<p>The use of synthetic materials for tissue and organ reconstruction, i. e. tissue engineering, has become a promising alternative to current surgical therapies and may overcome the shortcomings of the methods in use today. The challenge is in the design and reproducible fabrication of biocompatible and bioresorbable polymers, with suitable surface chemistry, desirable mechanical properties, and the wanted degradation profile. These material properties can be achieved in various manners, including the synthesis of homo- and copolymers along with linear and star-shaped architectures. In many applications the materials’ three-dimensional structure is almost as important as its composition and porous scaffolds with high porosity and interconnected pores that facilitate the in-growth of cells and transportation of nutrients and metabolic waste is desired.</p><p>In this work linear and star-shaped polymers have been synthesized by ring-opening polymerization using a stannous-based catalyst and a spirocyclic tin initiator. A series of linear copolymers with various combinations of 1,5-dioxepane-2-one (DXO), Llactide (LLA) and ε-caprolactone (CL) have been polymerized using stannous octoate as catalyst. It is shown that the composition of the polymers can be chosen in such a manner that the materials’ mechanical and thermal properties can be predetermined. A solvent-casting and particulate leaching scaffold preparation technique has been developed and used to create three-dimensional structures with interconnected pores. The achieved physical properties of these materials’ should facilitate their use in both soft and hard tissue regeneration.</p><p>Well defined star-shaped polyesters have been synthesized using a spirocyclic tin initiator where L-lactide was chosen as a model system for the investigation of the polymerization kinetics. Neither the temperature nor the solvent affects the molecular weight or the molecular weight distribution of the star-shaped polymers, which all show a molecular weight distribution below 1.19 and a molecular weight determined by the initial monomer-to-initiator concentration.</p>

La performance d'un système d'optique adaptative (AO) est intrinsèquement liée à sa capacité à mesurer les déformations subies par le front d'onde incident lors de sa traversée de l'atmosphère. Or un certain nombre de limitations restreignent l'efficacité de cette analyse de front d'onde. Les plus importantes sont le bruit de mesure et l'anisoplanétisme. Le premier limite la magnitude des objets astronomiques pouvant servir de guides aux systèmes d'AO, tandis que le second restreint leur champ corrigé à quelques dizaines de secondes d'arc, du fait de la distribution volumique de la turbulence atmosphérique. A elles deux, ces limitations réduisent à quelques pourcents la couverture de ciel des instruments assistés par AO. Pour cette raison, les nouvelles générations d'optiques adaptatives ont pour objectif soit la très haute performance, impliquant entre autres une bonne robustesse au bruit de mesure, soit l'élargissement du champ corrigé, impliquant la connaissance de la répartition 3D de la turbulence atmosphérique. Pour ces systèmes d'AO à large champ, il est indispensable d'utiliser plusieurs directions d'analyse. La problématique de l'analyse de front d'onde s'articule alors autour de trois pôles : les étoiles guides dont on dispose pour effectuer la multi-analyse, le concept d'analyse de front d'onde considéré pour mesurer le volume de turbulence et la capacité des senseurs de front d'onde à fournir des mesures de qualité. L'objectif de cette thèse est d'étudier chacun de ces trois aspects. Ainsi, une redéfinition de la notion de couverture de ciel est proposée pour les AO à large champ, permettant de prendre en compte le nombre d'étoiles guides et leur magnitude, mais également la fraction du champ scientifique qu'elles permettent de couvrir, le concept d'analyse de front d'onde considéré et l'objectif de performance de l'instrument. Par ailleurs une étude comparative des concepts d'analyse de front d'onde Star Oriented et Layer Oriented est présentée, sur laquelle on s'appuie pour proposer une optimisation de chaque concept. On montre ainsi qu'une fois optimisés ils présentent tous deux des performances très proches. Enfin, on propose dans un troisième temps une étude comparative de plusieurs estimateurs de pente pour l'analyseur Shack-Hartmann. On étudie en particulier l'estimateur centre de gravité pondéré, qui offre à la fois une bonne robustesse au bruit et de bonnes propriétés de linéarité. Cette dernière étude est utile aussi bien pour l'AO à large champ que pour l'AO à très haute performance.

