Spatially-resolved ¹H NMR relaxation-exchange measurements in heterogeneous media

In the last decades, the ¹H NMR T₂-T₂ relaxation-exchange (REXSY) technique has become an essential tool for the molecular investigation of simple and complex fluids in heterogeneous porous solids and soft matter, where the mixing-time-evolution of cross-correlated T₂-T₂ peaks enables a quantitative study of diffusive exchange kinetics in multi-component systems. Here, we present a spatially-resolved implementation of the T₂-T₂ correlation technique, named z-T₂-T₂, based on one-dimensional spatial mapping along z using a rapid frequency-encode imaging scheme. Compared to other phase-encoding methods, the adopted MRI technique has two distinct advantages: (i) is has the same experimental duration of a standard (bulk) T₂-T₂ measurement, and (ii) it provides a high spatial resolution. The proposed z-T₂-T₂ method is first validated against bulk T₂-T₂ measurements on homogeneous phantom consisting of cyclohexane uniformly imbibed in finely-sized α-Al₂O₃ particles at a spatial resolution of 0.47 mm; thereafter, its performance is demonstrated, on a layered bed of multi-sized α-Al₂O₃ particles, for revealing spatially-dependent molecular exchange kinetics properties of intra- and inter-particle cyclohexane as a function of particle size. It is found that localised z-T₂-T₂ spectra provide well resolved cross peaks whilst such resolution is lost in standard bulk T₂-T₂ data. Future prospective applications of the method lie, in particular, in the local characterisation of mass transport phenomena in multi-component porous media, such as rock cores and heterogeneous catalysts.