The processing of polyelectrolyte-covered magnetite nanoparticles in the form of nanostructured thin films

Magnetic nanoparticles are promising for a variety of applications, such as biomedical devices, spin electronics, magnetic data storage media, to name a few. However, these goals may only be reached if stable and organized structures are fabricated. In this article, we report on a single-step synthetic route with the coprecipitation method, in which iron oxide magnetic nanoparticles (Fe3O4 NPs) were stabilized in aqueous media using the poly(diallyldimethylammonium chloride) (PDAC) polyelectrolyte. The Fe3O4 NPs had a diameter of ca. 5 nm, according to transmission electron microscopy (TEM) images, being arranged in an inverse spinel structure typical of magnetite. An investigation with infrared spectroscopy indicated that the mechanisms of stabilization in the polymer matrix were based on the interaction between quaternary amide groups from PDAC and the nanoparticle surface. The Fe3O4-PDAC NPs exhibited considerable magnetic susceptibility, with a monotonic increase in the magnetization with decreasing temperature. These Fe3O4-PDAC NPs were immobilized in layer-by-layer (LbL) films, being alternated with layers of poly(vinylsulfonic acid) (PVS). The LbL films were much rougher than typical films made with polyelectrolytes, and Fe3O4-PDAC NPs have been responsible for the high electrocatalytic activity toward H2O2 reduction, with an overpotential shift of 0.69 V. Overall, the stability, magnetic properties and film-forming ability indicate that the Fe3O4-PDAC NPs may be used for nanoelectronics and bioelectrochemical devices requiring reversible and magnetic redox materials.

Optically active photoresponsive multifunctional polymeric materials

In the last year [1], Angiolini and co-workers have synthesized and investigated methacrylic polymers bearing in the side chain the chiral cyclic (S)-3-hydroxypyrrolidine moiety interposed between the main chain and the trans-azoaromatic chromophore, substituted or not in the 4’ position by an electron-withdrawing group. In these materials, the presence of a rigid chiral moiety of one prevailing absolute configuration favours the establishment of a chiral conformation of one prevailing helical handedness, at least within chain segments of the macromolecules, which can be observed by circular dichroism (CD). The simultaneous presence of the azoaromatic and chiral functionalities allows the polymers to display both the properties typical of dissymmetric systems (optical activity, exciton splitting of dichroic absorptions), as well as the features typical of photochromic materials (photorefractivity, photoresponsiveness, NLO properties). The first part of this research was to synthesize analogue homopolymers and copolymers based on bisazoaromatic moiety and compare their properties to those of the above mentioned analogue derivatives bearing only one azoaromatic chromophore in the side chain. We focused also the attention on the effects induced on the thermal and chiroptical behaviours by the insertion of particulars achiral comonomers characterized by different side-chain mobility and grown hindrance (MMA, tert-BMA and TrMA). On the other hand carbazole containing polymers [2] have attracted much attention because of their unique features. The use of these materials in advanced micro- and nanotechnologies spreads in many different applications such as photoconductive and photorefractive polymers, electroluminescent devices, programmable optical interconnections, data storage, chemical photoreceptors, NLO, surface relief gratings, blue emitting materials and holographic memory. The second part of the work was focused on the synthesis and the characterization polymeric derivatives bearing in the side chain carbazole or phenylcarbazole moieties linked to the (S)- 2-hydroxy succinimide or the (S)-3-hydroxy pyrrolidinyl ring as chiral groups covalently linked to the main chain through ester bonds. The last objective of this research was to design, synthesize, and characterize multifunctional methacrylic homopolymers and copolymers bearing three distinct functional groups (i.e. azoaromatic, carbazole and chiral group of one single configuration) directly linked in the side chain. This polymeric derivatives could be of potential interest for several advanced application fields, such as optical storage, waveguides, chiroptical switches, chemical photoreceptors, NLO, surface relief gratings, photoconductive materials, etc.

