Abstract

Signal Amplification by Reversible Exchange (SABRE) is an inexpensive and simple hyperpolarization technique that is capable of boosting nuclear magnetic resonance sensitivity by several orders of magnitude. It utilizes the reversible binding of para-hydrogen, as hydride ligands, and a substrate of interest to a metal catalyst to allow for polarization transfer from para-hydrogen into substrate nuclear spins. While the resulting nuclear spin populations can be dramatically larger than those normally created, their lifetime sets a strict upper limit on the experimental timeframe. Consequently, short nuclear spin lifetimes are a challenge for hyperpolarized metabolic imaging. In this report, we demonstrate how both hyperpolarization and long nuclear spin lifetime can be simultaneously achieved in nitrogen-15 containing derivatives of pyridazine and phthalazine by SABRE. These substrates were chosen to reflect two distinct classes of 15N2-coupled species that differ according to their chemical symmetry and thereby achieve different nuclear spin lifetimes. The pyridazine derivative proves to exhibit a signal lifetime of ∼2.5 min and can be produced with a signal enhancement of ∼2700. In contrast, while the phthalazine derivative yields a superior 15 000-fold 15N signal enhancement at 11.7 T, it has a much shorter signal lifetime.

Highlights

  • Despite the many significant advances that have taken place in Nuclear Magnetic Resonance (NMR) since its inception, poor sensitivity still limits full utility

  • We demonstrate how both hyperpolarization and long nuclear spin lifetime can be simultaneously achieved in nitrogen-15 containing derivatives of pyridazine and phthalazine by Signal Amplification by Reversible Exchange (SABRE)

  • We expected to be able to prepare them in a singlet state through low-field polarization transfer via an SABRE catalyst of the form [Ir(H)2(NHC)(sub)3]Cl where the associated hydride-hydride coupling will be of the order of −8 Hz

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Summary

Introduction

Despite the many significant advances that have taken place in Nuclear Magnetic Resonance (NMR) since its inception, poor sensitivity still limits full utility. Recent developments in hyperpolarization techniques that improve sensitivity have allowed the development of magnetic resonance applications that were previously thought to be beyond the techniques’ reach.[3] This builds from the fact that techniques such as Dynamic Nuclear Polarization (DNP)[4] and Spin Exchange Optical Pumping (SEOP)[5] provide unprecedented levels of signal enhancement for carbon-13, nitrogen-15, and xenon-129 spin detection While these developments have been applied to the in vivo study,[6,7,8] they often involve high-cost instrumentation[4] which acts to restrict their utilization

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