Spectroscopic Study of Acid-base Equilibria and Ion Pairing in Supercritical Methanol

Acid-base equilibria between 2,5-dichlorophenol (DCP) and various bases (LiOH, NaOH, and KOH) were studied in ambient to supercritical methanol, by measuring the absorption spectrum of DCP at alkali metal hydroxide molalities ranging up to 10 mmol⋅kg⁻¹, at temperatures up to 250 °C and a pressure of 25.0 MPa. The spectrum was deconvoluted into contributions for the acidic (HA) and basic (A⁻) forms of DCP, taking into account a blue shift of the phenolate (A⁻) spectrum due to the effect of ion pairing with an alkali metal cation. Degrees of dissociation of DCP determined from the spectra suggested that the dissociation constant of DCP has a maximum around 150 °C, whereas that of KOH decreases with temperature. The phenolate-alkali metal ion pairing was examined from the peak shift of the phenolate spectrum in the presence of Li⁺, Na⁺, and K⁺. A smaller cation radius and higher temperature (thus a lower dielectric constant for methanol) give rise to stronger electrostatic interaction in the ion pair. The basicities of the alkali metal hydroxides in supercritical methanol were compared using DCP as an indicator, and were shown to follow the order LiOH < NaOH ≤ KOH. This order is the same as that for the catalytic effect of alkali metal hydroxides on the methylation of phenol in supercritical methanol (Takebayashi et al.: Ind. Eng. Chem. Res. 47:704–709, 2008). Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Stability and Synchronization of a Ring of Identical Cells with Delayed Coupling

We consider a ring of identical elements with time delayed, nearest neighbour coupling. The individual elements are modelled by a scalar delay differential equation which includes linear decay and nonlinear delayed feedback. The linear stability of the trivial solution is completely analyzed and illustrated in the parameter space of the coupling strength and the coupling delay. Conditions for global stability of the trivial solution are also given. The bifurcation and stability of nontrivial synchronous solutions from the trivial solution is analyzed using a centre manifold construction.Dedicated to Professor Shui-Nee Chow on the occasion of his 60th birthday.     

The effect of stoichiometry on chain segment and ion mobility in partially polymerized epoxy systems

The temperature dependence of steady-shear viscosity and ionic conductivity were measured for a series of unreacted mixtures and partially cured, ungelled samples of diglycidyl ether of bisphenol-A (DGEBA) and an amine cross-linking agent, diamino diphenyl sulfone (DDS). Six stoichiometric ratios of epoxide groups to amine hydrogens were examined. Free volume expressions were used to model the temperature dependence of the conductivity and viscosity for the unreacted DGEBA-DDS mixtures. In addition, these expressions were combined to successfully correlate changes in viscosity and conductivity during the DGEBA-DDS polymerization prior to gelation. It also was demonstrated that the change in weight average molecular weight during polymerization could be interpreted from the dielectric data. Through studying variations in the stoichiometry, it was possible to examine the effects of changes in chemical structure and ion concentration on the fitted parameters in the free volume models. The inherent ion transport factor (ζ₀) was found to be inversely proportional to the concentration of ions in the test samples. The fractional free volume for segmental motion (B) was found to increase with an increase in the glass transition temperature and to be a function of the rigidity of the polymer. ©1995 John Wiley & Sons, Inc.     

Menus of kuratowski subgraphs

Motivated by heuristic embedding algorithms, this paper is concerned with the organization of potentially large lists of Kuratowski subgraphs of an arbitrary nonpianar graph. A graphical structure called a "nearly Hamiltonian" graph is defined. It is shown that lists of Kuralowski subgraphs can be lexicographically organized in such structures. It is shown that any nonpianar graph contains such structures and at least one such structure with a nonempty list of Kuratowski subgraphs can be located in linear time in ihe edges of the graph.     

Evidence for a role of glutamate as an efferent transmitter in taste buds

Background  

Glutamate has been proposed as a transmitter in the peripheral taste system in addition to its well-documented role as an umami taste stimulus. Evidence for a role as a transmitter includes the presence of ionotropic glutamate receptors in nerve fibers and taste cells, as well as the expression of the glutamate transporter GLAST in Type I taste cells. However, the source and targets of glutamate in lingual tissue are unclear. In the present study, we used molecular, physiological and immunohistochemical methods to investigate the origin of glutamate as well as the targeted receptors in taste buds.