Architectures for Context Aware Services in Smart Environments

This thesis deals with Context Aware Services, Smart Environments, Context Management and solutions for Devices and Service Interoperability. Multi-vendor devices offer an increasing number of services and end-user applications that base their value on the ability to exploit the information originating from the surrounding environment by means of an increasing number of embedded sensors, e.g. GPS, compass, RFID readers, cameras and so on. However, usually such devices are not able to exchange information because of the lack of a shared data storage and common information exchange methods. A large number of standards and domain specific building blocks are available and are heavily used in today's products. However, the use of these solutions based on ready-to-use modules is not without problems. The integration and cooperation of different kinds of modules can be daunting because of growing complexity and dependency. In this scenarios it might be interesting to have an infrastructure that makes the coexistence of multi-vendor devices easy, while enabling low cost development and smooth access to services. This sort of technologies glue should reduce both software and hardware integration costs by removing the trouble of interoperability. The result should also lead to faster and simplified design, development and, deployment of cross-domain applications. This thesis is mainly focused on SW architectures supporting context aware service providers especially on the following subjects: - user preferences service adaptation - context management - content management - information interoperability - multivendor device interoperability - communication and connectivity interoperability Experimental activities were carried out in several domains including Cultural Heritage, indoor and personal smart spaces – all of which are considered significant test-beds in Context Aware Computing. The work evolved within european and national projects: on the europen side, I carried out my research activity within EPOCH, the FP6 Network of Excellence on “Processing Open Cultural Heritage” and within SOFIA, a project of the ARTEMIS JU on embedded systems. I worked in cooperation with several international establishments, including the University of Kent, VTT (the Technical Reserarch Center of Finland) and Eurotech. On the national side I contributed to a one-to-one research contract between ARCES and Telecom Italia. The first part of the thesis is focused on problem statement and related work and addresses interoperability issues and related architecture components. The second part is focused on specific architectures and frameworks: - MobiComp: a context management framework that I used in cultural heritage applications - CAB: a context, preference and profile based application broker which I designed within EPOCH Network of Excellence - M3: "Semantic Web based" information sharing infrastructure for smart spaces designed by Nokia within the European project SOFIA - NoTa: a service and transport independent connectivity framework - OSGi: the well known Java based service support framework The final section is dedicated to the middleware, the tools and, the SW agents developed during my Doctorate time to support context-aware services in smart environments.

Polymergebundene Nitrone

In den letzten Jahren ist die Nachfrage nach Datenspeichern und ihrer Speicherkapazität immer größer geworden. Dazu sind neue Speichermaterialien notwendig sind, wofür sich in vielen Fällen polymere schaltbare Materialien eignen.Aus diesem Grunde wurden in der vorliegenden Arbeit polymergebundene Nitrone hergestellt, um diese als photoreaktives Material zu untersuchen. Die direkte freie radikalische Polymerisation war nicht möglich. Um zu den polymergebundenen Nitronen zu gelangen, mussten zuerst die Doppelbindungen enthaltenden Aldehyde polymerisiert und dann polymeranalog, meist quantitativ mit den N?Alkylhydroxylaminen zum Nitron kondensiert werden. Des weiteren wurden nitronhaltige Polymere auf direktem Weg durch enzymatisch-oxidative Polymerisation von nitronhaltigen Phenolen erhalten.Auch wurden Aldehydmonomere mit dem sperrigen dimethylierten b-Cyclodextrin als 'Schutzgruppe' komplexiert und im wässrigen Medium radikalisch polymerisiert, was zu höheren Molgewichten führte. Hierbei trat auch ein interessanter Verzögerungseffekt bei der Polymerisation von 4-Vinylbenzaldehyd auf, was sich in längeren Polymerisationszeiten und geringeren Polymerisationsausbeuten bemerkbar machte.Die UV-Bestrahlung der Nitronfunktion führt zum entsprechenden dreigliedrigen Oxaziridinring, der eine geringere Polarität als das Nitron besitzt. Die Wellenleitermodenspektroskopie der nitronhaltigen Polymerfilme zeigte, dass die Schichtdicke weitgehend konstant bleibt, während die Brechungsindices stark abnehmen. Eine thermische Ringöffnung der polymergebundenen Oxaziridine zu den entsprechenden Nitronen scheint bei dieser Art von Polymeren nicht möglich zu sein.

