until they are trapped on the fluorenone defects on that chain or transferred onto neighbouring chains by Förster-type interchain energy transfer process. These results imply that the red-shifted emission in polyfluorenes can originate from (usually undesirable) keto groups at the bridging carbon atoms-especially if the samples have been subject to photo- or electro-oxidation or if fluorenone units are present due to an improper purification of the monomers prior to polymerization.

Echtzeitsuche nach Neutrinoausbrüchen von Supernovae mit dem AMANDA-II-Detektor

Der AMANDA-II Detektor ist primär für den richtungsaufgelösten Nachweis hochenergetischer Neutrinos konzipiert. Trotzdem können auch niederenergetische Neutrinoausbrüche, wie sie von Supernovae erwartet werden, mit hoher Signifikanz nachgewiesen werden, sofern sie innerhalb der Milchstraße stattfinden. Die experimentelle Signatur im Detektor ist ein kollektiver Anstieg der Rauschraten aller optischen Module. Zur Abschätzung der Stärke des erwarteten Signals wurden theoretische Modelle und Simulationen zu Supernovae und experimentelle Daten der Supernova SN1987A studiert. Außerdem wurden die Sensitivitäten der optischen Module neu bestimmt. Dazu mussten für den Fall des südpolaren Eises die Energieverluste geladener Teilchen untersucht und eine Simulation der Propagation von Photonen entwickelt werden. Schließlich konnte das im Kamiokande-II Detektor gemessene Signal auf die Verhältnisse des AMANDA-II Detektors skaliert werden. Im Rahmen dieser Arbeit wurde ein Algorithmus zur Echtzeit-Suche nach Signalen von Supernovae als Teilmodul der Datennahme implementiert. Dieser beinhaltet diverse Verbesserungen gegenüber der zuvor von der AMANDA-Kollaboration verwendeten Version. Aufgrund einer Optimierung auf Rechengeschwindigkeit können nun mehrere Echtzeit-Suchen mit verschiedenen Analyse-Zeitbasen im Rahmen der Datennahme simultan laufen. Die Disqualifikation optischer Module mit ungeeignetem Verhalten geschieht in Echtzeit. Allerdings muss das Verhalten der Module zu diesem Zweck anhand von gepufferten Daten beurteilt werden. Dadurch kann die Analyse der Daten der qualifizierten Module nicht ohne eine Verzögerung von etwa 5 Minuten geschehen. Im Falle einer erkannten Supernova werden die Daten für die Zeitdauer mehrerer Minuten zur späteren Auswertung in 10 Millisekunden-Intervallen archiviert. Da die Daten des Rauschverhaltens der optischen Module ansonsten in Intervallen von 500 ms zur Verfgung stehen, ist die Zeitbasis der Analyse in Einheiten von 500 ms frei wählbar. Im Rahmen dieser Arbeit wurden drei Analysen dieser Art am Südpol aktiviert: Eine mit der Zeitbasis der Datennahme von 500 ms, eine mit der Zeitbasis 4 s und eine mit der Zeitbasis 10 s. Dadurch wird die Sensitivität für Signale maximiert, die eine charakteristische exponentielle Zerfallszeit von 3 s aufweisen und gleichzeitig eine gute Sensitivität über einen weiten Bereich exponentieller Zerfallszeiten gewahrt. Anhand von Daten der Jahre 2000 bis 2003 wurden diese Analysen ausführlich untersucht. Während die Ergebnisse der Analyse mit t = 500 ms nicht vollständig nachvollziehbare Ergebnisse produzierte, konnten die Resultate der beiden Analysen mit den längeren Zeitbasen durch Simulationen reproduziert und entsprechend gut verstanden werden. Auf der Grundlage der gemessenen Daten wurden die erwarteten Signale von Supernovae simuliert. Aus einem Vergleich zwischen dieser Simulation den gemessenen Daten der Jahre 2000 bis 2003 und der Simulation des erwarteten statistischen Untergrunds kann mit einem Konfidenz-Niveau von mindestens 90 % gefolgert werden, dass in der Milchstraße nicht mehr als 3.2 Supernovae pro Jahr stattfinden. Zur Identifikation einer Supernova wird ein Ratenanstieg mit einer Signifikanz von mindestens 7.4 Standardabweichungen verlangt. Die Anzahl erwarteter Ereignisse aus dem statistischen Untergrund beträgt auf diesem Niveau weniger als ein Millionstel. Dennoch wurde ein solches Ereignis gemessen. Mit der gewählten Signifikanzschwelle werden 74 % aller möglichen Vorläufer-Sterne von Supernovae in der Galaxis überwacht. In Kombination mit dem letzten von der AMANDA-Kollaboration veröffentlicheten Ergebnis ergibt sich sogar eine obere Grenze von nur 2.6 Supernovae pro Jahr. Im Rahmen der Echtzeit-Analyse wird für die kollektive Ratenüberhöhung eine Signifikanz von mindestens 5.5 Standardabweichungen verlangt, bevor eine Meldung über die Detektion eines Supernova-Kandidaten verschickt wird. Damit liegt der überwachte Anteil Sterne der Galaxis bei 81 %, aber auch die Frequenz falscher Alarme steigt auf bei etwa 2 Ereignissen pro Woche. Die Alarm-Meldungen werden über ein Iridium-Modem in die nördliche Hemisphäre übertragen, und sollen schon bald zu SNEWS beitragen, dem weltweiten Netzwerk zur Früherkennung von Supernovae.

