Self-diffusion, dynamical molecular conformation, and liquid structures of n-saturated and unsaturated fatty acids

The translational movement, the dynamical molecular conformation, and the aggregate structure in the liquid state for three kinds of cis-type unsaturated fatty acids (cis-6-, cis-9-, and cis-11-octadecenoic acids), trans-type unsaturated acid (trans-9-octadecenoic acid), and n-saturated acid (octadecanoic acid) have been studied through the measurements of density, self-diffusion coefficient, C-13 NMR spin-lattice relaxation time, and X-ray diffraction. The magnitude of the self-diffusion coefficient, D, fell in sequence of cis-type unsaturated acids > trans-type acid > saturated acid below 350 K. Above 350 K the value of D for the trans-type acid rose to those for the cis-type acids. On the other hand, the density rho for the acids also fell in the order of cis-type acids > cans-type acid > saturated acid; the order of the density is just opposite to that expected from the results of the self-diffusion coefficient and other physical properties such as melting point and heat of fusion. This discrepancy between D and rho values for the acids is well explained by the models of the clusters in their liquids.