Triplet dynamic nuclear polarization of pyruvate via supramolecular chemistry

Abstract

Dynamic nuclear polarization (DNP) significantly improves the sensitivity of magnetic resonance imaging, and its most important medical application is cancer diagnosis via hyperpolarized ¹³C-labeled pyruvate. Unlike cryogenic DNP, triplet-DNP uses photoexcited triplet electrons under mild conditions. However, triplet-DNP of pyruvate has not been observed because of incompatibility of the hydrophobic polarizing agent with hydrophilic pyruvate. This work demonstrates that supramolecular complexation with β-cyclodextrin can disperse 4,4′-(pentacene-6,13-diyl)dibenzoate (NaPDBA), a pentacene derivative with hydrophilic substituents, even in the presence of high sodium pyruvate concentrations. The polarization of photoexcited triplet electron spins in NaPDBA was transferred to the ¹³C spins of sodium pyruvate via triplet-DNP of ¹H spins in water and ¹H-to-¹³C cross-polarization. This provides an important step toward the widespread use of ultra-sensitive MRI for cancer diagnosis.