Proton polarization enhancement of up to 150 with dynamic nuclear polarization of plasma-treated glucose powder

Dynamic nuclear polarization (DNP) for the enhancement of the NMR signals of specific metabolites has recently found applications in the context of magnetic resonance imaging (MRI). Currently, DNP signal enhancement is implemented in clinical systems through the use of exogenous stable organic free radicals, known as polarization agents (PAs), mixed in a solution with the metabolite of interest. These PAs are medically undesirable and thus must be filtered out prior to patient injection - a task that involves considerable technical complexity and consumes valuable time during which the polarization decays. Here, we aim to demonstrate DNP enhancements large enough for clinical relevance using a process free of exogenous PAs. This is achieved by processing (soft grinding) the metabolite in its solid form and subsequently exposing it to plasma in a dilute atmosphere to produce chemically-unstable free radicals (herein referred to as electrical-discharge-induced radicals EDIRs) within the powder. These samples are then subjected to the normal DNP procedure of microwave irradiation while placed under a high static magnetic field, and their NMR signal is measured to quantify the enhancement of the protons' signal in the solid. Proton signal enhancements (measured as the ratio of the NMR signal with microwave irradiation to the NMR signal without microwave irradiation) of up to 150 are demonstrated in glucose. Upon fast dissolution, the free radicals are annihilated, leaving the sample in its original chemical composition (which is safe for clinical use) without any need for filtration and cumbersome quality control procedures. We thus conclude that EDIRs are found to be highly efficient in providing DNP enhancement levels that are on par with those achieved with the exogenous PAs, while being safe for clinical use. This opens up the possibility of applying our method to clinical scenarios with minimal risks and lower costs per procedure.