Toward a molecular understanding of the detection of amyloid proteins with flexible conjugated oligothiophenes.

Molecular and electronic structures and optical absorption properties of oligothiophenes used for spectral assignment of amyloid deposits have been investigated for a family of probes known as luminescent conjugated oligothiophenes (LCOs). Theoretical absorption spectra have been determined using conformational averaging, combining classical molecular dynamics (MD) simulations with quantum mechanical/molecular mechanics (QM/MM) time-dependent density functional theory (TD-DFT) spectrum calculations. Theoretical absorption spectra are in excellent agreement with experiments, showing average errors below 5 nm for absorption maxima. To couple observed properties to molecular structures, a measure of planarity is defined, revealing a strong correlation between the transition wavelength of the first and dominating electronically excited state and dihedral rotations. It is shown that from this correlation, predictions can be made of the absorption properties of probes based only on information from MD trajectories. We show experimentally that red shifts observed in the excitation maxima of LCOs when bound to amyloid protein aggregates are also evident in absorption spectra. We predict that these red shifts are due to conformational restriction of the LCO in a protein binding pocket, causing a planarization of the conjugated backbone. On the basis of our studies of planarity, it is shown that such shifts are both possible and realistic.

Parametric model of the Mueller matrix of a Spectralon white reflectance standard deduced by polar decomposition techniques.

Decomposition methods have been applied to in-plane Mueller matrix ellipsometric scattering data of the Spectralon reflectance standard. Data were measured at the wavelengths 532 nm and 1500 nm, using an achromatic optimal Mueller matrix scatterometer applying a photomultiplier tube and a high gain InGaAs detector for the two wavelengths. A parametric model with physical significance was deduced through analysis of the product decomposed matrices. It is found that when the data are analyzed as a function of the scattering angle, similar to particle scattering, the matrix elements are largely independent of incidence angle. To the first order, we propose that a Guassian lineshape is appropriate to describe the polarization index, while the decomposed diagonal elements of the retardance matrix have a form resembling Rayleigh single scattering. New models are proposed for the off diagonal elements of the measured Mueller matrix.

Solution based synthesis of simple fcc Si nano-crystals under ambient conditions.

We demonstrate for the first time that simple face-centered cubic (fcc) silicon nano-crystals can be produced by a solution based bottom-up synthesis route under ambient conditions. Simple fcc Si nano-crystals (2-7 nm) were prepared at room temperature by using sodium cyclopentadienide as a reducing agent for silicon tetrachloride. Photoluminescence emission at 550 nm was observed for the fcc silicon nano-crystals upon excitation at 340 nm, indicating that fcc Si nano-crystals were exhibiting direct bandgap like semiconductor properties with very fast radiative recombination rates. The new synthesis route makes possible the production and study of simple fcc polymorphs of Si nano-crystals with an easy alteration of surface termination groups.

Mueller matrix measurements and modeling pertaining to Spectralon white reflectance standards.

The full Mueller matrix for a Spectralon white reflectance standard was measured in the incidence plane, to obtain the polarization state of the scattered light for different angles of illumination. The experimental setup was a Mueller matrix ellipsometer, by which measurements were performed for scattering angles measured relative to the normal of the Spectralon surface from -90° to 90° sampled at every 2.5° for an illumination wavelength of 532 nm. Previously, the polarization of light scattered from Spectralon white reflectance standards was measured only for four of the elements of the Muller matrix. As in previous investigations, the reflection properties of the Spectralon white reflectance standard was found to be close to those of a Lambertian surface for small scattering and illumination angles. At large scattering and illumination angles, all elements of the Mueller matrix were found to deviate from those of a Lambertian surface. A simple empirical model with only two parameters, was developed, and used to simulate the measured results with fairly good accuracy.