Heterogeneous 1 H and 13 C Parahydrogen-Induced Polarization of Acetate and Pyruvate Esters.

Abstract

Magnetic resonance imaging of [1-13 C]hyperpolarized carboxylates (most notably, [1-13 C]pyruvate) allows one to visualize abnormal metabolism in tumors and other pathologies. Herein, we investigate the efficiency of 1 H and 13 C hyperpolarization of acetate and pyruvate esters with ethyl, propyl and allyl alcoholic moieties using heterogeneous hydrogenation of corresponding vinyl, allyl and propargyl precursors in isotopically unlabeled and 1-13 C-enriched forms with parahydrogen over Rh/TiO2 catalysts in methanol-d4 and in D2 O. The maximum obtained 1 H polarization was 0.6±0.2 % (for propyl acetate in CD3 OD), while the highest 13 C polarization was 0.10±0.03 % (for ethyl acetate in CD3 OD). Hyperpolarization of acetate esters surpassed that of pyruvates, while esters with a triple carbon-carbon bond in unsaturated alcoholic moiety were less efficient as parahydrogen-induced polarization precursors than esters with a double bond. Among the compounds studied, the maximum 1 H and 13 C NMR signal intensities were observed for propyl acetate. Ethyl acetate yielded slightly less intense NMR signals which were dramatically greater than those of other esters under study.