We have investigated the mechanism of relaxivity for two magnetic resonance imaging contrast agents that both employ a cluster-nanocarrier design. The first system termed Mn8Fe4-coPS comprises the cluster Mn8Fe4O12(L)16(H2O)4 or Mn8Fe4 (1) (L = carboxylate) co-polymerized with polystyrene to form ∼75 nm nanobeads. The second system termed Mn3Bpy-PAm used the cluster Mn3(O2CCH3)6(Bpy)2 or Mn3Bpy (2) where Bpy = 2,2'-bipyridine, entrapped in ∼180 nm polyacrylamide nanobeads. Here, we investigate the rate of water exchange of the two clusters, and corresponding cluster-nanocarriers, in order to elucidate the mechanism of relaxivity in the cluster-nanocarrier. Swift-Connick analysis of O-17 NMR was used to determine the water exchange rates of the clusters and cluster-nanocarriers. We found distinct differences in the water exchange rate between Mn8Fe4 and Mn8Fe4-coPS, and we utilized these differences to elucidate the nanobead structure. Using the transverse relaxivity from O-17 NMR line widths, we were able to determine the hydration state of the Mn3Bpy (2) cluster as well as Mn3Bpy-PAm. Using these hydration states in the Swift-Connick analysis of O-17 NMR, we found the water exchange rate to be extremely close in value for the cluster Mn3Bpy and cluster-nanocarrier Mn3Bpy-PAm.
Keywords: MRI contrast agent; O-17 NMR; nanobead; relaxivity; water exchange.