Absolute determination of photoluminescence quantum efficiency using an integrating sphere setup.

An integrating sphere-based setup to obtain a quick and reliable determination of the internal quantum efficiency of strongly scattering luminescent materials is presented. In literature, two distinct but similar measurement procedures are frequently mentioned: a "two measurement" and a "three measurement" approach. Both methods are evaluated by applying the rigorous integrating sphere theory. It was found that both measurement procedures are valid. Additionally, the two methods are compared with respect to the uncertainty budget of the obtained values of the quantum efficiency. An inter-laboratory validation using the two distinct procedures was performed. The conclusions from the theoretical study were confirmed by the experimental data.

Route of entry and tissue distribution of Yersinia ruckeri in experimentally infected rainbow trout Oncorhynchus mykiss.

Yersinia ruckeri is the causative agent of enteric redmouth disease, which leads to significant losses in salmonid aquaculture worldwide. Despite the significance of the disease, little information is available on the pathogenesis. In this study, the portal of entry was investigated using a contact-exposure infection method in rainbow trout Oncorhynchus mykiss with 4 different Y. ruckeri strains. Bacteriological and histological examination revealed the presence of high numbers of bacteria in the gills immediately after infection resulting in a rapid spread of Y. ruckeri in the internal organs. However, only a virulent strain was able to survive and multiply in the host, causing septicaemia and death several days after infection. These findings indicate that gills may be an important site of entry and that Y. ruckeri virulence is related to immune evasion.

Structure and dynamics of cylindrical micelles at equilibrium and under shear flow.

The dynamics and rheology of semidilute unentangled micellar solutions are investigated by Langevin dynamics mesoscopic simulations coupled to a microreversible kinetic model for scissions and recombinations. Two equilibrium state points, differing by the scission energy and therefore by the corresponding average micelle length, have been examined. The kinetic rates are tuned by an independent parameter of the model, whose range is chosen in such a way that the kinetics always strongly couple to the chain dynamics. Our results confirm, as predicted by Faivre and Gardissat, that the stress relaxation, as well as the monomer diffusion, is characterized by a time tauLambda, defined by the lifetime of a segment Lambda, whose Rouse relaxation time is equal to its lifetime. Moreover, the power-law dependence of the zero-shear viscosity versus tauLambda was evidenced. Under stationary shear, the chains are deformed and their average bond length is increased, which enhances the overall scission frequency. In turn, this induces an overall shortening of the chains in order to increase the overall corresponding chain-end recombination frequency, as required by the stationary conditions. Nonequilibrium simulations show that the chain deformation and orientation, as well as the rheology of the system, can be expressed as universal functions of a single reduced shear rate betaLambda=gammatauLambda (with gamma the bare shear rate). Furthermore, local analysis of the kinetics under stationary shear gives insights on the variation of the average length with shear rate.

Kinetics and dynamic properties of equilibrium polymers.

The statistical mechanics and scission-recombination mechanism of self-assembling linear micelles are investigated by Brownian dynamics using a newly proposed mesoscopic model representing the micelles as equilibrium polymer chains. A semidilute concentration regime, yet dynamically unentangled, is considered over a wide range of scission/recombination rates. We focus on the analysis of short and long time behaviors of the scission and recombination mechanisms. Our results show that at time scales larger than the life time of the average chain length, the kinetics is in agreement with the mean-field kinetic model proposed by Cates and Candau [J. Phys.: Condens. Matter 2, 6869 (1990)] provided the kinetic constants are estimated as effective ones. These values do take into account through a transmission coefficient that a fraction of scission/recombination events is correlated over a short time (diffusion controlled mechanism) and thus turn out to be ineffective reactive events by annihilation effects. By studying macroscopic relaxation phenomena such as the average micelle length evolution after a T jump, the monomer diffusion, and the zero shear stress relaxation function, we confirm that the effective kinetic constants found are indeed the relevant parameters when macroscopic relaxation is coupled to the kinetics of micelles.

Surface ordering of diskotic liquid crystals.

We present Monte Carlo simulations of diskotic molecules using the Gay-Berne potential in a slab geometry. The disk-wall interaction is described by two different functions according to whether or not the equilibrium distance is dependent on the relative orientation of the disk to the wall. Furthermore, by changing the parameters of these potentials, we model either homeotropic (face-on) or planar (edge-on) anchoring of the disks. We have found that the isotropic-nematic transition does not change in comparison with the bulk situation. The temperature of the nematic-columnar transition, on the contrary, is found to increase for homeotropic anchoring, and decrease for planar anchoring, independently of the details of the potential. We explain the decrease of the transition temperature in the planar anchoring situation as the result of an induced frustration, due to the competition between the two orientations induced independently by the upper and lower walls.

Influence of shape and energy anisotropies on the phase diagram of discotic molecules.

We present Monte Carlo simulations of discotic molecules using the Gay-Berne potential with shape (kappa) and energy (kappa(')) anisotropies. Following the previous work of Bates and Luckhurst [J. Chem. Phys. 104, 6696 (1996)] at kappa=0.345, kappa(')=0.2 when we determine the sequence of different phases at the same reduced pressure P(*)=50, we find an additional phase at low temperatures corresponding to an orthorhombic crystalline phase and we characterize it. Keeping the shape anisotropy fixed at kappa=0.2, we determine the evolution of the phase diagram with varying energy anisotropy. At high kappa('), low anisotropy, the system is not able to build columns while at low kappa('), the system exhibits both orthorhombic crystal as well as hexagonal liquid crystal phases over a wide range of pressures and temperatures. The domain of stability of the nematic phase is found to systematically shift towards higher pressures as kappa(') decreases.

Different statistical mechanical ensembles for a stretched polymer.

Imposing to a single polymer chain of N monomers either a fixed pair of forces +/-f acting at the chain ends (stress ensemble) or a fixed end-to-end vector R (strain ensemble) does correspond to the use of different statistical mechanical ensembles. In particular, the two elasticity laws, R(f)=g(f) and f(R)=h(R), where R(f) is the length of the average end-to-end vector (f) in the stress ensemble and f(R) is the intensity of the average internal force (R) in the strain ensemble, are not equivalent. For these conjugated ensembles, the quantity Delta(f)=f-h(g(f)) and more generally Delta(O)=(f)-(R) where O is an arbitrary observable, is studied systematically in this paper for a wide class of polymer models corresponding to chains at temperatures equal or above the theta point. The leading term Delta((2))(O) of an expansion of Delta(O) in terms of the successive moments of the end-to-end vector fluctuations in the stress ensemble can be used to analyze the scaling properties of Delta(f). For the Gaussian and the freely jointed chain models, Delta(O) proportional to 1/N for large N with the particularity that, for the elasticity law, Delta(f) strictly vanishes for the Gaussian chain at any finite N. For chains in good solvent, the usual result Delta(f) proportional to 1/N at fixed f is only valid in the highly stretched chain regime (Pincus regime). N independent large ensemble differences of the order of 20% on Delta(f) are noticed when the chain is stretched over a distance of the order of the unstretched chain average end-to-end distance R0. These effects decrease to the 1% level for R(f)>3R(0). Monte Carlo calculations for a chain model containing both excluded volume and finite extensibility features illustrate the distinction between the elasticity laws in the two ensembles over all stretching regimes. Our study suggests that the nature of the constraints used in single chain micromanipulations could be relevant to the interpretation of experimental elasticity law data.