Competitive video gaming is experiencing exponential growth. Advances in technology and global Internet penetration has created highly dedicated fan bases for games played at a competitive level. Game developing companies are beginning to focus their attention on making games for the new eSports market. How avid eSports fans view competitive gaming is disrupting traditional consumption models. Twitch.TV a site that streams live gaming content is seeing massive growth. Now, more than ever, dedicated gamers can live off of playing games – whether by competing in tournaments as sponsored players or running ads on their Twitch.TV live stream while they play. The communities that have developed around different genres of competitive games are as varied as traditional sports such as Major League Baseball or the National Football League. A new industry with a complex infrastructure is developing in this new market. / text

Cover title: Draft technical appendix. / Phoenix Urban Study: Final Report / The work upon which this publication is based was supported by funds provided by the U.S. Army Corps of Engineers, Los Angeles District, as authorized by resolution of the Senate Public Works Committee on July 31, 1973. This report was prepared as a contribution to the Phoenix Urban Study under auspices of the U.S. Army Engineer District, Los Angeles.

Αντικείμενο της παρούσας διδακτορικής διατριβής αποτελεί η ανάπτυξη της πειραματικής Μεθόδου Διέγερσης Επιφανειακών Πλασμονίων (Surface Plasmon Resoanance, SPR) για τη μελέτη διεπιφανειακών φαινομένων και ειδικότερα των ιδιοτήτων ισορροπίας και της κινητικής της προσρόφησης πολυμερών και ολιγομερών στη διεπιφάνεια υγρού / στερεού. Στα πλαίσια της διατριβής, κατασκευάσθηκε εξ’ αρχής πειραματική διάταξη συντονισμού επιφανειακών πλασμονίων, η οποία χρησιμοποιήθηκε για την μελέτη του φαινομένου της προσρόφησης. Παράλληλα αναπτύχθηκε θεωρητικό υπόδειγμα και υπολογιστικά εργαλεία ανάλυσης των πειραματικών μετρήσεων. Με τη χρήση της πειραματικής διάταξης μελετήθηκε η διαδικασία της προσρόφησης γραμμικών και αστεροειδών πολυμερών στη διεπιφάνεια υγρού / στερεού όπως επίσης και τασιενεργών ολιγομερών τα οποία σχηματίζουν Αυτό-οργανούμενα Μονομοριακά Στρώματα (Self Assembled Monolayers) σε επιφάνειες οξειδίου του αλουμινίου. Επιπλέον διερευνήθηκε η επίδραση της αρχιτεκτονικής των πολυμερικών αλυσίδων σε σχέση με την ικανότητά τους να αυτο-οργανώνονται σε στρώματα πολυμερικών ψηκτρών (polymer brushes). Τα πειραματικά αποτελέσματα συγκρίνονται με μετρήσεις οι οποίες έγιναν με τη μέθοδο ανάκλασης νετρονίων. Για την κατανόηση των μικροσκοπικών μηχανισμών που υπεισέρχονται κατά την αυτό-οργάνωση των πολυμερών, γίνεται χρήση θεωρητικών υποδειγμάτων κλίμακας και υπολογιστικών προσομοιώσεων Monte Carlo. Περαιτέρω, μέσω της χρήσης λεπτών στρωμάτων νανο-πορώδους αλουμίνας, προτείνεται μια νέα παραλλαγή της μεθόδου διέγερσης επιφανειακών πλασμονίων η οποία όπως αποδεικνύεται, αυξάνει την ευαισθησία της μεθόδου κατά μια τάξη μεγέθους, στην περίπτωση της ανίχνευσης της προσρόφησης ολιγομερών. Η διατριβή παρουσιάζει ολοκληρωμένα τη χρήση της μεθόδου διέγερσης επιφανειακών πλασμονίων για την αναλυτική μελέτη της προσρόφησης μορίων σε επιφάνειες. Η επέκταση της μεθόδου με τη χρήση νανο-δομημένων υλικών ανοίγει τον δρόμο για πλειάδα νέων εφαρμογών στο πεδίο της ανίχνευσης προσροφημένων μορίων από διαλύματα ιδιαίτερα χαμηλών συγκεντρώσεων. / The objective of the present PhD thesis is the development of the experimental Surface Plasmon Resonance (SPR) method, for the study of interfacial phenomena such as the equilibrium properties and kinetics of polymer and oligomer adsorption at the liquid / solid interface. For the purposes of this work a custom-made experimental apparatus has been build and used for the acquisition of SPR experimental results. A theoretical model and various computational tools were also developed for the analysis