Coupled ion and network dynamics in polymer electrolytes: Monte Carlo study of a lattice model

Monte Carlo simulations are used to study ion and polymer chain dynamic properties in a simplified lattice model with only one species of mobile ions. The ions interact attractively with specific beads in the host chains, while polymer beads repel each other. Cross linking of chains by the ions reduces chain mobilities which in turn suppresses ionic diffusion. Diffusion constants for ions and chains as a function of temperature follow the Vogel-Tammann-Fulcher (VTF) law with a common VTF temperature at low ion concentration, but both decouple at higher concentrations, in agreement with experimental observations. Our model allows us to introduce pressure as an independent variable through calculations of the equation of state using the quasichemical approximation, and to detect an exponential pressure dependence of the ionic diffusion.     

β-Amino alcohol selectors for enantioselective separation of amino acids by ligand-exchange capillary zone electrophoresis in a low molecular weight organogel

A new family of copper ligand-exchange selectors, L- or D-β-amino alcohols, is employed for the chiral separation of D,L-dansyl-amino acids, unmodified amino acid racemates, phenylalanine and tryptophan, and β-blocker L,D-propranolol by SDS-micellar electrokinetic chromatography and by electrophoretic chromatography in a low molecular weight organogel (LMOG)-filled capillary. The LMOG comprised a self-assembled fibrillar gel of trans-(1S,2S)-1,2-bis-(dodecylamido) cyclohexane in methanol. The di-L-valinol-copper complex exhibited the best performance on LMOG-CE compared with all other β-amino alcohol-copper selectors. The dependence of chiral resolution on the pH*, the ratio between the copper and the L-valinol ligand and the concentration of added selector complex in the run buffer were investigated revealing a marked difference between the activity of the copper-valinol and the previously studied copper-valine selector. The optimal separation conditions were achieved using a 2:1 valinol/copper ratio, in accordance with the 2:1 structure of the complex, which was proven by single crystal and powder X-ray diffractions and by elemental analysis. Unlike the copper-valine selectors that could be used only under acidic conditions (pH* 3.5), the copper-valinol selectors could be used under near-neutral conditions and even at pH* 9.1. A comparison between SDS-micellar electrokinetic chromatography and LMOG-CE under otherwise identical conditions revealed a significant superior separation on the LMOG-filled capillaries.     

Bactericidal effects of photoactivated porphyrins--an alternative approach to antimicrobial drugs

Photoactivated porphyrins display a potent cytotoxic activity towards a variety of Gram positive bacteria, mycoplasma and yeasts, but not Gram negative cells. The prerequisite for photosensitization of a microbial cell is the binding of porphyrin to the cytoplasmic membrane in a pH-dependent manner. On illumination, the membrane bound, and possibly, cytoplasmic porphyrin molecules generate singlet oxygen and radicals which sensitize biomolecules and lead to cell death. The immediate inhibition of cell growth on photodynamic treatment is accompanied by alterations in cell wall and membrane synthesis, leading to the formation of large mesosomes adjacent to the unaccomplished septa. Hemin bound to microbial cells exerts cytotoxic activity by peroxidative and oxidative reactions independent of light. Future research in the field may enhance the possibility of using porphyrin photosensitization for treatment of microbial infections. Such clinical use will be unrelated to the antibiotic resistance of the pathogen. Resistance of Gram negative bacteria to porphyrin photosensitization is the main impediment to its use as a broad spectrum antibacterial method.     

Durability of polyurethanes elastomers

The effect of thermal aging on three different elastomeric polyurethane adhesives was studied. Consequently, an attempt was made to predict the polyurethanes' service lifetimes from the changes in tensile properties, hardness of bulk specimens and adhesion strength properties (lap shear and butt joints) of polycarbonate bonded joints. Aging temperatures ranged from ambient to 70 °C (at 50% relative humidity) for durations from 20 days to 18 months. Experimental results were analyzed according to a kinetic rate theory and using limit values for the various properties. Consequently, service lifetimes were determined and compared to results from actual service life. Predictions of long-term performance from accelerated tests proved to be reasonable for the properties and materials studied.     

The higher lower central series

The Baer invariants Γ _n (G) of a group are central extensions of the elementsγ _n (G) of the lower central series. We show that the inclusionsγ _n +1 ⊂γ _n can be lifted to functor morphisms Γ _n+1→Γ _n and a canonical Lie algebra, analogous to Lazard’s Lie algebra, can be constructed which is explicitly computable. This is applied in various ways.     

Random graphs in the monadic theory of order

We continue the works of Gurevich-Shelah and Lifsches-Shelah by showing that it is consistent with ZFC that the first-order theory of random graphs is not interpretable in the monadic theory of all chains. It is provable from ZFC that the theory of random graphs is not interpretable in the monadic second order theory of short chains (hence, in the monadic theory of the real line). Received: 18 July 1996     

A new algorithm for generation of permutations

A new algorithm for generating permutations is presented, that generates the next permutation by reversing a certain suffix of its predecessor. The average size of this suffix is less thane 2.8. It is shown how to find the position of a given permutation and how to construct the permutation of a given position, where the position refers to the order in which the permutations are generated, and is also new.On leave from the Department of Computer Science, Technion, Haifa, Israel. This work was supported by NSF grant MCS-8302391.     

Mechanics of composites with two families of finitely extensible fibers undergoing large deformations

Motivated by experimental measurements of the uniaxial response of collagen fibers, a new strain energy-density function for a solid which is finitely extensible along a preferred direction is proposed. Next, by application of a homogenization technique, the macroscopic strain energy-density function of composites with one and two families of fibers of this material embedded in a neo-Hookean matrix are determined. The resulting explicit expressions for the macroscopic strain energy-density functions are given in terms of the behaviors of the individual phases and their volume fractions. The responses of a few specific composites are investigated, revealing the lock-up surfaces of these composites. Finally, we examine the ability of the macroscopic model to capture experimentally measured stress-strain curves for the medial layer of a human abdominal aorta.     

Stable quantum resonances in atom optics

A theory for stabilization of quantum resonances by a mechanism similar to one leading to classical resonances in nonlinear systems is presented. It explains recent surprising experimental results, obtained for cold cesium atoms when driven in the presence of gravity, and leads to further predictions. The theory makes use of invariance properties of the system allowing for separation into independent kicked rotor problems. The analysis relies on a fictitious classical limit where the small parameter is not Planck's constant, but rather the detuning from the frequency that is resonant in the absence of gravity.