Elaeocarpacae-Alkaloide: flexible Synthese optisch aktiver (-) Elaeokanin C Schlüsselbausteine

Kurzzusammenfassung Elaeocarpacae-Alkaloide: flexible Synthesen optisch aktiver (-) Elaeokanin C Schlüsselbausteine Im Tier- und Pflanzenreich sind Alkaloide weit verbreitet und werden von der Biogenese her als Produkte des Aminosäure-Stoffwechsels angesehen. Die Elaeocarpacae-Alkaloide zählen zu den Indolizidinen, welche durch ein Azabicyclo-[4.3.0]-nonan Grundgerüst charakterisiert sind und erstmals Ende der 60er Jahre des letzten Jahrhunderts aus den Blättern der in Neu Guinea beheimateten Ölbaumgewächse isoliert wurden. Für verschiedene Vertreter dieses Alkaloid-Typs wurden sowohl racemische als auch asymmetrische Totalsynthesen entwickelt. Während für das (+) Elaeokanin C bereits Totalsynthesen existieren, gibt es für das (-) Elaeokanin C bis heute keine asymmetrische Synthese. Als Fernziel der vorliegenden Arbeit wurde die erste Totalsynthese von (-) Elaeokanin C ausgewählt. Der Syntheseplan sieht zunächst den diastereoselektiven Aufbau eines optisch aktiven Schlüsselbausteins mit Naturstoff-Stereotriade im Sinne einer konvergenten ex-chiral-pool Synthese vor. Im Rahmen dieser Arbeit konnte dies durch die Aza-Claisen-Umlagerung realisiert werden. Ausgehend von diesem Schlüsselbaustein wurden verschiedene Synthesewege verfolgt um sowohl das Substitutionsmuster der Seitenkette als auch das des Piperidinsegments vielfältig variieren zu können. Die Einführung der Seitenkette erwies sich durch vielfältige Nachbargruppeneffekte wie die unerwünschte 5-exo-trig Cyclisierung zu einem Pyrrolizidin Derivat als große Hürde. Eine geänderte Synthesestrategie mit einem schrittweisen Aufbau der Kette lieferte schließlich den Baustein, aus dem nun in wenigen Stufen das (-) Elaeokanin C sowie vielfältige Analoga herzustellen sein sollten.

Continuos Flow Single Cell Separation into Open Microwell Arrays

A novel design based on electric field-free open microwell arrays for the automated continuous-flow sorting of single or small clusters of cells is presented. The main feature of the proposed device is the parallel analysis of cell-cell and cell-particle interactions in each microwell of the array. High throughput sample recovery with a fast and separate transfer from the microsites to standard microtiter plates is also possible thanks to the flexible printed circuit board technology which permits to produce cost effective large area arrays featuring geometries compatible with laboratory equipment. The particle isolation is performed via negative dielectrophoretic forces which convey the particles’ into the microwells. Particles such as cells and beads flow in electrically active microchannels on whose substrate the electrodes are patterned. The introduction of particles within the microwells is automatically performed by generating the required feedback signal by a microscope-based optical counting and detection routine. In order to isolate a controlled number of particles we created two particular configurations of the electric field within the structure. The first one permits their isolation whereas the second one creates a net force which repels the particles from the microwell entrance. To increase the parallelism at which the cell-isolation function is implemented, a new technique based on coplanar electrodes to detect particle presence was implemented. A lock-in amplifying scheme was used to monitor the impedance of the channel perturbed by flowing particles in high-conductivity suspension mediums. The impedance measurement module was also combined with the dielectrophoretic focusing stage situated upstream of the measurement stage, to limit the measured signal amplitude dispersion due to the particles position variation within the microchannel. In conclusion, the designed system complies with the initial specifications making it suitable for cellomics and biotechnology applications.

