Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) can boost magnetic resonance sensitivity by several orders of magnitude. The method relies on the transfer of electron spin polarization to the surrounding nuclear spins in the solid-state at low temperatures and moderate magnetic fields. One critical aspect for the success of a dDNP experiment is the sample formulation. Sample formulations have continually evolved, from frozen glassy solutions to complex hybrid polarizing solids, enabling faster and more repeatable DNP, as well as new applications to molecular systems that could not have be addressed before. In this review, we present some of the most important scientific advances related to sample formulations with a historical perspective, from the invention of DNP until today.
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