Imaging chiroptical artifacts.

It is well-known that circular dichroism (CD) measurements of anisotropic media may contain artifacts that result from mixed linear anisotropies. Such artifacts are generally considered a nuisance. However, systematic artifacts, carefully measured, may contain valuable information. Herein, polycrystalline spherulites of D-sorbitol grown from the melt were analyzed with a Mueller matrix microscope, among other differential polarization images devices. As spherulites grew into one another they developed strong apparent optical rotation and CD signals at the boundaries between spherulites. These signals are shown not to have a chiroptical origin but rather result from the interactions of linear anisotropies in polycrystalline bodies. Such chiroptical artifacts should not be dismissed reflexively. Rather, they are comprehensible crystal-optical effects that serve to define mesoscale structure.

Orientational dependence of linear dichroism exemplified by dyed spherulites.

D-sorbitol forms so-called spherulites from under-cooled melts. These polycrystalline formations have optically uniaxial radii. Melts pressed between glasses crystallize as plane sections of spheres. Dyes that are soluble in molten sorbitol become oriented as the crystallization front passes through the melt so as to form disks with large linear dichroism in the absorption bands of the dyes. The dyeing of spherulites is thus a general method of solute alignment. The linear optical properties of sorbitol spherulites containing the azo dye amaranth were analyzed in detail so as to correct a persistent confusion in the literature regarding the orientational dependence of linear dichroism. In cases involving thin film dichroism of multilayered samples requiring many corrections of intensity data in non-normal incidence, some authors have taken transmittance and others absorbance as having a cosine-squared angular dependence on the plane of the electric vector of linearly polarized light. Plane sections of doped spherulites present all orientations of an electric dipole oscillator in spatially localized region in normal incidence. As such, the samples described herein are ideally suited to resolving this confusion. Images of transmittance of dyed spherulites in polarized light were recorded with a CCD camera and simulated under the assumption that both absorbance and transmittance show a cosine-squared angular dependence but with respect to different angles. Transmittance with a cosine-squared dependence follows azimuthal rotations of the spherulite radii around the wave vector, while absorbance with a cosine-squared dependence follows rotations about axes perpendicular to the wave vector, natural consequences of the properties of the optical indicatrix that are often overlooked. Spherulites obviate the substantial experimental complexities that are engendered in non-normal incidence by sample reorientation. Thus, the principles of anisotropic absorption are given in a complete and intuitive fashion.

Dendritic crystal growth, differential circular scattering, and the origin of biomolecular homochirality.

Phthalic acid rapidly crystallizing in thin aqueous films is deposited radially and rhythmically as dendritic banded spherulites that have heterochiral meso-textures in hemi-circles. The chiral fields differentially scatter left and right circularly polarized light. A scenario for chiral amplification and the origin of biomolecular homochirality is thus proposed that combines the influences of crystals and light.

The first crystal structure of a monomeric phenoxyl radical: 2,4,6-tri-tert-butylphenoxyl radical.

Crystals of the 2,4,6-tri-tert-butylphenoxyl radical have been isolated and characterized by X-ray diffraction, and calculations have been performed that give the distribution of spin density in the radical.