Interactive simulation of flexible parts

Computer simulations play an ever growing role for the development of automotive products. Assembly simulation, as well as many other processes, are used systematically even before the first physical prototype of a vehicle is built in order to check whether particular components can be assembled easily or whether another part is in the way. Usually, this kind of simulation is limited to rigid bodies. However, a vehicle contains a multitude of flexible parts of various types: cables, hoses, carpets, seat surfaces, insulations, weatherstrips... Since most of the problems using these simulations concern one-dimensional components and since an intuitive tool for cable routing is still needed, we have chosen to concentrate on this category, which includes cables, hoses and wiring harnesses. In this thesis, we present a system for simulating one dimensional flexible parts such as cables or hoses. The modeling of bending and torsion follows the Cosserat model. For this purpose we use a generalized spring-mass system and describe its configuration by a carefully chosen set of coordinates. Gravity and contact forces as well as the forces responsible for length conservation are expressed in Cartesian coordinates. But bending and torsion effects can be dealt with more effectively by using quaternions to represent the orientation of the segments joining two neighboring mass points. This augmented system allows an easy formulation of all interactions with the best appropriate coordinate type and yields a strongly banded Hessian matrix. An energy minimizing process accounts for a solution exempt from the oscillations that are typical of spring-mass systems. The use of integral forces, similar to an integral controller, allows to enforce exactly the constraints. The whole system is numerically stable and can be solved at interactive frame rates. It is integrated in the DaimlerChrysler in-house Virtual Reality Software veo for use in applications such as cable routing and assembly simulation and has been well received by users. Parts of this work have been published at the ACM Solid and Physical Modeling Conference 2006 and have been selected for the special issue of the Computer-Aided-Design Journal to the conference.

Luminescent Ionic Transition-Metal Complexes for Light-Emitting Electrochemical Cells

The European Union set the ambitious target of reducing energy consumption by 20% within 2020. This goal demands a tremendous change in how we generate and consume energy and urgently calls for an aggressive policy on energy efficiency. Since 19% of the European electrical energy is used for lighting, considerable savings can be achieved with the development of novel and more efficient lighting systems. In this thesis, accomplished in the frame of the EU project CELLO, I report some selected goals we achieved attempting to develop highly efficient, flat, low cost and flexible light sources using Light-Emitting Electrochemical Cells (LECs), based on ionic cyclometalated iridium(III) complexes. After an extensive introduction about LECs and solid-state lighting in general, I focus on the research we carried out on cyclometalated iridium(III) complexes displaying deep-blue emission, which has turned out to be a rather challenging task. In order to demonstrate the wide versatility of this class of compounds, I also report a case in which some tailored iridium(III) complexes act as near-infrared (NIR) sources. In fact, standard NIR emitting devices are typically expensive and, also in this case, LECs could serve as low-cost alternatives in fields were NIR luminescence is crucial, such as telecommunications and bioimaging. Since LECs are based on only one active material, in the last chapter I stress the importance of an integrated approach toward the right selection of suitable emitters not only from the photophysical, but also from the point of view of material science. An iridium(III) complex, once in the device, is interacting with ionic liquids, metal cathodes, electric fields, etc. All these interactions should be taken in to account if Europe really wants to implement more efficient lighting paradigms, generating light beyond research labs.

Cognitive radio applications for enhanced spectrum efficiency

The aim of this thesis is the study of techniques for efficient management and use of the spectrum based on cognitive radio technology. The ability of cognitive radio technologies to adapt to the real-time conditions of its operating environment, offers the potential for more flexible use of the available spectrum. In this context, the international interest is particularly focused on the “white spaces” in the UHF band of digital terrestrial television. Spectrum sensing and geo-location database have been considered in order to obtain information on the electromagnetic environment. Different methodologies have been considered in order to investigate spectral resources potentially available for the white space devices in the TV band. The adopted methodologies are based on the geo-location database approach used either in autonomous operation or in combination with sensing techniques. A novel and computationally efficient methodology for the calculation of the maximum permitted white space device EIRP is then proposed. The methodology is suitable for implementation in TV white space databases. Different Italian scenarios are analyzed in order to identify both the available spectrum and the white space device emission limits. Finally two different applications of cognitive radio technology are considered. The first considered application is the emergency management. The attention is focused on the consideration of both cognitive and autonomic networking approaches when deploying an emergency management system. The cognitive technology is then considered in applications related to satellite systems. In particular a hybrid cognitive satellite-terrestrial is introduced and an analysis of coexistence between terrestrial and satellite networks by considering a cognitive approach is performed.