of the experimental data. With the aid of this apparatus, the adsorption process of linear and star-like polymers at the liquid / solid interface was studied together with the self-assembly of functional oligomer monolayers on alumina surfaces. In addition, the effect of different chain structure (molecular architecture) on the formation of polymer brush layers was investigated. The experimental results are compared with measurements by neutron reflectivity experiments. For the investigation of the microscopic mechanisms that are involved in the polymer self-assembly, scaling theoretical calculations and Monte Carlo computer simulations were performed. Furthermore, by the use of thin nano-porous alumina films, a new variation of the SPR method is proposed. It is demonstrated, that this improved method is characterized by over one order of magnitude higher sensitivity in the case of the detection of adsorbed oligomers. The present thesis describes in detail the use of the SPR method for the analytical study of molecular adsorption on surfaces. The improvement of the SPR technique by the use of nano-structured materials opens new prospects for many new applications in the field of molecular detection in very dilute solutions.

The objectives of this dissertation were to find a principal domain of promising and technologically feasible reactor physics characteristics for a multi-purpose, modular-sized, lead-cooled, fast neutron spectrum reactor fueled with an advanced uranium-transuranic-nitride fuel and to determine the principal limitations for the design of an autonomous long-term multi-purpose fast reactor (ALM-FR) within the principal reactor physics characteristic domain. The objectives were accomplished by producing a conceptual design for an ALM-FR and by analysis of the potential ALM-FR performance characteristics. The ALM-FR design developed in this dissertation is based on the concept of a secure transportable autonomous reactor for hydrogen production (STAR-H2) and represents further refinement of the STAR-H2 concept towards an economical, proliferation-resistant, sustainable, multi-purpose nuclear energy system. The development of the ALM-FR design has been performed considering this reactor within the frame of the concept of a self-consistent nuclear energy system (SCNES) that satisfies virtually all of the requirements for future nuclear energy systems: efficient energy production, safety, self-feeding, non-proliferation, and radionuclide burning. The analysis takes into consideration a wide range of reactor design aspects including selection of technologically feasible fuels and structural materials, core configuration optimization, dynamics and safety of long-term operation on one fuel loading, and nuclear material non-proliferation. Plutonium and higher actinides are considered as essential components of an advanced fuel that maintains long-term operation. Flexibility of the ALM-FR with respect to fuel compositions is demonstrated acknowledging the principal limitations of the long-term burning of plutonium and higher actinides. To ensure consistency and accuracy, the modeling has been performed using state-of-the-art computer codes developed at Argonne National Laboratory. As a result of the computational analysis performed in this work, the ALM-FR design provides for the possibility of continuous operation during about 40 years on one fuel loading containing mixture of depleted uranium with plutonium and higher actinides. All reactor physics characteristics of the ALM-FR are kept within technological limits ensuring safety of ultra-long autonomous operation. The results obtained provide for identification of physical features of the ALM-FR that significantly influence flexibility of the design and its applications. The special emphasis is given to existing limitations on the utilization of higher actinides as a fuel component.

