Functionalized Controlled Porous Glasses for Producing Radical-Free Hyperpolarized Liquids by Overhauser DNP

Overhauser dynamic nuclear polarization (ODNP) can be used as a tool for NMR signal enhancement and happens on very short time scales. Therefore, ODNP is well suited for the measurement of fast-flowing samples, even in compact magnets, which is beneficial for the real-time monitoring of chemical reactions or processes. ODNP requires the presence of unpaired electrons in the sample, which is usually accomplished by the addition of stable radicals. However, radicals affect the nuclear relaxation times and can hamper the NMR detection. This is circumvented by immobilizing radicals in a packed bed allowing for the measurement of radical-free samples when using ex situ DNP techniques (DNP build-up and NMR detection happen at different places) and flow-induced separation of the hyperpolarized liquid from the radicals. Therefore, the synthesis of robust and chemically inert immobilized radical matrices is mandatory. In the present work, this is accomplished by immobilizing the radical glycidyloxy-tetramethylpiperidinyloxyl with a polyethyleneimine (PEI) linker on the surface of controlled porous glasses (CPG). Both the porosity of the CPGs and also the size of the PEI-linker were varied, resulting in a set of distinct radical matrices for continuous-flow ODNP. The study shows that CPGs with PEI-linkers provide robust, inert and efficient ODNP matrices.

Automated summary

Overhauser dynamic nuclear polarization (ODNP) is a tool for enhancing NMR signal, especially suitable for measuring fast-flowing samples in compact magnets for real-time monitoring of chemical reactions or processes. Immobilizing radicals in a packed bed allows for the measurement of radical-free samples and separation of hyperpolarized liquid from radicals. In this study, robust and chemically inert immobilized radical matrices were synthesized using controlled porous glasses with polyethyleneimine (PEI) linker.