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Orientational Distributions (orientational + distribution)

Distribution by Scientific Domains

Chemistry	40%

Selected Abstracts

Cover Picture: Anisotropy and Dynamic Ranges in Effective Properties of Sheared Nematic Polymer Nanocomposites (Adv. Funct.

ADVANCED FUNCTIONAL MATERIALS, Issue 12 2005
Mater.
Abstract Forest and co-workers report on p.,2029 that nematic polymer nanocomposite (NPNC) films can be processed in steady shear flows, which generate complex orientational distributions of the nanorod inclusions. Distribution functions for a benchmark NPNC (11,vol.-% of 1,nm,×,200,nm rods) are computed for a range of shear rates, yielding a bifurcation diagram with steady states at very low (logrolling) and high (flow-aligning) shear rates, and limit cycles (tumbling, wagging, kayaking) at intermediate shear rates. The orientational distributions dictate the effective conductivity tensor of the NPNC film, which is computed for all distribution functions, and extract the maximum principal conductivity enhancement (Emax, averaged in time for periodic distributions) relative to the matrix. The result is a "property bifurcation diagram" for NPNC films, which predicts an optimal shear rate that maximizes Emax. Nematic, or liquid-crystalline, polymer nanocomposites (NPNCs) are composed of large aspect ratio, rod-like or platelet, rigid macromolecules in a matrix or solvent, which itself may be aqueous or polymeric. NPNCs are engineered for high-performance material applications, ranging across mechanical, electrical, piezoelectric, thermal, and barrier properties. The rods or platelets possess enormous property contrasts relative to the solvent, yet the composite properties are strongly affected by the orientational distribution of the nanophase. Nematic polymer film processing flows are shear-dominated, for which orientational distributions are well known to be highly sensitive to shear rate and volume fraction of the nematogens, with unsteady response being the most expected outcome at typical low shear rates and volume fractions. The focus of this article is a determination of the ranges of anisotropy and dynamic fluctuations in effective properties arising from orientational probability distribution functions generated by steady shear of NPNC monodomains. We combine numerical databases for sheared monodomain distributions[1,2] of thin rod or platelet dispersions together with homogenization theory for low-volume-fraction spheroidal inclusions[3] to calculate effective conductivity tensors of steady and oscillatory sheared mesophases. We then extract maximum scalar conductivity enhancement and anisotropy for each type of sheared monodomain (flow-aligned, tumbling, kayaking, and chaotic). [source]

Weak alignment offers new NMR opportunities to study protein structure and dynamics

PROTEIN SCIENCE, Issue 1 2003
Ad Bax
Protein solution nuclear magnetic resonance (NMR) can be conducted in a slightly anisotropic environment, where the orientational distribution of the proteins is no longer random. In such an environment, the large one-bond internuclear dipolar interactions no longer average to zero and report on the average orientation of the corresponding vectors relative to the magnetic field. The desired very weak ordering, on the order of 10,3, can be induced conveniently by the use of aqueous nematic liquid crystalline suspensions or by anisotropically compressed hydrogels. The resulting residual dipolar interactions are scaled down by three orders of magnitude relative to their static values, but nevertheless can be measured at high accuracy. They are very precise reporters on the average orientation of bonds relative to the molecular alignment frame, and they can be used in a variety of ways to enrich our understanding of protein structure and function. Applications to date have focused primarily on validation of structures, determined by NMR, X-ray crystallography, or homology modeling, and on refinement of structures determined by conventional NMR approaches. Although de novo structure determination on the basis of dipolar couplings suffers from a severe multiple minimum problem, related to the degeneracy of dipolar coupling relative to inversion of the internuclear vector, a number of approaches can address this problem and potentially can accelerate the NMR structure determination process considerably. In favorable cases, where large numbers of dipolar couplings can be measured, inconsistency between measured values can report on internal motions. [source]

Cover Picture: Anisotropy and Dynamic Ranges in Effective Properties of Sheared Nematic Polymer Nanocomposites (Adv. Funct.

Oriented Ensembles in Ultrafast Electron Diffraction

CHEMPHYSCHEM, Issue 7 2006
J. Spencer Baskin
Abstract Electron scattering expressions are presented which are applicable to very general conditions of implementation of anisotropic ultrafast electron diffraction (UED) experiments on the femto- and picosecond time scale. "Magic angle" methods for extracting from the experimental diffraction patterns both the isotropic scalar contribution (population dynamics) and the angular (orientation-dependent) contribution are described. To achieve this result, the molecular scattering intensity is given as an expansion in terms of the moments of the transition-dipole distribution created by the linearly polarized excitation laser pulse. The isotropic component (n=0 moment) depends only on population and scalar internuclear separations, and the higher moments reflect bond angles and evolve in time due to rotational motion of the molecules. This clear analytical separation facilitates assessment of the role of experimental variables in determining the influence of anisotropic orientational distributions of the molecular ensembles on the measured diffraction patterns. Practical procedures to separate the isotropic and anisotropic components of experimental data are evaluated and demonstrated with application to reactions. The influence of vectorial properties (bond angles and rotational dynamics) on the anisotropic component adds a new dimension to UED, arising through the imposition of spatial order on otherwise randomly oriented ensembles. [source]