Bakgrund: Den svenska hälso- och sjukvården står idag inför en mängd problem som kommer att förvärras i framtiden. Ökande kostnader, bristande tillgänglighet och växande förväntningar från medborgarna är några av problemen som måste lösas. För att möta dessa problem måste den svenska hälso- och sjukvården förändra sig, något som de historiskt har haft svårigheter med. I andra länder har man använt sig av designtänkande för att förändra sig, med goda resultat.  Problem: Vilka faktorer är viktiga för att man ska kunna lösa upp det organisatoriska motståndet mot förändring inom den svenska hälso- och sjukvården?  Syfte: Syftet med denna undersökning är att analysera och utvärdera designtänkande som hjälpmedel för förändring av hälso- och sjukvårdsorganisationen.  Metod: Undersökningen är kvalitativ och består av en jämförelse mellan förändringsarbeten som genomförts med respektive utan designtänkande.  Teorier: Professionsbyråkrati, dominerande idéer och företagets kultur, förändringsanalys, designtänkande och värdestjärnan.  Empiri: 17 kvalitativa intervjuer med anställda vid tre sjukhus (Karolinska sjukhuset, S:t Görans sjukhus AB och Mälarsjukhuset) samt tre intervjuer med industridesigners som har genomfört förändringsarbete inom sjukvården.  Analys: Analysen är uppdelad i två delar. Först analyserar författarna de förändringsarbeten som har genomförts utan designtänkande följt av en analys av de förändringsarbeten som genomförts med designtänkande. Variabler som är centrala för analysen är; motstånd vid förändring, förankring och involvering.  Resultat: Denna undersökning visar att designtänkande är ett utmärkt hjälpmedel för förändring eftersom det är en användarfokuserad och involverande metod som baseras på goda faktaunderlag. Genom att ta in designkompetens utifrån kan hälso- och sjukvården få en bättre helhetssyn av sin egen verksamhet och få hjälp att lösa problem som de ännu inte lyckats lösa själva.  Slutsats: De faktorer som är viktiga för att man ska kunna lösa upp det organisatoriska motståndet mot förändring inom den svenska hälso- och sjukvården är att beslutsfattarna närmar sig verksamheten, att man tillför resurser, att förändringar är bättre förankrade i verksamheten och involverar de anställda samt att man tar in kompetens utifrån som kan skapa en samverkan mellan de avdelningar och vårdinstanser som idag inte samarbetar. / Background: Swedish healthcare is facing a number of problems that will only get worse in the future. Increasing costs, lack of accessibility and growing expactasions from citizens are just some of the problems. The Swedish healthcare system has to change, something that they, from a historical point of view, have had great difficulties with. In other countries design thinking has been a succesful method for change.  Problem: Which factors are essential to disolve the organizational resistance to change in Swedish healthcare?  Objective: The objective of this study is to analyse and evaluate the design thinking as a method for change in Swedish healthcare.  Method: This study uses a cualitative method and compares organizational change processes performed with and without design thinking.  Theories: Professional bureaucracy, dominating ideas and company culture, change analysis, design thinking and value star.  Empiric: 17 qualitative interviews with employes at three different hospital (Karolinska hospital, S:t Görans hospital AB and Mälarsjukhuset) and three interviews with industrial designers who’ve worked with design thinking and service design within the Swedish healthcare system.  Analysis: The analysis consists of two parts. First the authors analyse organizational change processes without design thinking as a method followed by an analysis of organizational change processes with design thinking as a method. Variables that are central for the analysis are; resistance to change, the anchoring of change in the organization and involvement.  Result: This paper shows that design thinking is a good method for change in healthcare because it is a user oriented, involving and fact based method. By bringing in design skills from outside the organisation, Swedish healthcare can gain an improved holistic view of its operations and get the help they need to solve the problems that they have yet to solve on their own.  Conclusion: Factors that are essential to disolve the organizational resistance to change in Swedish healthcare is that the decision makers must get closer to the organization floor, more resources, better anchored changes processes, involvement of the staff and seeking help outside of the organization to create collaboration between divisions.