Middleware for quality-based context distribution in mobile systems

The continuous advancements and enhancements of wireless systems are enabling new compelling scenarios where mobile services can adapt according to the current execution context, represented by the computational resources available at the local device, current physical location, people in physical proximity, and so forth. Such services called context-aware require the timely delivery of all relevant information describing the current context, and that introduces several unsolved complexities, spanning from low-level context data transmission up to context data storage and replication into the mobile system. In addition, to ensure correct and scalable context provisioning, it is crucial to integrate and interoperate with different wireless technologies (WiFi, Bluetooth, etc.) and modes (infrastructure-based and ad-hoc), and to use decentralized solutions to store and replicate context data on mobile devices. These challenges call for novel middleware solutions, here called Context Data Distribution Infrastructures (CDDIs), capable of delivering relevant context data to mobile devices, while hiding all the issues introduced by data distribution in heterogeneous and large-scale mobile settings. This dissertation thoroughly analyzes CDDIs for mobile systems, with the main goal of achieving a holistic approach to the design of such type of middleware solutions. We discuss the main functions needed by context data distribution in large mobile systems, and we claim the precise definition and clean respect of quality-based contracts between context consumers and CDDI to reconfigure main middleware components at runtime. We present the design and the implementation of our proposals, both in simulation-based and in real-world scenarios, along with an extensive evaluation that confirms the technical soundness of proposed CDDI solutions. Finally, we consider three highly heterogeneous scenarios, namely disaster areas, smart campuses, and smart cities, to better remark the wide technical validity of our analysis and solutions under different network deployments and quality constraints.

Caratteristiche innovative nell'acquisizione di dati di informatica forense in ambienti virtuali

Come risposta positiva alle richieste provenienti dal mondo dei giuristi, spesso troppo distante da quello scientifico, si vuole sviluppare un sistema solido dal punto di vista tecnico e chiaro dal punto di vista giurico finalizzato ad migliore ricerca della verità. L’obiettivo ci si prefigge è quello di creare uno strumento versatile e di facile utilizzo da mettere a disposizione dell’A.G. ed eventualmente della P.G. operante finalizzato a consentire il proseguo dell’attività d’indagine in tempi molto rapidi e con un notevole contenimento dei costi di giustizia rispetto ad una normale CTU. La progetto verterà su analisi informatiche forensi di supporti digitali inerenti vari tipi di procedimento per cui si dovrebbe richiedere una CTU o una perizia. La sperimentazione scientifica prevede un sistema di partecipazione diretta della P.G. e della A.G. all’analisi informatica rendendo disponibile, sottoforma di macchina virtuale, il contenuto dei supporti sequestrati in modo che possa essere visionato alla pari del supporto originale. In questo modo il CT diventa una mera guida per la PG e l’AG nell’ambito dell’indagine informatica forense che accompagna il giudice e le parti alla migliore comprensione delle informazioni richieste dal quesito. Le fasi chiave della sperimentazione sono: • la ripetibilità delle operazioni svolte • dettare delle chiare linee guida per la catena di custodia dalla presa in carico dei supporti • i metodi di conservazione e trasmissione dei dati tali da poter garantire integrità e riservatezza degli stessi • tempi e costi ridotti rispetto alle normali CTU/perizie • visualizzazione diretta dei contenuti dei supporti analizzati delle Parti e del Giudice circoscritte alle informazioni utili ai fini di giustizia

