Roles of rhenium diimine complexes as metal‐ion probes and photosensitizers in functional polyurethanes

Polyurethanes incorporated with rhenium diimine complexes were synthesized. The polymers exhibited interesting morphologies and solution properties. Results from gel permeation chromatography suggested the formation of polymer aggregates in solutions. The polymers could act as probes for metal ions. The addition of metal ions to polymer solutions led to significant changes in the electronic absorption properties of the polymer solutions. This was attributed to the interactions between the polyether moieties and metal ions. The metal complexes could also act as efficient photosensitizers. After doping with charge‐transport viologens, the photoconductivity of the polymers was greatly enhanced. The experimental quantum efficiency was simulated with Onsager's theory. The thermalization distances and the primary yields were typically 12–14 Å and 10^?3, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1708–1715, 2003     

The synthesis of 6-trifluoroethyl-l-lysine: a method to introduce functionality at C-6 of l-lysine

Described is a method of introducing trifluoroalkyl groups at C-6 of lysine. This chemistry has the potential to introduce a variety of functionality at C-6 of lysine.     

Dark cure studies of cationic photopolymerizations of epoxides: Characterization of kinetic rate constants at high conversions

The effective propagation rate constant (k_p; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the k_p as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the k_p values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004     

Multiphysical modeling and meshless simulation of electric‐sensitive hydrogels

According to a multiphase mixture theory, we have mathematically developed a multiphysical model with chemoelectromechanical coupling considerations, termed the multieffect‐coupling electric‐stimulus (MECe) model, to simulate the responsive behavior of electric‐sensitive hydrogels immersed in a bath solution under an externally applied electric field. For solutions of the MECe model consisting of coupled nonlinear partial differential governing equations, a meshless Hermite–Cloud method with a hierarchical iteration technique has been used for a one‐dimensional steady‐state analysis of a hydrogel strip. The computed results are compared with the experimental data, and there is very good agreement. Simulations within the domains of both hydrogels and surrounding solutions also present distributions of the ionic concentrations and electric potential as well as the hydrogel displacement. The effects of various physical parameters on the response behavior of electric‐stimulus responsive hydrogels are discussed in detail. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1514–1531, 2004     

Time-harmonic response of a vertical crack in plates

A technique for the characterization of an interior crack perpendicular to the surface of the plates is presented. A time-harmonic line load is applied on the upper surface of the plate. The scattered displacement field is calculated by using the strip element method. It is found that there are additional superimposed oscillations in the curve of the absolute values of the displacement in the region between the load and the crack. The mean value of the peaks of the additional oscillations increases with the crack length, and is less dependent on the distance from the load to the crack. The crack position is determined from the displacement distribution curve and the crack length is determined from the mean value of the peaks of the additional oscillations. Approximate polynomial formula of degree four for predicting the length of interior vertical cracks in isotropic homogeneous plates is also proposed. Numerical examples are given to demonstrate the present technique.     

OXIDATION OF ASCORBIC ACID AS AN INDICATOR OF PHOTOOXIDATIVE STRESS IN THE EYE

When whole retinal pigmented epithelium (RPE) cells isolated from bovine eyes are incubated with 14C-labeled ascorbic acid and exposed to a visible laser, the ascorbic acid is oxidized to dehydro-L-ascorbic acid (DHA). The amount of ascorbic acid which is oxidized is proportional to the radiant exposure of the sample (i.e. the total amount of radiation per unit area delivered over the exposure time). Blue light is more effective than red light in driving the reaction. The amount of label appearing in the DHA fraction is increased if unlabeled DHA is present in the reaction mixture, indicating that some redox cycling of ascorbate is occurring in the RPE cells. The ascorbic acid oxidizing activity does not depend on intact cells, is not inactivated by heating the cells to 80 degrees C, and appears to reside mainly in the subcellular fraction which contains melanin pigment granules. The ascorbic acid oxidation may be caused by free radicals formed when melanin is illuminated with light. This reaction appears to be a useful method for quantifying the production of free radicals during photooxidative stress.     

Cell transfer and monomial positivity

We give combinatorial proofs that certain families of differences of products of Schur functions are monomial-positive. We show in addition that such monomial-positivity is to be expected of a large class of generating functions with combinatorial definitions similar to Schur functions. These generating functions are defined on posets with labelled Hasse diagrams and include for example generating functions of Stanley's (P,ω)-partitions. T.L. was supported in part by NSF DMS-0600677.     

Magic neutrino mass matrix and the Bjorken–Harrison–Scott parameterization

Observed neutrino mixing can be described by a tribimaximal MNS matrix. The resulting neutrino mass matrix in the basis of a diagonal charged lepton mass matrix is both 2–3 symmetric and magic. By a magic matrix, I mean one whose row sums and column sums are all identical. I study what happens if 2–3 symmetry is broken but the magic symmetry is kept intact. In that case, the mixing matrix is parameterized by a single complex parameter U_e3, in a form discussed recently by Bjorken, Harrison, and Scott.