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Sample Ripening through Nanophase Separation Influences the Performance of Dynamic Nuclear Polarization
Authors:Emmanuelle M M Weber  Dr Giuseppe Sicoli  Dr Hervé Vezin  Ghislaine Frébourg  Dr Daniel Abergel  Prof Geoffrey Bodenhausen  Dr Dennis Kurzbach
Institution:1. Laboratoire des biomolécules, LBM, Département de chimie, école normale supérieure, PSL University, Sorbonne Université, CNRS, Paris, France;2. Université Lille, UMR CNRS 8516—LASIR, Laboratoire de Spectrochimie Infrarouge et Raman, Lille, France;3. Institut de Biologie Paris-Seine, Sorbonne Université/ CNRS, Paris, France
Abstract:Mixtures of water and glycerol provide popular matrices for low‐temperature spectroscopy of vitrified samples. However, they involve counterintuitive physicochemical properties, such as spontaneous nanoscopic phase separations (NPS) in solutions that appear macroscopically homogeneous. We demonstrate that such phenomena can substantially influence the efficiency of dynamic nuclear polarization (DNP) by factors up to 20 % by causing fluctuations in local concentrations of polarization agents (radicals). Thus, a spontaneous NPS of water/glycerol mixtures that takes place on time scales on the order of 30–60 min results in a confinement of polarization agents in nanoscopic water‐rich vesicles, which in return affects the DNP. Such effects were found for three common polarization agents, TEMPOL, AMUPol and Trityl.
Keywords:dynamic nuclear polarization  nanophases  nuclear magnetic resonance  phase separation
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