There is a need for multifunctional polymer-particle complexes for use in biomedical applications such as for drug delivery or as MRI contrast agents where composition and stability are essential for the complexes to function. This work outlines a general methodology for rationally designing complexes stabilized with polymer brush layers using adapted star polymer models for brush extension and pair potential. Block copolymer micelles were first utilized for experimental validation by using the brush extension model to predict the size and the interaction model to predict the second virial coefficient, A2. Subsequently, the models were used to predict the size and colloidal stability of magnetite-polymer complexes using the modified Deryaguin-Verwey-Landau-Overbeek theory. Novel hydrophilic triblock copolymers comprised of poly(ethylene oxide) tailblocks and a carboxylic acid containing polyurethane center block were examined by static and dynamic light scattering (SLS and DLS), small angle neutron scattering (SANS), and densiometry. Under conditions when the charge is suppressed such as at low pH and/or high ionic strength, the polymer chains self-assemble into micelles, whereas unimers alone are present under conditions where charge effects are important, such as high pH and low ionic strength. A model for effective interaction between star polymers was used to obtain an expression for the second virial coefficient (A2) for micelles in solution. The values of A2 obtained using this method were compared with experimentally determined values for star polymers and micelles. In doing so, not only was a new means of calculating A2 a priori introduced, but the applicability of star polymer expressions to micellar systems was established. Through the analogy of micelles to sterically stabilized nanoparticles, this model was applied to water-soluble block copolymers adsorbed on magnetite nanoparticles for the purpose of tailoring a steric stabilizing brush layer. The sizes of the magnetite-polymer complexes were predicted using the star polymer model employed for the micelle study with an added layer to account for the anchor block. Colloidal stability was predicted from extended DLVO theory using the pair interaction. This work will lead to a better understanding of how to design ion-containing block copolymers for steric stabilization of metal oxide nanoparticles. / Ph. D.

We have measured the flavor dependence of multiplicities for $\pi^+$ and $\pi^-$ production in semi-inclusive deep-inelastic scattering (SIDIS) on proton and deuteron targets. We used a 10.6 GeV electron beam at Jefferson Lab, and 4 msr solid angle spectrometers (HMS for electrons, SHMS for pions), the lepton vertex spanned the kinematic range $0.3

No / The latest advances in mesocrystal formation and non-classical crystallization of pre-synthesised nanoparticles have been reviewed with the focus on providing a fuller description of a number of complex systems and their properties and applications through examination of the crystallisation mechanisms at work. Two main crystallization principles have been identified; classical crystallization and particle based aggregation modes of non-classical pathways. To understand the non-classical pathways classical crystallization and its basics are introduced before non-classical pathways, such as oriented attachment and mesocrystal formation, are examined. In particular, the various destabilization mechanisms as applied to the pre-synthesized building blocks in order to form mesocrystalline materials as well as the interparticular influences providing the driving forces are analyzed and compared to the mechanisms at work within classical crystallization. Furthermore, the new properties of the mesocrystalline materials that derive from the collective properties of the nanoparticular building units, and their applications potential are presented. It is shown that this new class of materials has the potential to impact in a number of important areas such as sensor applications, energy conversion, photonic crystals as well as for energy storage, optoelectronics and heterogeneous catalysis or photocatalysis.

No description available.

