Isolation, properties and structural studies on a compound from tunicate blood cells that may be involved in vanadium accumulation

Abstract

A novel compound, for which the trivial name tunichrome is proposed, was isolated from the vanadium-rich blood cells of the tunicate Ascidia niga. Preliminary structural studies suggest a molecular weight of about 390, the presence of conjugated vinyl groups, and an acidic group, possibly carboxyl, with an apparent pKa of 3.0. Elements C, H, N and O comprise 98.4% of the sample weight, the number of atoms per mol of tunichrome being 14.1, 22.2, 1.5 and 10.6 respectively, which indicates some heterogeneity in the sample. Tunichrome readily reduces Fe(III) and V(V). In an initial fast step, 2 mol of V(V) are reduced, or 4 mol of Fe(III)-phenanthroline per mol of tunichrome; in a further slow reaction, another 9 mol of Fe(III)-phenanthroline or Fe(III)-bipyridine are reduced. The initial reaction is first-order with respect to tunichrome and Fe(III). Above pH 3.5, tunichrome is rapidly hydrolysed, 13 mol of OH- being consumed per mol of tunichrome. The hydrolysis involves polymerization and loss of the characteristic absorption peak at 325 nm. It is suggested that the presence of tunichrome may be linked to vanadium accumulation by the blood cells. The mechanism involves entry of vanadate via an anionic channel into vacuoles of the blood cells, where it is reduced to V(IV) or V(III), both of which, being cationic, cannot escape from the vacuole.