Polymer surfaces on small length- and short time-scales

The behaviour of a polymer depends strongly on the length- and time scale as well as on the temperature rnat which it is probed. In this work, I describe investigations of polymer surfaces using scanning probe rnmicroscopy with heatable probes. With these probes, surfaces can be heated within seconds down to rnmicroseconds. I introduce experiments for the local and fast determination of glass transition and melting rntemperatures. I developed a method which allows the determination of glass transition and melting rntemperatures on films with thicknesses below 100 nm: A background measurement on the substrate was rnperformed. The resulting curve was subtracted from the measurement on the polymer film. The rndifferential measurement on polystyrene films with thicknesses between 35 nm and 160 nm showed rncharacteristic signals at 95 ± 1 °C, in accordance with the glass transition of polystyrene. Pressing heated rnprobes into polymer films causes plastic deformation. Nanometer sized deformations are currently rninvestigated in novel concepts for high density data storage. A suitable medium for such a storage system rnhas to be easily indentable on one hand, but on the other hand it also has to be very stable towards rnsurface induced wear. For developing such a medium I investigated a new approach: A comparably soft rnmaterial, namely polystyrene, was protected with a thin but very hard layer made of plasma polymerized rnnorbornene. The resulting bilayered media were tested for surface stability and deformability. I showed rnthat the bilayered material combines the deformability of polystyrene with the surface stability of the rnplasma polymer, and that the material therefore is a very good storage medium. In addition we rninvestigated the glass transition temperature of polystyrene at timescales of 10 µs and found it to be rnapprox. 220 °C. The increase of this characteristic temperature of the polymer results from the short time rnat which the polymer was probed and reflects the well-known time-temperature superposition principle. rnHeatable probes were also used for the characterization of silverazide filled nanocapsules. The use of rnheatable probes allowed determining the decomposition temperature of the capsules from few rnnanograms of material. The measured decomposition temperatures ranged from 180 °C to 225 °C, in rnaccordance with literature values. The investigation of small amounts of sample was necessary due to the rnlimited availability of the material. Furthermore, investigating larger amounts of the capsules using rnconventional thermal gravimetric analysis could lead to contamination or even damage of the instrument. rnBesides the analysis of material parameters I used the heatable probes for the local thermal rndecomposition of pentacene precursor material in order to form nanoscale conductive structures. Here, rnthe thickness of the precursor layer was important for complete thermal decomposition. rnAnother aspect of my work was the investigation of redox active polymers - Poly-10-(4-vinylbenzyl)-10H-rnphenothiazine (PVBPT)- for data storage. Data is stored by changing the local conductivity of the material rnby applying a voltage between tip and surface. The generated structures were stable for more than 16 h. It rnwas shown that the presence of water is essential for succesfull patterning.

Field-free control of magnetism in nanostructured materials probed with high resolution X-ray microscopy

Magnetic memories are a backbone of today's digital data storage technology, where the digital information is stored as the magnetic configuration of nanostructured ferromagnetic bits. Currently, the writing of the digital information on the magnetic memory is carried out with the help of magnetic fields. This approach, while viable, is not optimal due to its intrinsically high energy consumption and relatively poor scalability. For this reason, the research for different mechanisms that can be used to manipulate the magnetic configuration of a material is of interest. In this thesis, the control of the magnetization of different nanostructured materials with field-free mechanisms is investigated. The magnetic configuration of these nanostructured materials was imaged directly with high resolution x-ray magnetic microscopy. rnFirst of all, the control of the magnetic configuration of nanostructured ferromagnetic Heusler compounds by fabricating nanostructures with different geometries was analyzed. Here, it was observed that the magnetic configuration of the nanostructured elements is given by the competition of magneto-crystalline and shape anisotropy. By fabricating elements with different geometries, we could alter the point where these two effects equilibrate, allowing for the possibility to tailor the magnetic configuration of these nanostructured elements to the required necessities.rnThen, the control of the magnetic configuration of Ni nanostructures fabricated on top of a piezoelectric material with the magneto-elastic effect (i.e. by applying a piezoelectric strain to the Ni nanostructures) was investigated. Here, the magneto-elastic coupling effect gives rise to an additional anisotropy contribution, proportional to the strain applied to the magnetic material. For this system, a reproducible and reversible control of the magnetic configuration of the nanostructured Ni elements with the application of an electric field across the piezoelectric material was achieved.rnFinally, the control of the magnetic configuration of La0.7Sr0.3MnO3 (LSMO) nanostructures with spin-polarized currents was studied. Here, the spin-transfer torque effect was employed to achieve the displacement of magnetic domain walls in the LSMO nanostructures. A high spin-transfer torque efficiency was observed for LSMO at low temperatures, and a Joule-heating induced hopping of the magnetic domain walls was observed at room temperatures, allowing for the analysis of the energetics of the domain walls in LSMO.rnThe results presented in this thesis give thus an overview on the different field-free approaches that can be used to manipulate and tailor the magnetization configuration of a nanostructured material to the various technological requirements, opening up novel interesting possibilities for these materials.

