Inorganic Chemistry, Vol.35, No.11, 3375-3379, 1996
Water Exchange and Rotational-Dynamics of the Dimeric Gadolinium(III) Complex (BO(Gd(Do3A)(H2O))(2)) - a Variable-Temperature and Variable-Pressure O-17 NMR-Study
Rapid water exchange and slow rotation are essential for high relaxivity MRI contrast agents. A variable-temperature and -pressure O-17 NMR study at 14.1, 9.4, and 1.4 T has been performed on the dimeric BO(DO3A)(2), 2,11-dihydroxy-4,9-dioxa-1,12-bis[1,4,7,10-tetraaza-4,7,10-tris (carboxymethyl)cyclododecyl]dodecane, complex of Gd(III). This complex is of relevance to MRI as an attempt to gain higher H-1 relaxivity by slowing down the rotation of the molecule compared to monomeric Gd(III) complexes used as contrast agents. From the O-17 NMR longitudinal and transverse relaxation rates and chemical shifts we determined the parameters characterizing water exchange kinetics and the rotational motion of the complex, both of which influence H-1 relaxivity. The rate constant and the activation enthalpy for the water exchange, k(ex) and Delta H double dagger, are (1.0 +/- 0.1) x 10(6) s(-1) and (30.0 +/- 0.2) kJ mol(-1), respectively, and the activation volume, Delta V double dagger, of the process is (+0.5 +/- 0.2) cm(3) mol(-1), indicating an interchange mechanism. The rotational correlation time becomes about three times longer compared to monomeric Gd(III) polyamino-polyacetate complexes studied so far : tau(R) = (250 +/- 5) ps, which results in an enhanced proton relaxivity by raising the correlation time for the paramagnetic interaction.
Keywords:RELAXATION;IONS