VISCOELASTICITY AND IONIC CONDUCTIVITY OF TWO-COMPONENT EPOXY NETWORK CONTAINING LITHIUM PERCHLORATE*

Polymeric solid electrolyte system composed of triglycidyl ether of glycerol (TGEG), diglycidyl ether of polyethylene glycol (DGEPEG)and LiClO_4 salt were synthesized. In this" system the electrolyte has a pecularity that not merely can the LiClO_4 provide ionic carriers, but also catalyze the crosslinking reaction without adding an usual curing agent. The effect of salt content and degree of crosslinking on the viscoelasticity and ionic conductivity were studied. Both WLF and VTF equations were used to treat the experimental data in order to elucidate the mechanism of ionic conduction. It was found that the ionic conductivity of the system is carded out through the segmental motion mechanism. However, the data must be treated with care. For example, in evaluating WLF parameters, the contribution concerned with ionic carrier generation with temperature to the conductivity must be differentiated from that concerned with segmental motion. Besides, the temperature range suitable to WLF equation must also be considered. For VTF equation, it might be inapplicable ff the temperature is too low and close to the glass transition temperature of the specimen. Further study is needed in order to have a quantitative information on the limitation of these equations.     

Local quantum critical point in the pseudogap anderson model: finite-T dynamics and omega/T scaling

The pseudogap Anderson impurity model is a paradigm for locally critical quantum phase transitions. Within the framework of the local moment approach we study its finite-T dynamics, as embodied in the single-particle spectrum, in the vicinity of the symmetric quantum critical point (QCP) separating generalized Fermi liquid (Kondo screened) and local moment phases. The scaling spectra in both phases, and at the QCP itself, are obtained analytically. A key result is that pure omega/T scaling obtains at the QCP, where the Kondo resonance has just collapsed. The connection between the scaling spectra in either phase and that at the QCP is explored in detail.     

Residence time, loading force, pH, and ionic strength affect adhesion forces between colloids and biopolymer-coated surfaces

Exopolymers are thought to influence bacterial adhesion to surfaces, but the time-dependent nature of molecular-scale interactions of biopolymers with a surface are poorly understood. In this study, the adhesion forces between two proteins and a polysaccharide [Bovine serum albumin (BSA), lysozyme, or dextran] and colloids (uncoated or BSA-coated carboxylated latex microspheres) were analyzed using colloid probe atomic force microscopy (AFM). Increasing the residence time of an uncoated or BSA-coated microsphere on a surface consistently increased the adhesion force measured during retraction of the colloid from the surface, demonstrating the important contribution of polymer rearrangement to increased adhesion force. Increasing the force applied on the colloid (loading force) also increased the adhesion force. For example, at a lower loading force of approximately 0.6 nN there was little adhesion (less than -0.47 nN) measured between a microsphere and the BSA surface for an exposure time up to 10 s. Increasing the loading force to 5.4 nN increased the adhesion force to -4.1 nN for an uncoated microsphere to a BSA surface and to as much as -7.5 nN for a BSA-coated microsphere to a BSA-coated glass surface for a residence time of 10 s. Adhesion forces between colloids and biopolymer surfaces decreased inversely with pH over a pH range of 4.5-10.6, suggesting that hydrogen bonding and a reduction of electrostatic repulsion were dominant mechanisms of adhesion in lower pH solutions. Larger adhesion forces were observed at low (1 mM) versus high ionic strength (100 mM), consistent with previous AFM findings. These results show the importance of polymers for colloid adhesion to surfaces by demonstrating that adhesion forces increase with applied force and detention time, and that changes in the adhesion forces reflect changes in solution chemistry.     

A complete classification of homogeneous plane continua

We show that the only compact and connected subsets (i.e. continua) X of the plane \({\mathbb{R}^2}\) which contain more than one point and are homogeneous, in the sense that the group of homeomorphisms of X acts transitively on X, are, up to homeomorphism, the circle \({\mathbb{S}^1}\), the pseudo-arc, and the circle of pseudo-arcs. These latter two spaces are fractal-like objects which do not contain any arcs. It follows that any compact and homogeneous space in the plane has the form X × Z, where X is either a point or one of the three homogeneous continua above, and Z is either a finite set or the Cantor set.     

Dithiomethylether as a ligand in the hydrogenase h-cluster

An X-ray crystallographic refinement of the H-cluster of [FeFe]-hydrogenase from Clostridium pasteurianum has been carried out to close-to atomic resolution and is the highest resolution [FeFe]-hydrogenase presented to date. The 1.39 A, anisotropically refined [FeFe]-hydrogenase structure provides a basis for examining the outstanding issue of the composition of the unique nonprotein dithiolate ligand of the H-cluster. In addition to influencing the electronic structure of the H-cluster, the composition of the ligand has mechanistic implications due to the potential of the bridge-head gamma-group participating in proton transfer during catalysis. In this work, sequential density functional theory optimizations of the dithiolate ligand embedded in a 3.5-3.9 A protein environment provide an unbiased approach to examining the most likely composition of the ligand. Structural, conformational, and energetic considerations indicate a preference for dithiomethylether as an H-cluster ligand and strongly disfavor the dithiomethylammonium as a catalytic base for hydrogen production.     

Exciton-phonon coupling in indirect AlxGa1−xAs

Several persistent high-energy peaks in the photo-luminescence spectrum of indirect Al_xGa_1?xAs are reported. These transitions are assigned to zero-phonon and phonon-assisted bound-exciton annihilation processes. Symmetry determined selection rules indicate that the major interband recombination mechanism is due to LO phonon scattering of electrons near X(100) to the energetically adjacent Γ^CB₁ (000) intermediate state. Scattering associated with alloy disorder may also contribute to the spectrum. The change in the phonon-assisted spectra at x = 0.43 ± 0.01 provides an additional means of identification of the direct-indirect conduction band crossover.     

New Preparation Methodology of Functionalized Picolines

Under the organomagnesium complex n‐Bu₂CH₃MgLi conditions, picoline compounds provide a new entry to a broad range of polyfunctional picoline derivatives, after reaction with various electrophiles.