Modeling systems and vis/NIR device to improve peach and nectarine pre and post-harvest fruit maturity management

During the last decade peach and nectarine fruit have lost considerable market share, due to increased consumer dissatisfaction with quality at retail markets. This is mainly due to harvesting of too immature fruit and high ripening heterogeneity. The main problem is that the traditional used maturity indexes are not able to objectively detect fruit maturity stage, neither the variability present in the field, leading to a difficult post-harvest management of the product and to high fruit losses. To assess more precisely the fruit ripening other techniques and devices can be used. Recently, a new non-destructive maturity index, based on the vis-NIR technology, the Index of Absorbance Difference (IAD), that correlates with fruit degreening and ethylene production, was introduced and the IAD was used to study peach and nectarine fruit ripening from the “field to the fork”. In order to choose the best techniques to improve fruit quality, a detailed description of the tree structure, of fruit distribution and ripening evolution on the tree was faced. More in details, an architectural model (PlantToon®) was used to design the tree structure and the IAD was applied to characterize the maturity stage of each fruit. Their combined use provided an objective and precise evaluation of the fruit ripening variability, related to different training systems, crop load, fruit exposure and internal temperature. Based on simple field assessment of fruit maturity (as IAD) and growth, a model for an early prediction of harvest date and yield, was developed and validated. The relationship between the non-destructive maturity IAD, and the fruit shelf-life, was also confirmed. Finally the obtained results were validated by consumer test: the fruit sorted in different maturity classes obtained a different consumer acceptance. The improved knowledge, leaded to an innovative management of peach and nectarine fruit, from “field to market”.

Approccio combinato geo-location database e sensing per individuare i livelli di potenza trasmissibili da white space device

La Cognitive Radio è un dispositivo in grado di reagire ai cambiamenti dell’ambiente radio in cui opera, modificando autonomamente e dinamicamente i propri parametri funzionali tra cui la frequenza, la potenza di trasmissione e la modulazione. Il principio di base di questi dispositivi è l’accesso dinamico alle risorse radio potenzialmente non utilizzate, con cui utenti non in possesso di licenze possono sfruttare le frequenze che in un determinato spazio temporale non vengono usate, preoccupandosi di non interferire con gli utenti che hanno privilegi su quella parte di spettro. Devono quindi essere individuati i cosiddetti “spectrum holes” o “white spaces”, parti di spettro assegnate ma non utilizzate, dai quali prendono il nome i dispositivi.Uno dei modi per individuare gli “Spectrum holes” per una Cognitive Radio consiste nel cercare di captare il segnale destinato agli utenti primari; questa tecnica è nota con il nome di Spectrum Sensing e consente di ottenere essenzialmente una misura all’interno del canale considerato al fine di determinare la presenza o meno di un servizio protetto. La tecnica di sensing impiegata da un WSD che opera autonomamente non è però molto efficiente in quanto non garantisce una buona protezione ai ricevitori DTT che usano lo stesso canale sul quale il WSD intende trasmettere.A livello europeo la soluzione che è stata ritenuta più affidabile per evitare le interferenze sui ricevitori DTT è rappresentata dall’uso di un geo-location database che opera in collaborazione con il dispositivo cognitivo.Lo scopo di questa tesi è quello di presentare un algoritmo che permette di combinare i due approcci di geo-location database e Sensing per definire i livelli di potenza trasmissibile da un WSD.

Experimental and Numerical Analysis of Gas Forced Convection through Microtubes and Micro Heat Exchangers

The last decade has witnessed very fast development in microfabrication technologies. The increasing industrial applications of microfluidic systems call for more intensive and systematic knowledge on this newly emerging field. Especially for gaseous flow and heat transfer at microscale, the applicability of conventional theories developed at macro scale is not yet completely validated; this is mainly due to scarce experimental data available in literature for gas flows. The objective of this thesis is to investigate these unclear elements by analyzing forced convection for gaseous flows through microtubes and micro heat exchangers. Experimental tests have been performed with microtubes having various inner diameters, namely 750 m, 510 m and 170 m, over a wide range of Reynolds number covering the laminar region, the transitional zone and also the onset region of the turbulent regime. The results show that conventional theory is able to predict the flow friction factor when flow compressibility does not appear and the effect of fluid temperature-dependent properties is insignificant. A double-layered microchannel heat exchanger has been designed in order to study experimentally the efficiency of a gas-to-gas micro heat exchanger. This microdevice contains 133 parallel microchannels machined into polished PEEK plates for both the hot side and the cold side. The microchannels are 200 µm high, 200 µm wide and 39.8 mm long. The design of the micro device has been made in order to be able to test different materials as partition foil with flexible thickness. Experimental tests have been carried out for five different partition foils, with various mass flow rates and flow configurations. The experimental results indicate that the thermal performance of the countercurrent and cross flow micro heat exchanger can be strongly influenced by axial conduction in the partition foil separating the hot gas flow and cold gas flow.

Porting monitor di rete per gestione interfacce su device android.

