Multiscale nuclear magnetic relaxation dispersion of complex liquids in bulk and confinement

The nuclear magnetic relaxation dispersion (NMRD) technique consists of measurement of the magnetic-field dependence of the longitudinal nuclear-spin-lattice relaxation rate 1/T₁. Usually, the acquisition of the NMRD profiles is made using a fast field cycling (FFC) NMR technique that varies the magnetic field and explores a very large range of Larmor frequencies (10 kHz < ω₀/(2π) <40 MHz). This allows extensive explorations of the fluctuations to which nuclear spin relaxation is sensitive. The FFC technique thus offers opportunities on multiple scales of both time and distance for characterizing the molecular dynamics and transport properties of complex liquids in bulk or embedded in confined environments. This review presents the principles, theories and applications of NMRD for characterizing fundamental properties such as surface correlation times, diffusion coefficients and dynamical surface affinity (NMR wettability) for various confined liquids. The basic longitudinal and transverse relaxation equations are outlined for bulk liquids. The nuclear relaxation of a liquid confined in pores is considered in detail in order to find the biphasic fast exchange relations for a liquid at proximity of a solid surface. The physical-chemistry of liquids at solid surfaces induces striking differences between NMRD profiles of aprotic and protic (water) liquids embedded in calibrated porous disordered materials. A particular emphasis of this review concerns the extension of FFC NMR relaxation to industrial applications. For instance, it is shown that the FFC technique is sufficiently rapid for following the progressive setting of cement-based materials (plasters, cement pastes, concretes). The technique also allows studies of the dynamics of hydrocarbons in proximity of asphaltene nano-aggregates and macro-aggregates in heavy crude oils as a function of the concentration of asphaltenes. It also gives new information on the wettability of petroleum fluids (brine and oil) embedded in shale oil rocks. It is useful for understanding the relations and correlations between NMR relaxation times T₁ and T₂, diffusion coefficients D, and viscosity η of heavy crude oils. This is of particular importance for interpreting T₁, T₂, 2D T₁-T₂ and D-T₂ correlation spectra that could be obtained down-hole, thus giving a valuable tool for investigating in situ the molecular dynamics of petroleum fluids. Another domain of interest concerns biological applications. This is of particular importance for studying the complex dynamical spectrum of a folded polymeric structure that may span many decades in frequency or time. A direct NMRD characterization of water diffusional dynamics is presented at the protein interface. NMR experiments using a shuttle technique give results well above the frequency range accessible via the FFC technique; examples of this show protein dynamics over a range from fast and localized motions to slow and delocalized collective motions involving the whole protein. This review ends by an interpretation of the origin of the proton magnetic field dependence of T₁ for different biological tissues of animals; this includes a proposal for interpreting in vivo MRI data from human brain at variable magnetic fields, where the FFC relaxation analysis suggests that brain white-matter is distinct from grey-matter, in agreement with diffusion-weighted MRI imaging.