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Title: High-Field Magic Angle Spinning Dynamic Nuclear Polarization Using Radicals Created by γ-Irradiation

Abstract

High-field magic angle spinning dynamic nuclear polarization (MAS DNP) is often used to enhance the sensitivity of solid-state nuclear magnetic resonance experiments by transferring spin polarization from electron spins to nuclear spins. In this work, we demonstrate that γ-irradiation induces the formation of stable radicals in inorganic solids, such as fused quartz and borosilicate glasses, as well as organic solids, such as glucose, cellulose, and a urea/polyethylene polymer. The radicals were then used to polarize 29Si or 1H spins in the core of some of these materials. Significant MAS DNP enhancements (ε) of more than 400 and 30 were obtained for fused quartz and glucose, respectively. For other samples, negligible values of ε were obtained, likely due to low concentrations of radicals or the presence of abundant quadrupolar spins. These results demonstrate that ionizing radiation is an enticing alternative method for generating stable radicals that are suitable for high-field MAS DNP experiments.

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Ames Lab., Ames, IA (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1550797
Report Number(s):
BNL-211935-2019-JAAM
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
SC0012704; AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 10; Journal Issue: 17; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Carnahan, Scott L., Venkatesh, Amrit, Perras, Frédéric A., Wishart, James F., and Rossini, Aaron J. High-Field Magic Angle Spinning Dynamic Nuclear Polarization Using Radicals Created by γ-Irradiation. United States: N. p., 2019. Web. doi:10.1021/acs.jpclett.9b01655.
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Carnahan, Scott L., Venkatesh, Amrit, Perras, Frédéric A., Wishart, James F., & Rossini, Aaron J. High-Field Magic Angle Spinning Dynamic Nuclear Polarization Using Radicals Created by γ-Irradiation. United States. https://doi.org/10.1021/acs.jpclett.9b01655
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Carnahan, Scott L., Venkatesh, Amrit, Perras, Frédéric A., Wishart, James F., and Rossini, Aaron J. Fri . "High-Field Magic Angle Spinning Dynamic Nuclear Polarization Using Radicals Created by γ-Irradiation". United States. https://doi.org/10.1021/acs.jpclett.9b01655. https://www.osti.gov/servlets/purl/1550797.
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@article{osti_1550797,
title = {High-Field Magic Angle Spinning Dynamic Nuclear Polarization Using Radicals Created by γ-Irradiation},
author = {Carnahan, Scott L. and Venkatesh, Amrit and Perras, Frédéric A. and Wishart, James F. and Rossini, Aaron J.},
abstractNote = {High-field magic angle spinning dynamic nuclear polarization (MAS DNP) is often used to enhance the sensitivity of solid-state nuclear magnetic resonance experiments by transferring spin polarization from electron spins to nuclear spins. In this work, we demonstrate that γ-irradiation induces the formation of stable radicals in inorganic solids, such as fused quartz and borosilicate glasses, as well as organic solids, such as glucose, cellulose, and a urea/polyethylene polymer. The radicals were then used to polarize 29Si or 1H spins in the core of some of these materials. Significant MAS DNP enhancements (ε) of more than 400 and 30 were obtained for fused quartz and glucose, respectively. For other samples, negligible values of ε were obtained, likely due to low concentrations of radicals or the presence of abundant quadrupolar spins. These results demonstrate that ionizing radiation is an enticing alternative method for generating stable radicals that are suitable for high-field MAS DNP experiments.},
doi = {10.1021/acs.jpclett.9b01655},
journal = {Journal of Physical Chemistry Letters},
number = 17,
volume = 10,
place = {United States},
year = {Fri Jul 26 00:00:00 EDT 2019},
month = {Fri Jul 26 00:00:00 EDT 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.9b01655
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Cited by: 16 works
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Figures / Tables:

Scheme 1 Scheme 1: Different DNP polarization techniques as applied to SiO2 particles. A) DNP SENS where DNP is used to polarize surface 1H spins and 1H-29Si CP polarizes surface 29Si spins. B) Relayed DNP using homonuclear 29Si spin diffusion to polarize core 29Si. C) DNP on γ-irradiated SiO2 to polarize coremore » 29Si.« less
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    Works referencing / citing this record:

    Fast electron paramagnetic resonance magic angle spinning simulations using analytical powder averaging techniques
    journal, September 2019

    • Saliba, Edward P.; Barnes, Alexander B.
    • The Journal of Chemical Physics, Vol. 151, Issue 11
    • DOI: 10.1063/1.5113598
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