Il lavoro svolto in questa tesi consiste nell'effettuare il porting del Monitor di rete da Linux ad Android,facente parte di un sistema più complesso conosciuto come ABPS. Il ruolo del monitor è quello di configurare dinamicamente tutte le interfacce di rete disponibili sul dispositivo sul quale lavora,in modo da essere connessi sempre alla miglior rete conosciuta,ad esempio al miglior Access Point nel caso del interfaccia wireless.

Model reduction techniques in flexible multibody dynamics with application to engine cranktrain simulation

The development of a multibody model of a motorbike engine cranktrain is presented in this work, with an emphasis on flexible component model reduction. A modelling methodology based upon the adoption of non-ideal joints at interface locations, and the inclusion of component flexibility, is developed: both are necessary tasks if one wants to capture dynamic effects which arise in lightweight, high-speed applications. With regard to the first topic, both a ball bearing model and a journal bearing model are implemented, in order to properly capture the dynamic effects of the main connections in the system: angular contact ball bearings are modelled according to a five-DOF nonlinear scheme in order to grasp the crankshaft main bearings behaviour, while an impedance-based hydrodynamic bearing model is implemented providing an enhanced operation prediction at the conrod big end locations. Concerning the second matter, flexible models of the crankshaft and the connecting rod are produced. The well-established Craig-Bampton reduction technique is adopted as a general framework to obtain reduced model representations which are suitable for the subsequent multibody analyses. A particular component mode selection procedure is implemented, based on the concept of Effective Interface Mass, allowing an assessment of the accuracy of the reduced models prior to the nonlinear simulation phase. In addition, a procedure to alleviate the effects of modal truncation, based on the Modal Truncation Augmentation approach, is developed. In order to assess the performances of the proposed modal reduction schemes, numerical tests are performed onto the crankshaft and the conrod models in both frequency and modal domains. A multibody model of the cranktrain is eventually assembled and simulated using a commercial software. Numerical results are presented, demonstrating the effectiveness of the implemented flexible model reduction techniques. The advantages over the conventional frequency-based truncation approach are discussed.

La normativa tecnica sul software medical device: analisi del rischio ed impatto sulle aziende sanitarie

Quadro normativo sui Dispositivi Medici e la sua evoluzione (2007/47,UNI CEI EN ISO 14971). Software DM: processo di certificazione,gestione di reti IT medicali, ruoli e responsabilità (CEI 80001-1). Casi d'uso: Linee guida: MEDDEV e linee guida svedesi più relativi esempi applicabili alle aziende sanitarie.

Electrical scanning probe microscopy on organic optoelectronic structures

In the field of organic optoelectronics, the nanoscale structure of the materials has huge im-pact on the device performance. Here, scanning force microscopy (SFM) techniques become increasingly important. In addition to topographic information, various surface properties can be recorded on a nanometer length scale, such as electrical conductivity (conductive scanning force microscopy, C-SFM) and surface potential (Kelvin probe force microscopy, KPFM).rnrnIn the context of this work, the electrical SFM modes were applied to study the interplay be-tween morphology and electrical properties in hybrid optoelectronic structures, developed in the group of Prof. J. Gutmann (MPI-P Mainz). In particular, I investigated the working prin-ciple of a novel integrated electron blocking layer system. A structure of electrically conduct-ing pathways along crystalline TiO2 particles in an insulating matrix of a polymer derived ceramic was found and insulating defect structures could be identified. In order to get insights into the internal structure of a device I investigated a working hybrid solar cell by preparing a cross cut with focused ion beam polishing. With C-SFM, the functional layers could be identified and the charge transport properties of the novel active layer composite material could be studied. rnrnIn C-SFM, soft surfaces can be permanently damaged by (i) tip induced forces, (ii) high elec-tric fields and (iii) high current densities close to the SFM-tip. Thus, an alternative operation based on torsion mode topography imaging in combination with current mapping was intro-duced. In torsion mode, the SFM-tip vibrates laterally and in close proximity to the sample surface. Thus, an electrical contact between tip and sample can be established. In a series of reference experiments on standard surfaces, the working mechanism of scanning conductive torsion mode microscopy (SCTMM) was investigated. Moreover, I studied samples covered with free standing semiconducting polymer nano-pillars that were developed in the group of Dr. P. Theato (University Mainz). The application of SCTMM allowed non-destructive imag-ing of the flexible surface at high resolution while measuring the conductance on individual pillarsrnrnIn order to study light induced electrical effects on the level of single nanostructures, a new SFM setup was built. It is equipped with a laser sample illumination and placed in inert at-mosphere. With this photoelectric SFM, I investigated the light induced response in function-alized nanorods that were developed in the group of Prof. R. Zentel (University Mainz). A block-copolymer containing an anchor block and dye moiety and a semiconducting conju-gated polymer moiety was synthesized and covalently bound to ZnO nanorods. This system forms an electron donor/acceptor interface and can thus be seen as a model system of a solar cell on the nanoscale. With a KPFM study on the illuminated samples, the light induced charge separation between the nanorod and the polymeric corona could not only be visualized, but also quantified.rnrnThe results demonstrate that electrical scanning force microscopy can study fundamental processes in nanostructures and give invaluable feedback to the synthetic chemists for the optimization of functional nanomaterials.rn

