Coil-to-globule transition of poly(N-isopropylacrylamide) doped with chiral amino acidic comonomers.

By combined light scattering and circular dichroism measurements (CD), we have investigated the coil-to-globule transition of the thermosensitive polymer poly(N-isopropylacrylamide) (pNIPAAm) copolymerized with a 1/10 fraction of valine- or leucine-derived groups randomly positioned along the chains. The comonomers provide the pNIPAAm chains with chirality, electric charge, and increased hydrophobicity. For valine-derived copolymers, the coil-globule transition is basically unmodified with respect to pNIPAAm, whereas doping with leucine-derived groups significantly lowers the transition temperature and makes the transition discontinuous. We find the CD signal of the chiral comonomers to cleanly depend on the local chain density. We interpret this behavior as an effect of the whole chain conformation on the conformations accessible to the chiral groups.

Pretransitional behavior of a water in liquid crystal microemulsion close to the demixing transition: evidence for intermicellar attraction mediated by paranematic fluctuations.

We present a study of a water-in-oil microemulsion in which surfactant coated water nanodroplets are dispersed in the isotropic phase of the thermotropic liquid-crystal penthyl-cyanobiphenyl (5CB). As the temperature is lowered below the isotropic to nematic phase transition of pure 5CB, the system displays a demixing transition leading to a coexistence of a droplet-rich isotropic phase with a droplet-poor nematic. The transition is anticipated, in the high T side, by increasing pretransitional fluctuations in 5CB molecular orientation and in the nanodroplet concentration. The observed phase behavior supports the notion that the nanosized droplets, while large enough for their statistical behavior to be probed via light scattering, are also small enough to act as impurities, disturbing the local orientational ordering of the liquid crystal and thus experiencing pretransitional attractive interaction mediated by paranematic fluctuations. The pretransitional behavior, together with the topology of the phase diagram, can be understood on the basis of a diluted Lebwohl-Lasher model which describes the nanodroplets simply as holes in the liquid crystal.

Isotropic to nematic transition of aerosil-disordered liquid crystals.

We present a high-resolution study of the isotropic to nematic phase transition of a low birefringence liquid-crystal compound incorporating an aerosil gel. Calorimetry, light scattering, and microscopy data coherently combine to allow for an accurate determination of the temperature dependence of the onset of the nematic state. The nematic order develops on cooling through two distinct processes while the nematic correlation length mildly decreases. We understand the doubling of the phase transition as due to a crossover from a random-dilution regime, where the silica gel couples to the scalar part of the nematic order parameter, to a low-T random-field regime, where the coupling induces distortions in the director field.

Fluctuation mediated interaction and phase separation of nanoparticles in a liquid crystal solvent.

Water-in-oil microemulsions of nanodroplets in the isotropic phase of a thermotropic liquid crystal exhibit, with decreasing temperature and in anticipation of a demixing transition, enhanced correlation in fluctuations of both molecular orientation and droplet concentration. Mean field modeling of this pretransition behavior, on the basis of a lattice in which the nanodroplets are introduced as holes, shows that the observed interdroplet attractive interaction is produced by the disordering effect of the droplets on the liquid crystal and mediated solely by paranematic fluctuations.