No abstract

362 (1994).The thermodynamics of amino acid systems are key to the understanding of protein chemistry. We have found that many previous studies of the apparent molar volumes and heat capacities of aqueous solutions of amino acids were conducted at the standard temperature of 298.15 K. This does not allow for the fact that most biological processes occur at temperatures removed from this standard condition.In an attempt to address this imbalance we have measured densities and heat capacities for aqueous solutions of glycine, L-alanine, L-serine, and L-threonine at 288. 15, 298.15, 313.15, and 328.15 K using a Picker flow microcalorimeter. Apparent molar volumes and heat capacities, and the associated standard state partial molar properties have been calculated. Constant pressure variations of revised Helgeson, Kirkham, and Flowers equations have been fitted to calculated standard state volumes and heat capacities over the temperature range 288.15 to 328.15 K. These equations may be used to estimate standard state volumes and heat capacities, and hence equilibrium constants, for aqueous amino acid systems at higher temperatures.

A supramolecular species composed of a pair of nonequivalent Dy(III)-radical complexes exhibits single-molecule magnet (SMM) properties. The weak effective antiferromagnetic coupling between the Dy(III) ions can be compensated by application of a small (700 Oe) dc field, revealing the relaxation mode of the two distinct SMMs. These unique results illustrate how the dynamics of a supramolecular [Dy-Radical]2 SMM can be fine-tuned by the exchange-bias and an applied magnetic field.

Complexes of the 4-(2'-pyridyl)-1,2,3,5-dithiadiazolyl radical bidentate ligand with bis(hexafluoroacetylacetonato)manganese(II) and with bis(hexafluoroacetylacetonato)copper(II) have been prepared. Unlike the previously reported cobalt(II) complex, these complexes form dimers via intermolecular S...S contacts in the solid state. The spectroscopic and magnetic properties of these species in the solid state and in solution are reported and compared to the previously reported Co(II) complex, with emphasis on the elucidation of the a monomer/dimer equilibrium in the solution. The electrochemical properties of these species in solution are also presented and discussed.