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Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR
Published on: February 23, 2016
Detection of the Carcinogen Benzo[a]pyrene through Photochemically Induced Dynamic Nuclear Polarization: Linking
Mohd Humair Ali1,2, Guzel Musabirova1, Luca Gerhards3
1Institut für Analytische Chemie, Universität Leipzig, Linnéstr. 3, Leipzig D-04103, Germany.
Abstract:
Benzo[a]pyrene (BaP), a polycyclic aromatic hydrocarbon (PAH) with significant environmental prevalence and toxicological implications, is classified as a group 1 carcinogen. Nonetheless, the noninvasive in vivo traceability of BaP in biological systems faces a major challenge. In this study, we introduce a novel noninvasive NMR and MRI detection method for BaP utilizing light-induced signal enhancement through the photochemically induced dynamic nuclear polarization (photo-CIDNP) effect to achieve new limits in sensitivity, contrast, and spatial resolution. Liquid-state 1H NMR revealed a substantial photo-CIDNP signal enhancement of BaP in the presence of riboflavin, as a photosensitizer, under illumination, corroborating the hyperpolarization phenomenon. Furthermore, BaP signal enhancement in dodecylphosphocholine (DPC) micelles, a biological membrane-simulating environment, demonstrated the viability of employing photo-CIDNP in intricate, heterogeneous biological systems. The approach was subsequently expanded to MRI-based chemical shift imaging (CSI) to spatially map the radical-polarized signals from encoded voxels. The mapping of CSI images demonstrated that light-induced signals were confined to regions where the light was projected, hence affirming the spatial correlation between light illumination and increased signal intensity, laying a foundation for its potential as a diagnostic tool in 1H MRI. This study provides a viable application of 1H photo-CIDNP MRI as a sensitive approach that can be applied for monitoring environmental toxins noninvasively and establishes a robust link between photochemistry and in vivo molecular-level MRI visualization.
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