Diese Dissertation widmet sich der spektroskopischen Untersuchung verschiedener Aspekte der Strahlungsemis\-sion hochgeladener Krypton-Ionen mit Relevanz für die Fusionsforschung. Die Experimente hierzu erfolgten an der Berliner Elektronenstrahl-Ionenfalle (EBIT). Der erste Teil der Arbeit hat die Messung kanalspezifischer Wirkungsquerschnitte für die dielektronische Rekombination (DR) der KL$n$-Resonanzserie ($n$=2, \ldots, 5) von Helium- bis Kohlenstoff-ähnlichen Kr-Ionen ($\mbox{Kr}^{(34\, \ldots\,30)+}$) zum Inhalt, die relativ zum Wirkungsquerschnitt der nichtresonanten strahlenden Rekombination (RR) bestimmt wurden. Die Anpassung der Anregungskurven durch eine Modellfunktion aus berechneten Resonanzst ärken ermöglichte den Vergleich mit theoretischen DR-Wirkungsquerschnitten. Es zeigt sich, dass Vorhersagen des HULLAC-Atomstrukturcodes für die Resonanz\-st"ar\-ken der Kr-Ionen durch das Experiment innerhalb der Me"sunsicherheiten best"a\-tigt werden. Darüber hinaus wurde auch die Relaxation der einfach angeregten Ionen nach erfolgtem DR-Stabilisierungsübergang analysiert. Die zur Auswertung der DR-Anre\-gungs\-kurven angewandte Technik eröffnet gleichzeitig eine spektroskopische Methode für die Bestimmung der relativen Konzentration hochgeladener Ionen in EBIT. Die Messung der Strahlungskühlungsrate von Krypton, die den zweiten inhaltlichen Schwerpunkt der Dissertation darstellt, wäre ohne diese in situ Diagnostik der Ladungbilanz nicht möglich gewesen. Hier wurde die Ionenfalle so eingestellt, dass sich eine Ladungsverteilung herausbildet, die dem Ionisationsgleichgewicht eines Plasmas bei einer Temperatur von etwa $5\;\mbox{keV}$ entspricht. Die Bestimmung der Strahlungsk"uhlungsrate profitierte von dem Potential einer EBIT, die gefangenen Ionen mit Elektronenenergien aus einem weiten Bereich abzutasten und einzelne Strahlunsprozesse selektiv anzuregen. Die Röntgenemission verschiedener Strahlungskanäle, wie Bremsstrahlung, strahlende Rekombination, dielektronische Rekombination und Linienstrahlung nach direkter Anregung wurde separat erfaßt. Hieraus konnten erstmals kanalspezifische Strahlungskühlungsraten bestimmt werden. Es stellte sich heraus, dass der dominante Beitrag zur Strahlungskühlungsrate durch die direkt angeregte Linienstr ahlung des L-Schalen-Spektrums zustande kommt, die etwa 75\% der gesamten Verlustleistung ausmacht. Beim Vergleich der totalen Strahlungsverlustleistung mit Vorhersagen der Theorie sind Abweichungen festzustellen. Die berechneten Werte sind je nach Modell um einen Faktor 1.5 - 2.0 kleiner als das Ergebnis der Messung. Dieser Unterschied liegt außerhalb der experimentellen Unsicherheit von maximal 30\%. / This thesis deals with the spectroscopic investigation of various aspects of the x-ray emission of highly charged krypton ions with relevance for fusion research. The experiments have been performed at the Berlin electron beam ion trap (EBIT). One part of the work was devoted to the measurement of channel-specific cross sections for dielectronic recombination (DR) via the KL$n$ ($n$=2, \ldots, 5) resonance series of He- to C-like krypton ions ($\mbox{Kr}^{(34\, \ldots\,30)+}$). The DR cross sections were determined relative to the cross section for non-resonant radiative recombination (RR). A fit procedure was used to compare the measured data with theoretical calculations. Predictions of the HULLAC atomic structure code are confirmed within the experimental uncertainties. Additionally, the radiative relaxation mechanism following the stabilizing transition in the DR process was analyzed. The approach used to obtain the DR excitation function opens up a spectroscopic method to determine the relative abundance of the highly charged ions in the trap. This in situ diagnostic of the charge state balance allowed for the measurement of the radiative cooling rates of krypton being the second focus of the thesis. For this purpose EBIT was tuned to a charge state distribution approaching the ionization balance of a plasma at a temperature of about $5\;\mbox{keV}$. EBIT's capability to sample a wide range of electron-beam energies and distinguish between different radiation channels was utilized to determine the cooling rate. The x-ray emission from the various plasma radiation channels, like bremsstrahlung, radiative recombination, dielectronic recombination, and line radiation following electron-impact excitation was analyzed. For the first time, channel-specific cooling rates could be obtained from these data. It was found, that the dominant contribution to the cooling rate is made up by the directly excited x-rays of the L-shell spectra of krypton, producing more than 75\% of the total radiation loss. A difference with theoretical calculations is noted for the total cooling rate. The predicted values are lower by a factor of 1.5 - 2.0, depending on the theoretical model. This discrepancy is clearly beyond the experimental uncertainty of 30\% at maximum.

