Matrix‐Free DNP‐Enhanced NMR Spectroscopy of Liposomes Using a Lipid‐Anchored Biradical

Magic‐angle spinning dynamic nuclear polarization (MAS‐DNP) has been proven to be a powerful technique to enhance the sensitivity of solid‐state NMR (SSNMR) in a wide range of systems. Here, we show that DNP can be used to polarize lipids using a lipid‐anchored polarizing agent. More specifically, we introduce a C16‐functionalized biradical, which allows localization of the polarizing agents in the lipid bilayer and DNP experiments to be performed in the absence of excess cryo‐protectant molecules (glycerol, dimethyl sulfoxide, etc.). This constitutes another original example of the matrix‐free DNP approach that we recently introduced.     

Controlled Reactivity Tuning of Metal‐Functionalized Vanadium Oxide Clusters

Controlling the assembly and functionalization of molecular metal oxides [M_xO_y]^n? (M=Mo, W, V) allows the targeted design of functional molecular materials. While general methods exist that enable the predetermined functionalization of tungstates and molybdates, no such routes are available for molecular vanadium oxides. Controlled design of polyoxovanadates, however, would provide highly active materials for energy conversion, (photo‐) catalysis, molecular magnetism, and materials science. To this end, a new approach has been developed that allows the reactivity tuning of vanadium oxide clusters by selective metal functionalization. Organic, hydrogen‐bonding cations, for example, dimethylammonium are used as molecular placeholders to block metal binding sites within vanadate cluster shells. Stepwise replacement of the placeholder cations with reactive metal cations gives mono‐ and difunctionalized clusters. Initial reactivity studies illustrate the tunability of the magnetic, redox, and catalytic activity.