"Direct" 13 C Hyperpolarization of 13 C-Acetate by MicroTesla NMR Signal Amplification by Reversible Exchange (SABRE)

Abstract

Herein, we demonstrate "direct" ¹³ C hyperpolarization of ¹³ C-acetate via signal amplification by reversible exchange (SABRE). The standard SABRE homogeneous catalyst [Ir-IMes; [IrCl(COD)(IMes)], (IMes=1,3-bis(2,4,6-trimethylphenyl), imidazole-2-ylidene; COD=cyclooctadiene)] was first activated in the presence of an auxiliary substrate (pyridine) in alcohol. Following addition of sodium 1-¹³ C-acetate, parahydrogen bubbling within a microtesla magnetic field (i.e. under conditions of SABRE in shield enables alignment transfer to heteronuclei, SABRE-SHEATH) resulted in positive enhancements of up to ≈100-fold in the ¹³ C NMR signal compared to thermal equilibrium at 9.4 T. The present results are consistent with a mechanism of "direct" transfer of spin order from parahydrogen to ¹³ C spins of acetate weakly bound to the catalyst, under conditions of fast exchange with respect to the ¹³ C acetate resonance, but we find that relaxation dynamics at microtesla fields alter the optimal matching from the traditional SABRE-SHEATH picture. Further development of this approach could lead to new ways to rapidly, cheaply, and simply hyperpolarize a broad range of substrates (e.g. metabolites with carboxyl groups) for various applications, including biomedical NMR and MRI of cellular and in vivo metabolism.

Keywords: SABRE-SHEATH; acetate; heteronuclei; hyperpolarization; parahydrogen.