Functional Group Resolved Nuclear Spin Relaxation in Porous Media

Understanding solid-fluid interactions within porous materials is critical for their efficient utilisation across chemical reaction and separation processes. However, detailed characterisation of interfacial phenomena within such systems is hampered by their optically opaque nature. Motivated by the need to bridge this capability gap, we detail here the application of low magnetic field 2D ¹H nuclear spin relaxation measurements as a non-invasive probe of sorbate/sorbent interactions, exploring the relaxation characteristics exhibited by liquid adsorbates confined to a model mesoporous silica. For the first time, we demonstrate the capacity of such measurements to distinguish functional group-specific relaxation phenomena across a diverse range of protic adsorbates of wide importance as solvents, reagents, and hydrogen carriers, with distinct relaxation environments assigned to the alkyl and hydroxyl moieties of the confined liquids. Uniquely, this relaxation behaviour is shown to correlate with adsorbate acidity, with the observed relationship rationalised on the basis of surface-adsorbate proton exchange dynamics.

Functional Group Resolved Nuclear Spin Relaxation in Porous Media

Understanding solid-fluid interactions within porous materials is critical for their efficient utilisation across chemical reaction and separation processes. However, detailed characterisation of interfacial phenomena within such systems is hampered by their optically opaque nature. Motivated by the need to bridge this capability gap, we detail here the application of low magnetic field 2D ¹H nuclear spin relaxation measurements as a non-invasive probe of sorbate/sorbent interactions, exploring the relaxation characteristics exhibited by liquid adsorbates confined to a model mesoporous silica. For the first time, we demonstrate the capacity of such measurements to distinguish functional group-specific relaxation phenomena across a diverse range of protic adsorbates of wide importance as solvents, reagents, and hydrogen carriers, with distinct relaxation environments assigned to the alkyl and hydroxyl moieties of the confined liquids. Uniquely, this relaxation behaviour is shown to correlate with adsorbate acidity, with the observed relationship rationalised on the basis of surface-adsorbate proton exchange dynamics.

Nuclear Spin Relaxation of Longitudinal and Singlet Order in Liquid-CO2 Solutions

Hyperpolarization techniques can enormously enhance the NMR signal thus allowing the exploitation of hyperpolarized substrates for in-vivo MRI applications. The short lifetime of hyperpolarized spin order poses significant limitations in such applications. Spin order storage can be prolonged through the use of long-lived spin states. Additionally, the storage of spin polarization–either in the form of longitudinal or singlet order–can be prolonged in low viscosity solutions. Here, we report the use of low viscosity liquid-CO2 solutions to store nuclear spin polarization in the form of longitudinal and singlet order for extended periods. Our results demonstrate that this storage time can be considerably sustained in liquid-CO2 solutions in comparison to other low viscosity solvents, opening up the possibility of new, exciting storage experiments in the future.

Analysis of Conformational Exchange Processes using Methyl-TROSY-Based Hahn Echo Measurements of Quadruple-Quantum Relaxation

Transverse nuclear spin relaxation can be a sensitive probe of chemical exchange on timescales on the order of microseconds to milliseconds. Here we present an experiment for the simultaneous measurement of the relaxation rates of two four-spin transitions in selectively protonated methyl groups within perdeuterated biomacromolecules, alongside control experiments for measurement of 1H and 13C chemical shift anisotropies. We show that analysis of the static magnetic field dependence of zero-, double- and quadruple-quantum Hahn echo relaxation rates provides a robust indication of chemical exchange and determines the signed relative magnitudes of proton and carbon chemical shift differences between ground and excited states. The analysis can be combined with CPMG relaxation dispersion measurements to provide improved precision, particularly in the determination of 1H chemical shift differences.