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     

A Bicriterial Optimization Problem of Antenna Design

In this paper we consider a special optimization problem withtwo objectives which arises in antenna theory. It is shown that thisabstract bicriterial optimization problem has at least one solution.Discretized versions of this problem are also discussed, and therelationships between these finite dimensional problems and the infinitedimensional problem are investigated. Moreover, we presentnumerical results for special parameters using a multiobjectiveoptimization method.     

Lifshitz tails for periodic plus random potentials

We prove that the integrated density of states () for a potentialW =V _per +V has Lifshitz tails where V_per is a periodic potential with reflection symmetry andV is a random potential, e.g., of the formV =q _i ()f(x–i).research partially supported by DFG.research partially supported by USNSF under grant No. MCS-81-20833.     

On the integrated density of states for crystals with randomly distributed impurities

In the present paper, we discuss spectral properties of a periodic Schrödinger operator which is perturbed by randomly distributed impurities; such operators occur as simple models for crystals (or semi-conductors) with impurities. While the spectrum itself is independent of the concentrationp of impurities, for 0<p<1, we focus our attention on the limiting behavior of the integrated density of states _p of the random Schrödinger operator, inside a spectral gap of the periodic operator, asp0. Denoting byU ₀ the set of eigenvalues (in the gap) of the reference problem having precisely one impurity (located at the origin, say), we show that the integrated density of states concentrates around the points ofU ₀, in the sense that _p (U ) is of orderp, for any fixed -neighborhoodU ofU ₀, while _p (K)C·p ², for any compact subsetK of the gap which does not intersectU .Research partially supported by Deutsche Forschungsgemeinschaft     

IBX-mediated alpha-hydroxylation of alpha-alkynyl carbonyl systems. A convenient method for the synthesis of tertiary alcohols

[reaction: see text] IBX (o-iodoxybenzoic acid) is an excellent reagent for the alpha-hydroxylation of alpha-alkynyl carbonyl compounds without giving dehydrogenation products. The convenient procedure proves to be useful for the construction of a variety of tertiary alcohols (55-91%) under mildly acidic conditions.