Magnetic resonance techniques are successfully utilized in a broad range of scientific disciplines and in various practical applications, with medical magnetic resonance imaging being the most widely known example. Currently, both fundamental and applied magnetic resonance are enjoying a major boost owing to the rapidly developing field of spin hyperpolarization. Hyperpolarization techniques are able to enhance signal intensities in magnetic resonance by several orders of magnitude, and thus to largely overcome its major disadvantage of relatively low sensitivity. This provides new impetus for existing applications of magnetic resonance and opens the gates to exciting new possibilities. In this review, we provide a unified picture of the many methods and techniques that fall under the umbrella term "hyperpolarization" but are currently seldom perceived as integral parts of the same field. Specifically, before delving into the individual techniques, we provide a detailed analysis of the underlying principles of spin hyperpolarization. We attempt to uncover and classify the origins of hyperpolarization, to establish its sources and the specific mechanisms that enable the flow of polarization from a source to the target spins. We then give a more detailed analysis of individual hyperpolarization techniques: the mechanisms by which they work, fundamental and technical requirements, characteristic applications, unresolved issues, and possible future directions. We are seeing a continuous growth of activity in the field of spin hyperpolarization, and we expect the field to flourish as new and improved hyperpolarization techniques are implemented. Some key areas for development are in prolonging polarization lifetimes, making hyperpolarization techniques more generally applicable to chemical/biological systems, reducing the technical and equipment requirements, and creating more efficient excitation and detection schemes. We hope this review will facilitate the sharing of knowledge between subfields within the broad topic of hyperpolarization, to help overcome existing challenges in magnetic resonance and enable novel applications.

The endohedral fullerene CH₄@C₆₀, in which each C₆₀ fullerene cage encapsulates a single methane molecule, has been synthesized for the first time. Methane is the first organic molecule, as well as the largest, to have been encapsulated in C₆₀ to date. The key orifice contraction step, a photochemical desulfinylation of an open fullerene, was completed, even though it is inhibited by the endohedral molecule. The crystal structure of the nickel(II) octaethylporphyrin/ benzene solvate shows no significant distortion of the carbon cage, relative to the C₆₀ analogue, and shows the methane hydrogens as a shell of electron density around the central carbon, indicative of the quantum nature of the methane. The ¹H spin‐lattice relaxation times (T₁) for endohedral methane are similar to those observed in the gas phase, indicating that methane is freely rotating inside the C₆₀ cage. The synthesis of CH₄@C₆₀ opens a route to endofullerenes incorporating large guest molecules and atoms.

The resurgence of nuclear hyperpolarization brings new insights into spin diffusion processes near paramagnetic centers.

Water exists in two forms, para and ortho, that have nuclear spin states with different symmetries. Here we report the conversion of fullerene-encapsulated para water to ortho water. The enrichment of para water at low temperatures is monitored via changes in the electrical polarizability of the material. Upon rapid dissolution of the material in toluene the excess para water converts to ortho water. In ${\mathrm{H}}_2{}^{16}\mathrm{O}@{\mathrm{C}}_{60}$ the conversion leads to a slow increase in the NMR signal. In ${\mathrm{H}}_2{}^{17}\mathrm{O}@{\mathrm{C}}_{60}$ the conversion gives rise to weak signal enhancements attributed to quantum-rotor-induced nuclear spin polarization. The time constants for the para-to-ortho conversion of fullerene-encapsulated water in ambient temperature solution are estimated as $30\pm 4\mathrm{s}$ for the ${}^{16}\mathrm{O}$ isotopolog of water, and $16\pm 3\mathrm{s}$ for the ${}^{17}\mathrm{O}$ isotopolog.

Li-containing materials providing fast ion transport pathways are fundamental in Li solid electrolytes and the future of all-solid-state batteries. Understanding these pathways, which usually benefit from structural disorder and cation/anion substitution, is paramount for further developments in next-generation Li solid electrolytes. Here, we exploit a range of variable temperature ⁶Li and ⁷Li nuclear magnetic resonance approaches to determine Li-ion mobility pathways, quantify Li-ion jump rates, and subsequently identify the limiting factors for Li-ion diffusion in Li₃AlS₃ and chlorine-doped analogue Li_4.3AlS_3.3Cl_0.7. Static ⁷Li NMR line narrowing spectra of Li₃AlS₃ show the existence of both mobile and immobile Li ions, with the latter limiting long-range translational ion diffusion, while in Li_4.3AlS_3.3Cl_0.7, a single type of fast-moving ion is present and responsible for the higher conductivity of this phase. ⁶Li-⁶Li exchange spectroscopy spectra of Li₃AlS₃ reveal that the slower moving ions hop between non-equivalent Li positions in different structural layers. The absence of the immobile ions in Li_4.3AlS_3.3Cl_0.7, as revealed from ⁷Li line narrowing experiments, suggests an increased rate of ion exchange between the layers in this phase compared with Li₃AlS₃. Detailed analysis of spin-lattice relaxation data allows extraction of Li-ion jump rates that are significantly increased for the doped material and identify Li mobility pathways in both materials to be three-dimensional. The identification of factors limiting long-range translational Li diffusion and understanding the effects of structural modification (such as anion substitution) on Li-ion mobility provide a framework for the further development of more highly conductive Li solid electrolytes.