ABSTRACT
The interaction energetics, molecular packing, entanglement network properties, segmental dynamics, and elastic constants of atactic polystyrene-amorphous silica nanocomposites in the molten and the glassy state are studied via molecular simulations using two interconnected levels of representation: (a) a coarse-grained one, wherein each polystyrene repeat unit is mapped onto a single "superatom" and the silica nanoparticle is viewed as a solid sphere. Equilibration at all length scales at this level is achieved via connectivity-altering Monte Carlo simulations. (b) A united-atom (UA) level, wherein the polymer chains are represented in terms of a united-atom forcefield and the silica nanoparticle is represented in terms of a simplified, fully atomistic model. Initial configurations for UA molecular dynamics (MD) simulations are obtained by reverse mapping well-equilibrated coarse-grained configurations. By analysing microcanonical UA MD trajectories, the polymer density profile is studied and the polymer is found to exhibit layering in the vicinity of the nanoparticle surface. An estimate of the enthalpy of mixing between polymer and nanoparticles, derived from the UA simulations, compares favourably against available experimental values. The dynamical behaviour of polystyrene (in neat and filled melt systems) is characterized in terms of bond orientation and dihedral angle time autocorrelation functions. At low concentration in the molten polymer matrix, silica nanoparticles are found to cause a slight deceleration of the segmental dynamics close to their surface compared to the bulk polymer. Well-equilibrated coarse-grained long-chain configurations are reduced to entanglement networks via topological analysis with the CReTA algorithm, yielding a slightly lower density of entanglements in the filled than in the neat systems. UA melt configurations are glassified by MD cooling. The elastic moduli of the resulting glassy nanocomposites are computed through an analysis of strain fluctuations in the undeformed state and through explicit mechanical deformation by MD, showing a stiffening of the polymer in the presence of nanoparticles. UA simulation results for the elastic constants are compared to continuum micromechanical calculations invoked in homogenization models of the overall mechanical behaviour of heterogeneous materials. They can be interpreted in terms of the presence of an "interphase" of approximate thickness 2 nm around the nanoparticles, with elastic constants intermediate between those of the filler and the matrix.
ABSTRACT
BACKGROUND: The etiology of Kawasaki syndrome (KS) is unknown. Rickettsiae, intracellular microorganisms that invade the vascular endothelium, might cause KS. OBJECTIVES: To investigate whether there is an association between KS and infection with Rickettsia conorii, Rickettsia typhi, Coxiella burnetii or Ehrlichia phagocytophila group. METHODS: All children who were diagnosed with KS at the University of Athens Second Department of Pediatrics from December, 1999, through November, 2000, were prospectively studied. Paired serum specimens were obtained from all patients and antibody titers against R. conorii, R. typhi, C. burnetii and E. phagocytophila group were assessed by microimmunofluorescence assay. RESULTS: Eleven children with a median age of 2.5 years were included in the study. A 15-month-old child had a 4-fold rise of antibody titers against C. burnetii, which is indicative of acute Q fever. The patient had a history of recent exposure to possible sources of C. burnetii. The remaining patients tested negative for the presence of antibodies against R. conorii, R. typhi, C. burnetii and E. phagocytophila group. CONCLUSIONS: Our study does not provide serologic evidence that KS is the result of infection with R. conorii, R. typhi, C. burnetii or E. phagocytophila group. It is suggested that C. burnetii may cause a KS-like illness in young children.
