High‐and low‐resolution solid‐state nuclear magnetic resonance (SSNMR) applications to the study of pharmaceuticals are reviewed. Examples are shown involving the use of mono‐and bidimensional SSNMR techniques based on different nuclear interactions and the measurement of several nuclear parameters, such as chemical shifts, line widths, and relaxation times (T₁, T₂, T_1ρ). The systems investigated include pure active pharmaceutical ingredients (APIs), substances used as drug excipients, and solid dispersions formed by APIs and excipients, up to final drug formulations. The most important aspects treated concern structural, dynamic, and morphological properties, and, in particular, identification, characterization, and quantitation of polymorphs and related forms, conformational and crystalline packing behavior, amorphous phase properties and stability, effects of drug processing, molecular motions, API‐excipient and excipient‐excipient chemical and physical interactions, and phase mixing in heterophasic systems.

The characterization of a variety of organic/inorganic multicomponent materials (OIMM) through solid-state NMR (SSNMR) spectroscopy will be reviewed. Many examples of applications to OIMM will be described, based on the observation of different nuclei and the use of various SSNMR methods, such as 1D and 2D techniques, measurements on relaxation and spin diffusion processes. OIMM are a very general category of systems differing, for example, by chemical nature and relative amount of organic and inorganic components, shape and size of the domains, and type of organic-inorganic interface. Some of the most investigated classes of OIMM are organically modified silicates, polymer/clay composites, polymer/inorganic filler systems, polymer electrolytes, stationary chromatographic phases, zeolites, and mesoporous silicas including small organic molecules. The aspects most efficiently investigated by SSNMR and discussed in this review include physical and/or chemical interactions occurring at the organic-inorganic interface, structural and dynamic behavior of the organic components, and dimensions and dispersion of organic and inorganic domains.

Establishing mechanistic understanding of crystallization processes at the molecular level is challenging, as it requires both the detection of transient solid phases and monitoring the evolution of both liquid and solid phases as a function of time. Here, we demonstrate the application of dynamic nuclear polarization (DNP) enhanced NMR spectroscopy to study crystallization under nanoscopic confinement, revealing a viable approach to interrogate different stages of crystallization processes. We focus on crystallization of glycine within the nanometric pores (7–8 nm) of a tailored mesoporous SBA-15 silica material with wall-embedded TEMPO radicals. The results show that the early stages of crystallization, characterized by the transition from the solution phase to the first crystalline phase, are straightforwardly observed using this experimental strategy. Importantly, the NMR sensitivity enhancement provided by DNP allows the detection of intermediate phases that would not be observable using standard solid-state NMR experiments. Our results also show that the metastable β polymorph of glycine, which has only transient existence under bulk crystallization conditions, remains trapped within the pores of the mesoporous SBA-15 silica material for more than 200 days.