The behaviour of liquid crystal (LC) molecules near a surface is of both fundamental and technological interest: it gives rise to various surface phase-transition and wetting phenomena, and surface-induced ordering of the LC molecules is integral to the operation of LC displays. Here we report the observation of a pure isotropic-nematic (IN) surface phase transition-clearly separated from the bulk IN transition-in a nematic LC on a substrate. Differences in phase behaviour between surface and bulk are expected, but have hitherto proved difficult to distinguish, owing in part to the close proximity of their transition temperatures. We have overcome these difficulties by using a mixture of nematic LCs: small, surface-induced composition variations lead to complete separation of the surface and bulk transitions, which we then study independently as a function of substrate and applied magnetic field. We find the surface IN transition to be of first order on surfaces with a weak anchoring energy and continuous on surfaces with a strong anchoring. We show that the presence of high magnetic fields does not change the surface IN transition temperature, whereas the bulk IN transition temperature increases with field. We attribute this to the interaction energy between the surface and bulk phases, which is tuned by magnetic-field-induced order in the surface-wetting layer.
We perform Monte Carlo simulations of tau proteins bound to a cylinder that mimics a microtubule (MT), and then study them in solution. Tau protein binds to a highly anionic MT surface to stabilize the cylindrical structure of MT. The negatively charged tail domain floats away from the anionic MT surface while positively charged tau segments localize near the MT surface. Monte Carlo simulations demonstrate that, in 3RS tau isoform (which has three imperfect repeats (R) short (S) isoform), amino acids are more condensed near a highly charged interface compared to 4RL isoform (which has four imperfect repeats (R) long (L) isoform). In 4RL isoform, amino acids in tail domain stay mostly apart from the MT surface. In the bulk solution, dephosphorylated taus are separated due to Coulomb repulsion between similarly charged isoforms. Moderate phosphorylation of 3RS isoform decreases average intermolecular distance between dephosphorylated and phosphorylated taus and lead to their overlap. Further phosphorylation does not change noticeably the intermolecular distances.
Surface optical second-harmonic generation measurements were used to determine the change in the surface density and the surface orientational order parameter of the trans-cinnamoyl side groups of unidirectionally photopolymerized poly͑vinyl cinnamate͒ ͑PVCN͒ films. The observed surface features were compared to the bulk properties of the films, which were probed by their UV absorption spectra and birefringence measurements. We found that the surface and the bulk photoreaction kinetics of the trans cinnamoyl side groups of the PVCN are very similar. The two photoreaction processes ͑trans-cis photoisomerization and photo-induced cross linking͒ appear to affect the linear and nonlinear optical properties of the polymer differently. This may explain the discrepancy between the birefringence and the azimuthal anchoring force of the unidirectionally photopolymerized PVCN. ͓S1063-651X͑99͒06909-3͔
The adsorption kinetics and orientational ordering of 4Ј-n-octyl-4-cyanobiphenyl ͑8CB͒ liquid crystal films evaporated onto photosensitive poly͑vinyl-cinnamate͒ ͑PVCN͒ substrates were investigated by surface optical second-harmonic generation. The adsorption rate of the first monolayer decreases with increasing degree of photochemical modification of the polymer. The in-plane orientational anisotropy of the 8CB films grown on unidirectionally photopolymerized PVCN substrates is considerably lower than the intrinsic surface orientational anisotropy of these substrates, which can explain the generally found weak surface anchoring of liquid crystals on PVCN alignment layers.
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