A feasibility study for the provision of electronic healthcare tools and services in areas of Greece, Cyprus and Italy

Background Through this paper, we present the initial steps for the creation of an integrated platform for the provision of a series of eHealth tools and services to both citizens and travelers in isolated areas of thesoutheast Mediterranean, and on board ships travelling across it. The platform was created through an INTERREG IIIB ARCHIMED project called INTERMED. Methods The support of primary healthcare, home care and the continuous education of physicians are the three major issues that the proposed platform is trying to facilitate. The proposed system is based on state-of-the-art telemedicine systems and is able to provide the following healthcare services: i) Telecollaboration and teleconsultation services between remotely located healthcare providers, ii) telemedicine services in emergencies, iii) home telecare services for "at risk" citizens such as the elderly and patients with chronic diseases, and iv) eLearning services for the continuous training through seminars of both healthcare personnel (physicians, nurses etc) and persons supporting "at risk" citizens. These systems support data transmission over simple phone lines, internet connections, integrated services digital network/digital subscriber lines, satellite links, mobile networks (GPRS/3G), and wireless local area networks. The data corresponds, among others, to voice, vital biosignals, still medical images, video, and data used by eLearning applications. The proposed platform comprises several systems, each supporting different services. These were integrated using a common data storage and exchange scheme in order to achieve system interoperability in terms of software, language and national characteristics. Results The platform has been installed and evaluated in different rural and urban sites in Greece, Cyprus and Italy. The evaluation was mainly related to technical issues and user satisfaction. The selected sites are, among others, rural health centers, ambulances, homes of "at-risk" citizens, and a ferry. Conclusions The results proved the functionality and utilization of the platform in various rural places in Greece, Cyprus and Italy. However, further actions are needed to enable the local healthcare systems and the different population groups to be familiarized with, and use in their everyday lives, mature technological solutions for the provision of healthcare services.

SMARTDIAB: a communication and information technology approach for the intelligent monitoring, management and follow-up of type 1 diabetes patients

SMARTDIAB is a platform designed to support the monitoring, management, and treatment of patients with type 1 diabetes mellitus (T1DM), by combining state-of-the-art approaches in the fields of database (DB) technologies, communications, simulation algorithms, and data mining. SMARTDIAB consists mainly of two units: 1) the patient unit (PU); and 2) the patient management unit (PMU), which communicate with each other for data exchange. The PMU can be accessed by the PU through the internet using devices, such as PCs/laptops with direct internet access or mobile phones via a Wi-Fi/General Packet Radio Service access network. The PU consists of an insulin pump for subcutaneous insulin infusion to the patient and a continuous glucose measurement system. The aforementioned devices running a user-friendly application gather patient's related information and transmit it to the PMU. The PMU consists of a diabetes data management system (DDMS), a decision support system (DSS) that provides risk assessment for long-term diabetes complications, and an insulin infusion advisory system (IIAS), which reside on a Web server. The DDMS can be accessed from both medical personnel and patients, with appropriate security access rights and front-end interfaces. The DDMS, apart from being used for data storage/retrieval, provides also advanced tools for the intelligent processing of the patient's data, supporting the physician in decision making, regarding the patient's treatment. The IIAS is used to close the loop between the insulin pump and the continuous glucose monitoring system, by providing the pump with the appropriate insulin infusion rate in order to keep the patient's glucose levels within predefined limits. The pilot version of the SMARTDIAB has already been implemented, while the platform's evaluation in clinical environment is being in progress.

Analyse und Quantifizierung der Umweltaspekte von Fördermitteln in der Intralogistik

Das Projekt „Analyse und Quantifizierung der Umweltauswirkungen von Fördermitteln in der Intralogistik“ hat sich zum Ziel gesetzt, die Umweltaspekte verschiedener Fördermittel während des gesamten Lebenszyklus zu analysieren, zu quantifizieren und zu bewerten. Dazu werden für die Produktgruppen Flurförderzeuge, Krane & Hebezeuge und Lagertechnik Methoden entwickelt, um die Umweltaspekte, die von diesen Geräten bzw. Systemen zu erwarten sind, einer genaueren Untersuchung zu unterziehen.