Macromolecular biomaterials often require covalent crosslinking to achieve adequate stability and mechanical strength for their given application. However, the use of auxiliary chemicals may be associated with long-term toxicity in the body. Oppositely-charged polyelectrolytes (PEs) have the advantage that they can self-crosslink electrostatically and those derived from marine organisms are an inexpensive alternative to glycosaminoglycans present in the extracellular matrix of human tissues. A range of different combinations of PEs and preparation conditions have been reported in the literature. However, although there has been some work on complex formation between chitosan (CS) and carrageenan (CRG), much of the work undertaken has ignored the effect of pH on the consequent physicochemical properties of self-crosslinked polyelectrolyte complex (PEC) gels, films and scaffolds. Chitosan is a positively-charged polysaccharide with NH3+ side groups derived from shrimp shells and, carrageenan is a negatively-charged polysaccharide with OSO3- side groups derived from red seaweed. These abundant polysaccharides possess advantageous properties such as biodegradability and low toxicity. However, at present, there is no clear consensus on the cell binding properties of CS and CRG or CS-CRG PEC materials. The aim of this study was to explore the properties of crosslinker-free PEC gels, solvent-cast PEC films and freeze-dried PEC scaffolds based on CS and CRG precursors for medical applications. The objective was to characterise the effect of pH of the production conditions on the physicochemical and biological properties of CS-CRG PECs. Experimental work focused on the interaction between PEs, the composition of PECs, the rheological properties of PEC gels and the mechanical properties of PEC films and scaffolds. In addition, cell and protein attachment to the PEC films was assessed to determine their interactions in a biological environment. For biomedical applications, these materials should ideally be stable when produced such that they can be processed to form either a film or a scaffold and have mechanical properties comparable to those of collagenous soft tissues. FTIR was used to confirm PEC formation. Zeta potential measurements indicated that the PECs produced at pH 2-6 had a high strength of electrostatic interaction with the highest occurring at pH 4-5. This resulted in stronger intra-crosslinking in the PEC gels which led to the formation of higher yield, solid content, viscosity and fibre content in PEC gels. The weaker interaction at pH 7-12 resulted in higher levels of CS incorporated into the complex and the formation of inter-crosslinking through entanglements between PEC units. This resulted in the production of strong and stiff PEC films and scaffolds appropriate for soft tissue implants. The PECs prepared at pH 7.4 and 9 also exhibited low swelling and mass loss, which was thought to be due to the high CS content and entanglements. From the range of samples tested, the PECs produced at pH 7.4 appeared to show the optimum combination of yield, stability and homogeneity for soft tissue implants. Biological studies were performed on CS, CRG and PECs prepared at pH 3, 5, 7.4 and 9. All of the PE and PEC films were found to be non-cytotoxic. When the response of three different cell types and a high binding affinity protein (tropoelastin) was evaluated; it was found that the CS-CRG PEC films displayed anti-adhesive properties. Based on these experimental observations and previous studies, a mechanistic model of the anti-adhesive behaviour of PEC surfaces was proposed. It was therefore concluded that the CS-CRG PECs produced might be suitable for non-biofouling applications.

