Enhancement of the water proton relaxivity by trapping Gd3+ complexes in nanovesicles

We present a theoretical model for calculating the relaxivity of the water protons due to Gd3+ complexes trapped inside nanovesicles, which are permeable to water. The formalism is applied to the characterization of apoferritin systems [S. Aime et al., Angew. Chem., Int. Ed. 41, 1017 (2002); O. Vasalatiy et al., Contrast Media Mol. Imaging 1, 10 (2006)]. The very high relaxivity due to these systems is attributed to an increase of the local viscosity of the aqueous solution inside the vesicles and to an outer-sphere mechanism which largely dominates the inner-sphere contribution. We discuss how to tailor the dynamic parameters of the trapped complexes in order to optimize the relaxivity. More generally, the potential of relaxivity studies for investigating the local dynamics and residence time of exchangeable molecules in nanovesicles is pointed out.