Raw as Archival Still Image Format: A Consideration

Source materials like fine art, over-sized, fragile maps, and delicate artifacts have traditionally been digitally converted through the use of controlled lighting and high resolution scanners and camera backs. In addition the capture of items such as general and special collections bound monographs has recently grown both through consortial efforts like the Internet Archive's Open Content Alliance and locally at the individual institution level. These projects, in turn, have introduced increasingly higher resolution consumer-grade digital single lens reflex cameras or "DSLRs" as a significant part of the general cultural heritage digital conversion workflow. Central to the authors' discussion is the fact that both camera backs and DSLRs commonly share the ability to capture native raw file formats. Because these formats include such advantages as access to an image's raw mosaic sensor data within their architecture, many institutions choose raw for initial capture due to its high bit-level and unprocessed nature. However to date these same raw formats, so important to many at the point of capture, have yet to be considered "archival" within most published still imaging standards, if they are considered at all. Throughout many workflows raw files are deleted and thrown away after more traditionally "archival" uncompressed TIFF or JPEG 2000 files have been derived downstream from their raw source formats [1][2]. As a result, the authors examine the nature of raw anew and consider the basic questions, Should raw files be retained? What might their role be? Might they in fact form a new archival format space? Included in the discussion is a survey of assorted raw file types and their attributes. Also addressed are various sustainability issues as they pertain to archival formats with a special emphasis on both raw's positive and negative characteristics as they apply to archival practices. Current common archival workflows versus possible raw-based ones are investigated as well. These comparisons are noted in the context of each approach's differing levels of usable captured image data, various preservation virtues, and the divergent ideas of strictly fixed renditions versus the potential for improved renditions over time. Special attention is given to the DNG raw format through a detailed inspection of a number of its various structural components and the roles that they play in the format's latest specification. Finally an evaluation is drawn of both proprietary raw formats in general and DNG in particular as possible alternative archival formats for still imaging.

Sistemas de información geográfica aplicados al inventario y gestion de información rural

El objetivo del trabajo es explorar las ventajas de los SIG como herramienta para el inventario y gestión de información agropecuaria de pequeñas explotaciones. En el área de estudio, la planificación de la actividad rural muchas veces se realiza de manera intuitiva, lo que genera una deficiente utilización de la información y los recursos. Actualmente, los Sistemas de Información Geográfica (SIG) son una herramienta que posibilita el fácil almacenaje, acceso y gestión de datos. Los establecimientos ejemplo se seleccionaron por la disponibilidad de información registrada y porque las actividades realizadas son representativas del área. Se inventarió y relacionó la información, lo que generó cartografía que permitió visualizar diferentes escenarios productivos. Quedó demostrada la eficiencia de los SIG como una herramienta que mejora la gestión de la información inventariada y posibilita la planificación de la actividad futura

Sistemas de información geográfica aplicados al inventario y gestion de información rural

El objetivo del trabajo es explorar las ventajas de los SIG como herramienta para el inventario y gestión de información agropecuaria de pequeñas explotaciones. En el área de estudio, la planificación de la actividad rural muchas veces se realiza de manera intuitiva, lo que genera una deficiente utilización de la información y los recursos. Actualmente, los Sistemas de Información Geográfica (SIG) son una herramienta que posibilita el fácil almacenaje, acceso y gestión de datos. Los establecimientos ejemplo se seleccionaron por la disponibilidad de información registrada y porque las actividades realizadas son representativas del área. Se inventarió y relacionó la información, lo que generó cartografía que permitió visualizar diferentes escenarios productivos. Quedó demostrada la eficiencia de los SIG como una herramienta que mejora la gestión de la información inventariada y posibilita la planificación de la actividad futura

Sistemas de información geográfica aplicados al inventario y gestion de información rural

El objetivo del trabajo es explorar las ventajas de los SIG como herramienta para el inventario y gestión de información agropecuaria de pequeñas explotaciones. En el área de estudio, la planificación de la actividad rural muchas veces se realiza de manera intuitiva, lo que genera una deficiente utilización de la información y los recursos. Actualmente, los Sistemas de Información Geográfica (SIG) son una herramienta que posibilita el fácil almacenaje, acceso y gestión de datos. Los establecimientos ejemplo se seleccionaron por la disponibilidad de información registrada y porque las actividades realizadas son representativas del área. Se inventarió y relacionó la información, lo que generó cartografía que permitió visualizar diferentes escenarios productivos. Quedó demostrada la eficiencia de los SIG como una herramienta que mejora la gestión de la información inventariada y posibilita la planificación de la actividad futura