Porous functionalized polymers enable generating and transporting hyperpolarized mixtures of metabolites

Théo El Daraï,James Kempf,Samuel F Cousin,Morgan Ceillier,Olivier Cala,Laurent Gremillard,Damien Montarnal,Jonas Milani,Sami Jannin,Aurélien Bornet,Quentin Stern,Basile Vuichoud,Marc Schnell,Dmitry Eshchenko,Roberto Melzi

doi:10.1038/s41467-021-24279-2

Abstract

Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) has enabled promising applications in spectroscopy and imaging, but remains poorly widespread due to experimental complexity. Broad democratization of dDNP could be realized by remote preparation and distribution of hyperpolarized samples from dedicated facilities. Here we show the synthesis of hyperpolarizing polymers (HYPOPs) that can generate radical- and contaminant-free hyperpolarized samples within minutes with lifetimes exceeding hours in the solid state. HYPOPs feature tunable macroporous porosity, with porous volumes up to 80% and concentration of nitroxide radicals grafted in the bulk matrix up to 285 μmol g−1. Analytes can be efficiently impregnated as aqueous/alcoholic solutions and hyperpolarized up to P(13C) = 25% within 8 min, through the combination of 1H spin diffusion and 1H → 13C cross polarization. Solutions of 13C-analytes of biological interest hyperpolarized in HYPOPs display a very long solid-state 13C relaxation times of 5.7 h at 3.8 K, thus prefiguring transportation over long distances.

Highlights

Hyperpolarization by dissolution dynamic nuclear polarization has enabled promising applications in spectroscopy and imaging, but remains poorly widespread due to experimental complexity
hyperpolarizing polymers (HYPOPs) are able to withstand both extreme cryogenic temperatures and very fast temperature jumps from 1.2 K to ca. 350 K in a few milliseconds
HYPOPs can be loaded by incipient wetness impregnation (IWI) (Fig. 1b, c) with a variety of liquids ranging from pure pyruvic acid to complex aqueous solutions

Summary

Introduction

Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) has enabled promising applications in spectroscopy and imaging, but remains poorly widespread due to experimental complexity. This polarization originates from epoxy particles of HYPOP in which PAs are hosted, and spontaneously propagates to the frozen solution by 1H nuclear spin diffusion (Fig. 1d)[43].

Results

Conclusion