Les polymères amphiphiles sont largement utilisés pour les applications biomédicales et pharmaceutiques. Afin d’améliorer les chances de biocompatibilité des nouveaux polymères que nous voulons développer, nous avons utilisé des composés naturels, les acides biliaires, comme produits de départ dans la synthèse de ces polymères. De nouveaux polymères anioniques amphiphiles dérivés de l’acide cholique ont été préparés par polymérisation radicalaire par transfert d’atomes. Par un contrôle rigoureux des conditions de polymérisation, des bras de poly(acide acrylique) de différentes longueurs ont été greffés sur le squelette de l’acide cholique. L’architecture moléculaire des polymères a été étudiée par spectroscopie 1H RMN et par spectrométrie de masse. Ces polymères en étoile formés par l’acide biliaire modifié sont capables de s’agréger dans l’eau même si les groupements hydroxyles ont été remplacés par des segments plus volumineux. Il a été observé que les liaisons ester entre le polymère et le cœur d’acide cholique sont sensibles à l’hydrolyse en solution aqueuse. Pour remédier au problème de stabilité en solution aqueuse et pour avoir, en même temps, des bras hydrophiles non ioniques et biocompatibles, de l’oxyde d’éthylène a été polymérisé sur l’acide cholique par polymérisation anionique. Les liaisons éther formées entre le polymère et les groupements hydroxyles de l’acide biliaire sont plus stables que les liaisons ester sur le polymère de poly(acide acrylique). Les conditions de réaction de la polymérisation anionique ont été optimisées et ont donné des polymères aux architectures et aux masses molaires contrôlées. Les nouveaux polymères forment des agrégats sphériques tel qu’observé par microscopie électronique à transmission avec des échantillons préparés par la méthode de fracture à froid. Leur morphologie est différente de celle des agrégats cylindriques formés par les acides biliaires. Avec la méthode optimisée pour la polymérisation anionique, l’éther d’allyle et glycidyle a été polymérisé sur un dérivé d’acide cholique, suivi par une thiolation des liaisons doubles pour introduire l’amine ou l’acide sur la chaîne polymère. Cette addition radicalaire est efficace à plus de 90%. Les polymères qui en résultent sont solubles dans l’eau et s’agrègent à une certaine concentration critique. Il est particulièrement intéressant d’observer la thermosensibilité des polymères ayant des groupements amine, laquelle peut être modulée en acétylant partiellement les amines, donnant des points nuages entre 15 et 48°C. / Amphiphilic polymers are very useful in biomedical and pharmaceutical applications. To improve the biocompatibility of such polymers, we chose to use natural compounds such as bile acids as the starting material in the synthesis of the polymers. New anionic polymers have been prepared by atom transfer radical polymerization. Poly(acrylic acid) arms of various lengths have been grafted onto a bile acid core. The molecular architecture has been confirmed by 1H NMR spectroscopy and by mass spectrometry. The star polymers obtained from modified bile acid can aggregate in water, even though the hydroxyl groups were replaced by bulkier chains. The ester linkages between the polymers and the bile acid core are prone to hydrolysis in aqueous solutions. In order to improve the stability of the polymers in aqueous solutions and to introduce neutral and biocompatible hydrophilic arms, ethylene oxide has been polymerized onto a cholic acid core by anionic polymerization. The ether linkages formed between the hydroxyl groups of the bile acid and the poly(ethylene glycol) are more stable than the ester linkages formed with the poly(acrylic acid) polymers. The reaction conditions for the anionic polymerization have been optimized and provided well-defined polymers with narrow molecular weight distributions. The new polymers formed spherical aggregates as shown by transmission electron microscopy with samples prepared by the freeze-fracture technique. Their morphology is different from those of the cylindrical aggregates formed by bile salts. With the optimized method for anionic polymerization, allyl glycidyl ether was grafted onto a derivative of cholic acid, followed by thiolation, a radical addition, of the allyl groups to introduce amine or carboxylic acid groups to the polymer chains. This radical addition had an efficiency of more than 90%. The resulting polymers were water-soluble and were found to aggregate above a certain critical concentration. It is particularly interesting to observe thermosensitivity of the star polymers bearing amine groups. The thermosensitivity of such polymers can be further tuned by partial acetylation of the amine groups, yielding polymers with cloud points in the temperature range from 15 to 48°C.

