The anomalous relaxivity of Mn3+ (TPPS4)

It was recently reported (C-W. Chen et al., FEBS Lett. 168, 70 (1984)) that water solutions of Mn3+ (TPPS4) have a surprisingly high relaxivity at 20 MHz and 37 degrees C, greater than most Mn2+ complexes including the hexaaquoion. Because Mn3+ (TPPS4) is highly stable, and porphyrins in general are tumor-seeking, we have sought to understand the origin of the large relaxivity by comparing the 1/T1 NMRD profiles (magnetic field dependence of 1/T1 of solvent protons) of Mn3+ (TPPS4) solutions with those of a number of other small Fe3+ and Mn2+ complexes. By relating the measured NMRD profiles to the theory of relaxation by magnetic dipolar interactions, in a form appropriate for small paramagnetic solute molecules, we establish that the theory affords an excellent quantitative description of the relaxation behavior of all the samples, and confirm that the relaxivity of Mn3+ (TPPS4) is anomalously high. The effect is attributed, in part, to the anisotropy of the ground-state wavefunction of Mn3+ in the porphyrin complex, effectively bringing the spin density of the Mn3+ ions closer to the protons of the coordinated water molecules than would a spherically symmetric S-state ion. In addition, the paramagnetic relaxation time of the Mn3+ spins, though short, is longer than would be anticipated for a non-S-state ion, and increases substantially with magnetic field above about 2 MHz. In this regard, Mn3+ (TPPS4) may be one of a class of molecules with properties particularly favorable for use as contrast-enhancing agents in magnetic resonance imaging.