Improved Structural Elucidation of Synthetic Polymers by Dynamic Nuclear Polarization Solid-State NMR Spectroscopy.

Dynamic nuclear polarization (DNP) is shown to greatly improve the solid-state nuclear magnetic resonance (SSNMR) analysis of synthetic polymers by allowing structural assignment of intrinsically diluted NMR signals, which are typically not detected in conventional SSNMR. Specifically, SSNMR and DNP SSNMR were comparatively used to study functional polymers for which precise structural elucidation of chain ends is essential to control their reactivity and to eventually obtain advanced polymeric materials of complex architecture. Results show that the polymer chain-end signals, while hardly observable in conventional SSNMR, could be clearly identified in the DNP SSNMR spectrum owing to the increase in sensitivity afforded by the DNP setup (a factor ∼10 was achieved here), hence providing access to detailed structural characterization within realistic experimental times. This sizable gain in sensitivity opens new avenues for the characterization of "smart" functional polymeric materials and new analytical perspectives in polymer science.