<p>One of the most powerful aspects of conducting polymers is their ability to be nanostructured through innovative, synthetically manipulated, transformations, such as to tailor-make the polymers for specialized applications. In the exponentially increasing wide field of nanotechnology, some special attention is being paid to innovative hybrid dendrimer-core based polymeric smart materials. Star copolymers are a class of branched macromolecules having a central core with multiple linear polymer chains extending from the core. This intrinsic structural feature yields a unique 3D structure with extended conjugated linear polymer chains, resulting in star copolymers, which have higher ionic conductivities than their corresponding non-star conducting polymer counterparts. In this study an in-depth investigation was carried out into the preparation and characterization of specialized electronic &lsquo / smart materials&rsquo / . In particular, the preparation and characterization of novel conducting dendrimeric star copolymers which have a central poly(propylene imine) (PPI) dendrimer core with conducting polypyrrole (PPy) chains extending from the core was carried out. This involved, first, the preparation of a series of dendrimeric polypyrrole poly(propylene imine) star copolymers (PPI-co-PPy), using generations 1 to 4 (G1 to G4) PPI dendrimer precursors. The experimental approach involved the use of both chemical and electrochemical synthesis methods. The basic procedure involved a condensation reaction between the primary amine of a diamino functional PPI dendrimer surface and 2-pyrrole aldehyde, to afford the pyrrole functionalized PPI dendrimer (PPI-2Py). Polymerization of the intrinsically contained monomeric Py units situated within the dendrimer backbone was achieved via two distinctly different routes: the first involved chemical polymerization and the second was based on potentiodynamic oxidative electrochemical polymerization. The star copolymers were then characterized using various sophisticated analytical techniques, in-situ and ex-situ. Proton nuclear magnetic resonance spectroscopy (1HNMR) and Fourier transform infrared spectroscopy (FTIR) were used to determine the structures. Scanning electron microscopy (SEM) was used to determine the morphology. Themogravimetric analysis (TGA) was used to study the thermal stability of the prepared materials. X-ray diffraction analysis (XRD) was used to study the structural make-up of phases, crystallinity and amorphous content. Hall effect measurements were carried out to determine the electrical conductivity of the chemically prepared star copolymers. The PPI-co-PPy exhibited improved thermal stability compared to PPI-2Py, as confirmed by TGA. SEM results showed that the surface morphology of the functionalized dendrimer and star copolymer differed. The surface morphology of the chemically prepared star copolymers resembled that of a flaky, waxy material, compared to the ordered morphology of the electrochemically grown star copolymers, which resembled that of whelk-like helixes. In the case the electrochemically grown star copolymers, SEM images recorded at higher magnifications showed that the whelk-like helixes of the star copolymers were hollow tubes with openings at their tapered ends, and had an average base diameter of 2.0 &mu / m. X-ray diffraction analysis of the first generation star copolymer G1PPI-co-PPy revealed a broadly amorphous structure associated with PPy, and crystalline peaks for PPI. Cyclic voltammetry (CV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivity of the star copolymer materials. Electrochemical impedance spectroscopy data showed that the G1PPI-co-PPy exhibited slightly higher ionic conductivity than pristine PPy in lithium perchlorate. The second generation star copolymer G2PPI-co-PPy electrochemically deposited on a platinum (Pt) electrode had a lower electrochemical charge transfer resistance compared to electrodeposited polypyrrole (PPy) on a Pt electrode, and bare Pt. The decrease in charge transfer resistance was attributed to an increase in the conjugation length of the polymer as a result of the linking of the highly conjugated PPy to the PPI dendrimer. Bode impedimetric analysis indicated that G2PPI-co-PPI was a semiconductor, with a maximum phase angle shift of 45.3&deg / at 100 MHz. The star copolymer exhibited a 2- electron electrochemistry and a surface coverage of 99%. Results of Hall effect measurements showed that the star copolymer is a semiconducting material, having a conductivity of 0.7 S cm-1, in comparison to the 1.5 S cm-1 of PPy. To the best of my knowledge, these new star copolymers have not been reported in the open literature. Their properties make them potentially applicable for use in biosensors.</p>

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