Aqueous, Heterogeneous Parahydrogen-Induced ¹⁵N Polarization

The successful transfer of parahydrogen-induced polarization to ¹⁵N spins using heterogeneous catalysts in aqueous solutions was demonstrated. Hydrogenation of a synthesized unsaturated ¹⁵N-labeled precursor (neurine) with parahydrogen (p-H₂) over Rh/TiO₂ heterogeneous catalysts yielded a hyperpolarized structural analog of choline. As a result, ¹⁵N polarization enhancements of over two orders of magnitude were achieved for the ¹⁵N-ethyl trimethyl ammonium ion product in deuterated water at elevated temperatures. Enhanced ¹⁵N NMR spectra were successfully acquired at 9.4 T and 0.05 T. Importantly, long hyperpolarization lifetimes were observed at 9.4 T, with a ¹⁵N T₁ of ~6 min for the product molecules, and the T₁ of the deuterated form exceeded 8 min. Taken together, these results show that this approach for generating hyperpolarized species with extended lifetimes in aqueous, biologically compatible solutions is promising for various biomedical applications.