Differential scanning calorimetric studies on the thermotropic phase transitions of dry and hydrated forms of N-acylethanolamines of even chainlengths

Abstract

N-acylethanolamines (NAEs) have attracted the attention of researchers in the last two decades due to their occurrence in biological membranes under conditions of stress as well as under normal conditions. Differential scanning calorimetric studies have been carried out on dry and hydrated samples of a homologous series of N-acylethanolamines containing saturated acyl chains of even number of carbon atoms (n=8–20). In both cases a major sharp endothermic transition was observed which occurs at the melting point for the dry NAEs whereas for the hydrated samples it occurs at considerably lower temperatures. The enthalpies and entropies corresponding to this transition could be fitted, in each case, to a straight line suggesting that the transition enthalpy and transition entropy consist of a fixed component from the polar head group and the terminal methyl group, whereas the contribution of the methylene groups, (CH₂)_n, is linearly proportional to the number of carbon atoms in it. The contributions of each methylene unit to the transition enthalpy and transition entropy of NAEs were found to be ΔH_inc=0.82 (±0.02) and 0.96 (±0.06) kcal mol⁻¹, and ΔS_inc=2.01 (±0.06) and 2.37 (±0.17) cal mol⁻¹ K⁻¹, respectively, for the dry and hydrated samples of NAEs, whereas the end contributions arising from the head group and the terminal methyl group were determined to be ΔH_o=−0.10 (±0.26) and −0.52 (±0.82) kcal mol⁻¹ and ΔS_o=2.12 (±0.71) and 3.1 (±2.3) cal mol⁻¹ K⁻¹, respectively, for the dry and hydrated samples of NAEs. These results are relevant to an understanding of the thermodynamics of the phase properties of NAEs in membranes.