Entwicklung einer Fokalebenen-Driftkammer für niederenergetische Pionen und experimentelle Bestimmung einer inversen Transfermatrix für das Short-Orbit-Spektrometer

Die Drei-Spektrometer-Anlage am Mainzer Institut für Kernphysik wurde um ein zusätzliches Spektrometer ergänzt, welches sich durch seine kurze Baulänge auszeichnet und deshalb Short-Orbit-Spektrometer (SOS) genannt wird. Beim nominellen Abstand des SOS vom Target (66 cm) legen die nachzuweisenden Teilchen zwischen Reaktionsort und Detektor eine mittlere Bahnlänge von 165 cm zurück. Für die schwellennahe Pionproduktion erhöht sich dadurch im Vergleich zu den großen Spektrometern die Überlebenswahrscheinlichkeit geladener Pionen mit Impuls 100 MeV/c von 15% auf 73%. Demzufolge verringert sich der systematische Fehler ("Myon-Kontamination"), etwa bei der geplanten Messung der schwachen Formfaktoren G_A(Q²) und G_P(Q²), signifikant. Den Schwerpunkt der vorliegenden Arbeit bildet die Driftkammer des SOS. Ihre niedrige Massenbelegung (0,03% X_0) zur Reduzierung der Kleinwinkelstreuung ist auf den Nachweis niederenergetischer Pionen hin optimiert. Aufgrund der neuartigen Geometrie des Detektors musste eine eigene Software zur Spurrekonstruktion, Effizienzbestimmung etc. entwickelt werden. Eine komfortable Möglichkeit zur Eichung der Driftweg-Driftzeit-Relation, die durch kubische Splines dargestellt wird, wurde implementiert. Das Auflösungsvermögen des Spurdetektors liegt in der dispersiven Ebene bei 76 µm für die Orts- und 0,23° für die Winkelkoordinate (wahrscheinlichster Fehler) sowie entsprechend in der nicht-dispersiven Ebene bei 110 µm bzw. 0,29°. Zur Rückrechnung der Detektorkoordinaten auf den Reaktionsort wurde die inverse Transfermatrix des Spektrometers bestimmt. Hierzu wurden an Protonen im ¹²C-Kern quasielastisch gestreute Elektronen verwendet, deren Startwinkel durch einen Lochkollimator definiert wurden. Daraus ergeben sich experimentelle Werte für die mittlere Winkelauflösung am Target von sigma_phi = 1,3 mrad bzw. sigma_theta = 10,6 mrad. Da die Impulseichung des SOS nur mittels quasielastischer Streuung (Zweiarmexperiment) durchgeführt werden kann, muss man den Beitrag des Protonarms zur Breite des Piks der fehlenden Masse in einer Monte-Carlo-Simulation abschätzen und herausfalten. Zunächst lässt sich nur abschätzen, dass die Impulsauflösung sicher besser als 1% ist.

Cosmological perturbations in generalized theories of gravity

The first part of the thesis concerns the study of inflation in the context of a theory of gravity called "Induced Gravity" in which the gravitational coupling varies in time according to the dynamics of the very same scalar field (the "inflaton") driving inflation, while taking on the value measured today since the end of inflation. Through the analytical and numerical analysis of scalar and tensor cosmological perturbations we show that the model leads to consistent predictions for a broad variety of symmetry-breaking inflaton's potentials, once that a dimensionless parameter entering into the action is properly constrained. We also discuss the average expansion of the Universe after inflation (when the inflaton undergoes coherent oscillations about the minimum of its potential) and determine the effective equation of state. Finally, we analyze the resonant and perturbative decay of the inflaton during (p)reheating. The second part is devoted to the study of a proposal for a quantum theory of gravity dubbed "Horava-Lifshitz (HL) Gravity" which relies on power-counting renormalizability while explicitly breaking Lorentz invariance. We test a pair of variants of the theory ("projectable" and "non-projectable") on a cosmological background and with the inclusion of scalar field matter. By inspecting the quadratic action for the linear scalar cosmological perturbations we determine the actual number of propagating degrees of freedom and realize that the theory, being endowed with less symmetries than General Relativity, does admit an extra gravitational degree of freedom which is potentially unstable. More specifically, we conclude that in the case of projectable HL Gravity the extra mode is either a ghost or a tachyon, whereas in the case of non-projectable HL Gravity the extra mode can be made well-behaved for suitable choices of a pair of free dimensionless parameters and, moreover, turns out to decouple from the low-energy Physics.