Polydomain model predictions of liquid crystalline polymer orientation in mixed shear/extensional channel flows

 The Larson-Doi (LD) polydomain model is used to simulate orientation development along the centerline of slit-expansion and slit-contraction flows of liquid crystalline polymers (LCPs). Orientation is computed using the LD structural evolution equations, subject to an imposed velocity field that accounts for the spatial variation of both shear and extension rates characteristic of this class of flows. Computed axial distributions of orientation averaged through the sample thickness are qualitatively similar to birefringence and X-ray scattering measurements of molecular orientation in similar flows of lyotropic and thermotropic LCPs. In slit-expansion flows, the simulations predict a 90^∘ flip in orientation direction near the midplane due to transverse stretching in the expansion region. Far away from the midplane where shear gradients dominate, orientation remains primarily along the flow direction. Within the LD model, tumbling and flow aligning materials respond in a qualitatively similar manner to mixed shear and extension, although tumbling materials are systematically more susceptible to the effects of extension. Received: 22 October 1999/Accepted: 13 January 2000     

Synthesis of pyrido[2,3-d]pyridazines and pyrazino[2,3-d]-pyridazines—novel classes of GABAA receptor benzodiazepine binding site ligands

Novel syntheses of 2,3,8-trisubstituted pyrido[2,3-d]pyridazines and 2,3,5-trisubstituted pyrazino[2,3-d]pyridazines are described. Two complementary routes to pyrido[2,3-d]pyridazines were developed, the first of which began by constructing the pyridine ring, and the second of which started by constructing the pyridazine ring. Pyrazino[2,3-d]pyridazines were prepared in a route employing an aza-Wadsworth-Emmons cyclization as the key step. The resulting compounds were found to be high affinity ligands for the GABA_A receptor benzodiazepine binding site.     

Synthesis and properties of 1,3,5-benzene periodic mesoporous organosilica (PMO): novel aromatic PMO with three point attachments and unique thermal transformations

A new aromatic periodic mesoporous organosilica material containing benzene functional groups that are symmetrically integrated with three silicon atoms in an organosilica mesoporous framework is reported. The material has a high surface area, well-ordered mesoporous structure and thermally stable framework aromatic groups. The functional aromatic moieties were observed to undergo sequential thermal transformation from a three to two and then to a one point attachment within the framework upon continuous thermolysis under air before eventually being converted to periodic mesoporous silica devoid of aromatic groups at high temperatures and longer pyrolysis times. The mesoporosity of the material was characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and nitrogen porosimetry, whereas the presence and transformation of the aromatic groups in the walls of the materials were characterized by solid-state NMR spectroscopy, mass spectrometry, and thermogravimetric analysis. The attachment of a benzene ring symmetrically onto three siloxanes of the framework was used advantageously as a cross-linker to enhance the thermal stability of the organic group. Some of these properties are investigated in comparison with other aromatic PMOs that have only two point attachments and an amorphous phenylsilica gel that has only one point attachment. The successful synthesis of the first aromatic PMO with its organic group attached within the framework through more than two points is an important step toward the synthesis of PMOs having organic groups with more complex and multiple attachments within the framework.     

Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All‐Organic Redox Flow Battery

Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all‐organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical‐based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries.     

Field-induced anisotropy in concentrated systems of rigid particles and macromolecules

This paper presents experimental results on the use of spectroscopic optical polarimetry to study structure in dense systems of rigid particles and rigid polymer liquid crystals. These measurements probe microstructural anisotropy induced by the application of electric fields in the case of dense suspensions of rigid spheres, or flow fields in the case of polymer liquid crystals. It is demonstrated that conservative linear dichroism can measure moments of the particle pair distribution function in dense suspensions. In liquid crystals, the dichroism is a result of field-induced anisotropy in the defect structure of the material.     

Empirically correct electrodynamics

The electrodynamics that predicts all known relevant observations is based upon the force F=(qq ′R/R³) [1 − 2v·v′/c² + 3(v·R) (v′·R)/c²R² + (a — a′)·R/c²] on charge q at r with the absolute velocity v and acceleration a due to charge q′ at r′ with absolute velocity v′ and acceleration a′, where R=r − r′. This force yields Ampere’s original empirical law for the force between current elements, which predicts the many effects due to Ampere tension between colinear current elements. It yields Faraday induction as well as Müller’s localized unipolar induction. The force on an accelerating charge due to a stationary charge yields Lenz’s law for the induced back emf; and, when applied to gravitation, qq′ being replaced by — Gmm′, it yields the inertial force ma, confirming Mach’s priniciple. For charge velocities approaching the velocity of light c it predicts the results of the Kaufmann-Bucherer experiments and the Bertozzi experiment, assuming neomechanics, or mass change with velocity. It is readily written as a field theory. Introducing time retardation, it yields waves and radiation. It predicts the observed zero self-torque on the Pappas-Vaughan Z-shaped antenna. Energy is conserved. The Weber electrodynamic theory is shown to fail.     

Pseudo-spectral methods and linear instabilities in reaction-diffusion fronts

We explore the application of a pseudo-spectral Fourier method to a set of reaction-diffusion equations and compare it with a second-order finite difference method. The prototype cubic autocatalytic reaction-diffusion model as discussed by Gray and Scott [Chem. Eng. Sci. 42, 307 (1987)] with a nonequilibrium constraint is adopted. In a spatial resolution study we find that the phase speeds of one-dimensional finite amplitude waves converge more rapidly for the spectral method than for the finite difference method. Furthermore, in two dimensions the symmetry preserving properties of the spectral method are shown to be superior to those of the finite difference method. In studies of plane/axisymmetric nonlinear waves a symmetry breaking linear instability is shown to occur and is one possible route for the formation of patterns from infinitesimal perturbations to finite amplitude waves in this set of reaction-diffusion equations. (c) 1996 American Institute of Physics.     

Waiakeamide, a Cyclic Hexapeptide from the Sponge Ircinia dendroides(1)

From the sponge, Ircinia dendroides, collected in Indonesia we isolated a new cyclic hexapeptide, waiakeamide (1). Its structure, consisting of three proline residues, two methionine sulfoxides, and one thiazolylphenylalanine, was elucidated by spectral analysis and chemical degradation. Isolation and structural elucidation of waiakeamide is described.     

Energy transfer pathways in dinuclear heteroleptic polypyridyl complexes: through-space vs through-bond interaction mechanisms

A series of homo- and heteronuclear ruthenium and osmium polypyridyl complexes with the bridging ligands 1,3-bis(5-(2-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (H(2)mL) and 1,4-bis(5-(2-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (H(2)pL) are reported. The photophysical properties of these compounds are investigated, and particular attention is paid to the heteronuclear (RuOs) compounds, which exhibit dual emission. This is in contrast to phenyl-bridged polypyridine Ru-Os complexes with a similar metal-metal distance, in which the Ru emission is strongly quenched because the nature of the bridging ligand allows for an efficient through-bond coupling. The results obtained for the compounds reported here suggest that energy transfer is predominantly taking place via a dipole-dipole, F?rster type, mechanism, that may dominate when through-bond coupling is weak. This is in stark contrast to ground state interaction, which is found to be critically dependent on the nature of the bridging unit employed.