Sample Ripening through Nanophase Separation Influences the Performance of Dynamic Nuclear Polarization.

Angew Chem Int Ed Engl

Laboratoire des biomolécules, LBM, Département de chimie, École normale supérieure, PSL University, Sorbonne Université, CNRS, 75005, Paris, France.

Published: April 2018

AI Article Synopsis

  • Mixtures of water and glycerol are commonly used for low-temperature spectroscopy, but they exhibit unexpected behaviors, like nanoscopic phase separations (NPS) that can go unnoticed.
  • These phase separations can dramatically impact dynamic nuclear polarization (DNP) efficiency, altering the local concentration of polarization agents by up to 20%.
  • Specifically, the NPS occurs over 30-60 minutes, leading to the formation of nanoscopic water-rich vesicles that affect the distribution and effectiveness of popular polarization agents like TEMPOL, AMUPol, and Trityl.

Article 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.

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Source
http://dx.doi.org/10.1002/anie.201800493DOI Listing

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