Optical rotation of achiral compounds.

Oriented achiral molecules and crystals with D(2d) symmetry or one of its non-enantiomorphous subgroups, S(4), C(2v), or C(s), can rotate the plane of transmitted polarized light incident in a general direction. This well-established fact of crystal optics is contrary to the teaching of optical activity to students of organic chemistry. This Minireview gives an overview of the measurement and calculation of the chiroptical properties of some achiral compounds and crystals. Methane derivatives with four identical ligands related by reflection symmetry are quintessential optically inactive compounds according to the logic of van't Hoff. Analysis of the optical activity of simple achiral compounds such as H(2)O and NH(3) provides general aspects of chiroptics that are not readily broached when considering chiral compounds exclusively. We show here, through the use of group theoretical arguments, the transformation properties of tensors, and diagrams, why some achiral, acentric compounds are optically active while others are not.

The optical rotatory power of water.

Ab initio molecular orbital calculations of the optical rotatory response of a single oriented water molecule are described. The unique tensor element g(xy) was computed to be -0.047 bohr(3) with CCSD/6-311+G(d,p). A value of -0.033 was obtained with the minimal valence basis that was better suited to parsing the rotatory response among a limited number of excited states. Transition moments were calculated ab initio and qualitatively derived from the wave functions. Rotations were reckoned from the relative dispositions of the transition moments with respect to the wavevectors. In this way, it was possible to intuitively reckon the form of the optical rotation tensor consistent with that from higher levels of theory and to establish which excitations make the most significant contributions.

Optical rotation of achiral pentaerythritol.

The optical rotatory power of achiral crystals of achiral pentaerythritol molecules was measured. The maximum rotations were found to be +/-6 degrees /mm. The quantum mechanically computed rotation of pentaerythritol molecules using linear response theory was 6 times larger although the experimental and theoretical tensors were similarly oriented to within 5 degrees .

Polarimetric imaging of amyloid.

New developments in optical microscopy are discussed with relevance to the imaging of amyloid plaques that are pathognomonic of a variety of degenerative disorders. We present the results of linear birefringence, linear dichroism, and circular dichroism imaging of Congo red stained plaques ex vivo and in vitro. A new technique for measuring rapid changes in linear anisotropies is introduced. The application of polarimetric imaging as demonstrated here can be extended to broader pathological practice since polarimetric measurements are sensitive to transformations in tissues that are specific disease signatures.

Polarimetric imaging of crystals.

Classical crystal optics has recently undergone a renaissance as developments in optical microscopy and polarimetry, enabled in part by sensitive imaging CCD cameras and personal computers, now permit the analytical separation of various optical effects that are otherwise convolved in polarized light micrographs. In this tutorial review, we review recent developments in the measurement of the principal crystallo-optical quantities including linear birefringence, linear dichroism, circular birefringence, and circular dichroism, as well as new effects in crystal optics encountered in unusual mixed crystals. The new microscopies and polarimetries are applied to problems of crystallographic twinning, phase transformations, stress birefringence, symmetry reduction, and the design of new crystalline materials.

Circular dichroism imaging microscopy: application to enantiomorphous twinning in biaxial crystals of 1,8-dihydroxyanthraquinone.

A microscope was constructed for imaging circular dichroism of heterogeneous anisotropic media. To avoid linear biases that are common with electronic circular polarization modulation, we chose a retrogressive solution: mechanical light modulation by rotating a linear polarizer with respect to a quarter wave plate continuously tuned by tilting to the operating wavelength. Our comparatively slow technique succeeds with near-perfect circular input and signal averaging using a CCD camera. We have applied the method to anomalously birefringent crystals of 1,8-dihydroxyanthraquinone that are shown to have intergrown mirror image domains, undetected by X-ray diffraction because the twinning complexity renders differences in anomalous dispersion, already small, unreliable. The origin of the anomalous birefringence and the assignment of the absolute configuration are discussed.

Imaging linear birefringence and dichroism in cerebral amyloid pathologies.

New advances in polarized light microscopy were used to image Congo red-stained cerebral amyloidosis in sharp relief. The rotating-polarizer method was used to separate the optical effects of transmission, linear birefringence, extinction, linear dichroism, and orientation of the electric dipole transition moments and to display them as false-color maps. These effects are typically convolved in an ordinary polarized light microscope. In this way, we show that the amyloid deposits in Alzheimer's disease plaques contain structurally disordered centers, providing clues to mechanisms of crystallization of amyloid in vivo. Comparisons are made with plaques from tissues of subjects having Down's syndrome and a prion disease. In plaques characteristic of each disease, the Congo red molecules are oriented radially. The optical orientation in amyloid deposited in blood vessels from subjects having cerebral amyloid angiopathy was 90 degrees out of phase from that in the plaques, suggesting that the fibrils run tangentially with respect to the circumference of the blood vessels. Our result supports an early model in which Congo red molecules are aligned along the long fiber axis and is in contrast to the most recent binding models that are based on computation. This investigation illustrates that the latest methods for the optical analysis of heterogeneous substances are useful for in situ study of amyloid.