Self-Assembled Monolayers (SAMs) in Organic Field-Effect Transistors

Organic printed electronics is attracting an ever-growing interest in the last decades because of its impressive breakthroughs concerning the chemical design of π-conjugated materials and their processing. This has an impact on novel applications, such as flexible-large-area displays, low- cost printable circuits, plastic solar cells and lab-on-a-chip devices. The organic field-effect transistor (OFET) relies on a thin film of organic semiconductor that bridges source and drain electrodes. Since its first discovery in the 80s, intensive research activities were deployed in order to control the chemico-physical properties of these electronic devices and consequently their charge. Self-assembled monolayers (SAMs) are a versatile tool for tuning the properties of metallic, semi-conducting, and insulating surfaces. Within this context, OFETs represent reliable instruments for measuring the electrical properties of the SAMs in a Metal/SAM/OS junction. Our experimental approach, named Charge Injection Organic-Gauge (CIOG), uses OTFT in a charge-injection controlled regime. The CIOG sensitivity has been extensively demonstrated on different homologous self-assembling molecules that differ in either chain length or in anchor/terminal group. One of the latest applications of organic electronics is the so-called “bio-electronics” that makes use of electronic devices to encompass interests of the medical science, such as biosensors, biotransducers etc… As a result, thee second part of this thesis deals with the realization of an electronic transducer based on an Organic Field-Effect Transistor operating in aqueous media. Here, the conventional bottom gate/bottom contact configuration is replaced by top gate architecture with the electrolyte that ensures electrical contact between the top gold electrode and the semiconductor layer. This configuration is named Electrolyte-Gated Field-Effect Transistor (EGOFET). The functionalization of the top electrode is the sensing core of the device allowing the detection of dopamine as well as of protein biomarkers with ultra-low sensitivity.

Analisi del fenomeno bring your own device: La nuova sfida per affrontare la mobilita lavorativa analizzata all?interno di una multinazionale farmaceutica.

Imprese di piccole e grandi dimensioni hanno dovuto convivere con il ritmo di uscita di nuovi e più potenti modelli di PC, consolle per videogiochi, telefoni cellulari, tablet, fotocamere digitali. I cicli di vita si sono ridotti drasticamente, tanto da far sembrare un’emergenza il rilascio di un nuovo prodotto quasi ogni anno. Le aziende, se ancora non lo hanno fatto, sono chiamate ad affrontare una transizione interna per aggiornare le politiche aziendali in modo da stare al passo con il progresso tecnologico. Se un tempo le regole interne vietavano o scoraggiavano l’utilizzo di dispositivi personali nell’ambiente di lavoro, nell’era moderna sono costrette ad accettarlo se non addirittura ad incoraggiarlo ed il fenomeno che mi accingerò ad analizzare in questo elaborato, denominato Bring Your Own Device (BYOD), punta proprio all’esplorazione degli sforzi progettuali che sono richiesti ad una grande azienda multinazionale per poter recepire i trend informatici. Con più di cinque miliardi di dispositivi mobili in tutto il mondo – e solo 2 miliardi di computer – il passaggio al ‘mobile’ come forma principale di collegamento alle reti aziendali procede con sempre maggiore rapidità. Negli anni recenti si è potuto assistere all’evoluzione del panorama di dispositivi portatili che ha permesso ad un pubblico di users sempre più vasto di potersi permettere l’acquisto di dispositivi di ultima generazione a prezzi non proibitivi. I fornitori di tecnologie hanno confezionato prodotti sempre più pensati per un uso privato, fornendo un’ampia scelta di soluzioni non solo a livello enterprise, come accadeva agli albori del boom tecnologico, ma maggiormente rivolte al singolo consumatore. Guardando ai trend sviluppatisi negli anni recenti, è possibile riconoscere una scia di segnali che preannunciavano quanto sta avvenendo adesso con il BYOD.