Nuclear Magnetic Resonance (NMR) has found applications in fields running from physics, to chemistry, to structural biology and medicine. In all cases sensitivity has been a limitation, requiringmilligramquantitiesofsampleorexceedinglongsignalaveragingperiods. The latter can be particularly limiting for real-time metabolism studies where transit between substrate and product can occur on a time-scale of tens of seconds. Recently Dynamic Nuclear Polarization (DNP) has reemerged as a means of improving NMR sensitivity by many orders of magnitude. DNP enhanced in vivo monitoring of metabolism for cancer diagnosis is near the point of clinical application. Emphasis has been on the conversion one substrate (pyruvate) to a product (lactate). However, the potential for developing substrates that probe other metabolic pathways and elucidate mechanisms of participating enzymesisenormous. This presentation will cover some of the basic physics underlying DNP and illustrate applications with results from enzyme mechanism and in-cell studies on-going at UGA.