Double reentrance of surface arrangements in freestanding liquid crystal films.

The molecular arrangement of tilted surface layers on freestanding films above the bulk smectic-A-smectic-C(*) transition has been studied by null transmission ellipsometry. In the presence of an applied in-plane electric field, a synclinic-anticlinic-synclinic-anticlinic double reentrance has been observed. Furthermore, we have characterized a novel transition from the synclinic arrangement to a structure in which the interior layers tilt in the same orientation and the outermost surface layers tilt oppositely with the interior layers.

Unusual behavior of the surface-induced tilted layers in free-standing films of a non-layer-shrinkage liquid crystal compound.

Null-transmission ellipsometry has been conducted to study the molecular arrangements in free-standing films of one chiral compound above the bulk smectic-A-smectic-C* transition temperature. Upon cooling under a proper electric field, a nonplanar-anticlinic-synclinic or a nonplanar-synclinic transition has been observed. The nonplanar structure continuously evolves into the anticlinic or synclinic structures. Increasing electric field can induce a rare transition from a synclinic to an anticlinic structure.

Fluorimetric detection of tautomeric equilibria in 8-aminoquinolines.

The 1-methylquinolinium cations derived from 8-aminoquinoline and 8-amino-6-methoxyquinoline were prepared by methylation of the corresponding nitroquinolines and reduction of the nitro-compounds. The dissociation constants of the protonated species of these compounds are almost identical to those of doubly-protonated 8-aminoquinoline and 8-amino-6-methoxyquinoline, respectively, suggesting that the parent quinolines are exclusively first protonated at the ring nitrogen atom. However, the molar absorptivities of the 1-methyl derivatives at their longest-wavelength absorption maxima are substantially greater than the corresponding absorptivities of the unmethylated aminoquinolines, a result which suggests tautomerism of the singly-protonated parent quinolines, with a proportion of the population protonated at the amino group. Fluorescence spectroscopy reveals a single emission from the 8-amino-6-methoxy-1-methylquinolinium ion and two excitation-wavelength-dependent fluorescences from the 8-amino-6-methoxyquinolinium ion, confirming the occurrence of tautomerism and supporting choice of the absorptiometric approach rather than the titrimetric approach as the preferred method for the detection of tautomerism and the calculation of tautomeric equilibrium constants.