Application of Nonlinear Optical Microscopy for Imaging Skin†

Recent advances in the use of nonlinear optical microscopy (NLOM) in skin microscopy are presented. Nonresonant spectroscopies including second harmonic generation, coherent anti‐Stokes Raman and two‐photon absorption are described and applications to problems in skin biology are detailed. These nonlinear techniques have several advantages over traditional microscopy methods that rely on one‐photon excitation: intrinsic 3D imaging with <1 μm spatial resolution, decreased photodamage to tissue samples and penetration depths up to 1000 μm with the use of near‐infrared lasers. Thanks to these advantages, nonlinear optical spectroscopy has become a powerful tool to study the physical and biochemical properties of the skin. Structural information can be obtained using the response of endogenous chemical species in the skin, such as collagen or lipids, indicating that optical biopsy may replace current invasive, time‐consuming traditional histology methods. Insertion of specific probe molecules into the skin provides the opportunity to monitor specific biochemical processes such as skin transport, molecular penetration, barrier homeostasis and ultraviolet radiation‐induced reactive oxygen species generation. While the field is quite new, it seems likely that the use of NLOM to probe structure and biochemistry of live skin samples will only continue to grow.     

General relativistic axisymmetric rotating systems: Coordinates and equations

The Einstein equations for rotating axisymmetric configurations in asymptotically flat spacetimes are put in a form suitable for numerical calculations of dynamics. The discussion is motivated by the astrophysical problem of gravitational collapse with generation of gravitational radiation and possibly black hole formation. In the context of topologically spherical coordinates there are two spatial gauge conditions which greatly simplify the Einstein equations and are compatible with regularity at the origin. We focus on one, the radial gauge, which generalizes Schwarzschild coordinates and is asymptotically a transverse-traceless gauge for gravitational radiation. The shift vector equation and the Hamiltonian constraint are parabolic equations in the radial gauge, rather than the usual elliptic equations. Two hypersurface conditions are explored in detail, the maximal hypersurface condition and another “polar” hypersurface condition which fits naturally with the radial gauge.     

Exciton delocalization and superradiance in tetracene thin films and nanoaggregates

The structure and dynamics of luminescent excitons in tetracene thin films and nanoaggregates are investigated using time-resolved spectroscopy and theoretical calculations. The orientation of tetracene's transition dipole moment along its short molecular axis leads to properties qualitatively different from those observed in aggregates of phenylene-vinylene and thiophene oligomers, despite similar crystal structures. The spectral shape, temperature dependence, and radiative lifetime are consistent with a short-lived superradiant exciton delocalized over approximately 10 tetracene molecules.     

Using meta conjugation to enhance charge separation versus charge recombination in phenylacetylene donor-bridge-acceptor complexes

A pair of donor-bridge-acceptor electron-transfer complexes, with a carbazole donor and a naphthalimide acceptor connected by either a para- or meta-conjugated phenylacetylene bridge, are synthesized and studied using time-resolved and steady-state spectroscopy. These experiments show that the charge separation times, which depend on the coupling of the donor and acceptor through the excited bridge moiety, are similar for the two molecules (Meta and Para). The charge recombination time, however, is a factor of 10 slower for Meta than for Para. These results are related to changes in the electronic coupling of the bridge depending on its electronic state, and show that meta-conjugated bridges provide a possible motif for the design of asymmetric molecular wires.