Matéria orgânica natural (MON) é uma complexa matriz de compostos orgânicos originados de fontes naturais que estão presentes nas bacias hidrográficas e dentro dos corpos hídricos. MON é comprovado precursor de subprodutos da desinfecção (SPD), além de afetar processos de tratamento de água tais como coagulação, desinfecção, oxidação, adsorção em carvão ativado e filtração em membranas. Por estas razões, a redução da MON no tratamento de água para consumo humano é importante. Muitos métodos têm sido utilizados para caracterizar e quantificar a MON. Entre os métodos usados se encontram a adsorção em resinas e parâmetros de massa. Carbono orgânico total (COT), carbono orgânico dissolvido (COD), absorção à luz ultravioleta (UV254) e absorbância específica de luz ultravioleta (AEUV) são usualmente utilizados como parâmetros de massa. O fracionamento rápido é uma técnica que usa diferentes resinas para separar frações da MON. Nesse contexto, este trabalho teve como objetivo geral caracterizar a matéria orgânica dissolvida usando o método do fracionamento rápido e os parâmetros COD, UV254 e AEUV em processos de tratamento de água para consumo humano. Também foram analisados turbidez, cor, pH e alcalinidade. Foram avaliados os efeitos dos processos de coagulação, sedimentação, filtração em filtro de areia e adsorção em carvão ativado granular (CAG) nas frações que formam a MON. As amostras de água foram coletadas em estação de tratamento de água da cidade de Porto Alegre, RS. Os valores de turbidez, cor, pH, alcalinidade, UV254 e COD reduziram-se ao longo dos processos de tratamento, enquanto que a AEUV aumentou na sequência dos processos. Os valores de absorção de UV254 decresceram à medida que as amostras passavam através das distintas resinas do fracionamento rápido (DAX-8, XAD-4 e IRA-958). Estas frações tiveram reduções importantes em todas as amostras. Os AMH decresceram de 2,29 mg/L COD na água bruta para 0,25 mg/L COD no efluente da coluna de carvão ativado, enquanto que os ALH reduziram de 1,29 mg/L na água bruta para 0,22 mg/L no efluente do filtro de CAG. As concentrações observadas de matérias hidrofílicas carregadas (MHC) (ex., proteínas) e hidrofílicas neutras (MHN) (ex., carboidratos) foram próximas a zero em todas as amostras. Foi possível concluir que os processos de tratamento afetam a distribuição de frações da MON presente na água. / Natural organic matter (NOM) is a complex matrix of organic compounds originated from natural sources that are present in the watershed and in within water bodies. NOM is a known precursor of disinfection byproducts (DBP) and affects drinking water treatment processes such as coagulation, disinfection, oxidation, carbon adsorption and membrane filtration. For these reasons, the reduction of NOM in water treatment is important. Many methods have been used to characterize and quantify NOM, among them, the resin adsorption and the mass parameters methods. The latter include total organic carbon (TOC), dissolved organic carbon (DOC), ultraviolet absorption at 254 nm (UV254), and specific UV absorption (SUVA). Rapid fractionation is one of the resin adsorption methods. This study has as objective the characterization of dissolved organic matter using rapid fractionation and the parameters DOC, UV254 and SUVA in drinking water treatment processes. Turbidity, color, pH and alkalinity were also analyzed. It was evaluated the effect of coagulation, sedimentation, filtration in sand filter and granular activated carbon (GAC) adsorption in the fractions that form NOM. Samples were collected in a drinking water treatment plant in the city of Porto Alegre, RS. Values of turbidity, color, pH, alkalinity, UV254 and DOC decreased along treatment, while values of SUVA increased. UV254 reduced as the samples passed through the distinct resins used for rapid fractionation (DAX-8, XAD-4 e IRA-958). The main fraction of DOC in samples was very hydrophobic acids (VHA) (as humic acids) followed by slightly hydrophobic acids (SHA) (as fulvic acids). These fractions had major reductions as the samples run through the resins. VHA decreased from 2,29 mg/L COD in raw water to 0,25 mg/L COD in activated carbon column effluent, while SHA decreased from 1,29 mg/L in raw water to 0,22 mg/L in GAC filter effluent. Charged hydrophilic matters (CHA) (as proteins) and hydrophilic neutral (NEU) (as carbohydrates) were observed at concentrations next to zero in most samples. It was possible to conclude that drinking water treatment processes affect the fraction distribution of NOM in water.

Les propriétés d'un gaz électronique bidimensionnel soumis à champs magnétiques intenses et à bas champs magnétiques sont étudiés par la spectroscopie optique: l'effet Hall quantique fractionnaire (FQHE) par photoluminescence et diffusion inélastique de la lumière, puis un nouvel effet oscillatoire de la résistance induit par micro-ondes (MIROs) par transport et absorption des micro-ondes. Les effets des interactions entre électrons du 2DEG sont à l'origine de FQHE. Jusqu'à maintenant, les expériences d'optiques n'ont pas permis les études des interactions entre électrons sur toute la gamme de fractions. Les fractions 1/3, 2/5, 3/7, 3/5, 2/3 et 1 sont clairement observées dans les spectres non traités et montrent une symétrie autour du facteur de remplissage 1/2. La symétrie des fermions composites ets observée dans les spectres. A bas champ magnétique, sous irradiation micro-onde, les propriétés de transport s'écartent nettement des oscillations bien connues de Shubnikov - de Haas pour évoluer vers une série d'états de résistance zéro. Les résultats des mesures d'absorption des micro-ondes sont présentés pour deux échantillons. L'échantillon de basse mobilité montre seulement une absorption autour de la résonance cyclotron (CR). L' échantillon de haute mobilité montre aussi des signaux d'absorption aux harmoniques de la CR. Les mesures ont permis d'inférer l'existence de deux processus d'absorption différents et séparés. L'absorption non résonante est mieux visible en transport et observée comme MIROs, et l'absorption résonante, mieux observée dans les mesures d'absorption, suit probablement les règles de polarisation de résonance cyclotron.

<p>Neutron-carbon interactions have been studied with a focus on charged-particle production of relevance to radiation protection and medical applications, such as cancer therapy. The measurements have been performed using the particle-detection setup, MEDLEY, and the 96 MeV neutron beam at the The Svedberg Laboratory in Uppsala.</p><p>Double-differential cross sections of inclusive charged-particle production are compared with recent calculations from models based on the GNASH code including direct, preequilibrium and compound processes. For protons, the shapes of the cross-section spectra are reasonably well described by the calculations. For the other particles- <i>d</i>, <i>t</i>, ³He and α- there are important discrepancies, in particular for ³He-ions and α-particles, concerning both shape and magnitude of the spectra.</p><p>Using the new cross sections, partial as well as total KERMA coefficients have been determined. The coefficients have also been compared to previous experimental results and model calculations. The <i>p</i>, <i>d</i> and <i>t</i> KERMA coefficients are in good agreement with those from a previous measurement. For the helium isotopes, there are no previous measurements at this energy. The KERMA coefficients are considerably higher (by up to 30%) than those predicted by the calculations.</p><p>The KERMA results indicate that protons and α -particles are the main contributors to the dose. A 6x6x6 cm³ carbon phantom, exposed to a broad and a pencil-like beam, is used for the computation of the absorbed doses deposited by these two particles in spheres of 1 μm in diameter, located at various positions in the phantom. The maximum doses are deposited at ~3 cm from the surface of neutron impact for protons and within 1 cm for α-particles. For the pencil beam, deposited doses are spread over regions of ~1.5 cm and ~300 μm transverse to the beam for protons and α-particles, respectively. The results are consistent with previous integral measurements at lower energies.</p>

In the ATLAS experiment at the Large Hadron Collider (LHC) at CERN, direct searches for the elusive Higgs boson will be conducted, as well as for physics beyond the Standard Model. The charged Higgs boson (H±) is interesting both as a part of the Higgs sector, and as a clear sign of new physics. This thesis focuses on H± searches, with H± production in top-antitop pair events, and in particular the  bW± bH±, H±→τhadν, W±→qq channel. Its potential was investigated  as  part of a larger study of the expected performance of the entire ATLAS experiment. Full simulation of the ATLAS detector and trigger was used, and all dominant systematics considered. It was shown to be the most promising H± discovery channel for mH±&lt;mt. As hadronic τ decays are important for H± searches, their correct identification is critical. Possibilities of improving tau-jet identification in  pile-up and top-antitop pair events were investigated. Redundant or even performance-reducing variables in the default likelihood identification were identified, as were new variables showing discriminatory power. This allows for increased rejection of QCD jets in these environments, and higher robustness of the method. Before any physics studies, a commissioned and well-understood detector is required. The Lorentz angle of the ATLAS Semi-Conductor Tracker (SCT) barrel was measured using 2008 cosmic-ray data. It is an important observable for the performance of several detector aspects. Potential sources of systematics were investigated and evaluated. The Lorentz angle in the SCT barrel was measured as θL = 3.93 ± 0.03(stat) ± 0.10(syst) degrees, agreeing with the model prediction. The Compact Linear Collider (CLIC) is a proposed successor to the LHC. The potential for charged and heavy neutral Higgs bosons at CLIC was investigated, in terms of both discovery and precision measurement of parameters like tanβ or the Higgs masses, up to and beyond 1 TeV, which would be challenging at the LHC