Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Effects of biradical deuteration on the performance of DNP: Towards better performing polarizing agents

Abstract

We study the effects of the deuteration of biradical polarizing agents on the efficiency of dynamic nuclear polarization (DNP) via the cross-effect. To this end, we synthesized a series of bTbK and TOTAPol biradicals with systematically increased deuterium substitution. The deuteration increases the radicals' relaxation time, thus contributing to a higher saturation factor and larger DNP enhancement, and reduces the pool of protons within the so-called spin diffusion barrier. Notably, we report that full or partial deuteration leads to improved DNP enhancement factors in standard samples, but also slows down the build-up of hyperpolarization. Improvements in DNP enhancements factors of up to 70% and time savings of up to 38% are obtained upon full deuteration. As a result, it is foreseen that this approach may be applied to other DNP polarizing agents thus enabling further sensitivity improvements.

Authors:
 [1];  [2];  [2];  [2];  [2]
+ Show Author Affiliations
  1. Ames Lab., Ames, IA (United States)
  2. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1227445
Report Number(s):
IS-J-8842
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 18; Journal Issue: 1; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Perras, Frédéric A., Reinig, Regina R., Slowing, Igor I., Sadow, Aaron D., and Pruski, Marek. Effects of biradical deuteration on the performance of DNP: Towards better performing polarizing agents. United States: N. p., 2015. Web. doi:10.1039/C5CP06505D.
Copy to clipboard
Perras, Frédéric A., Reinig, Regina R., Slowing, Igor I., Sadow, Aaron D., & Pruski, Marek. Effects of biradical deuteration on the performance of DNP: Towards better performing polarizing agents. United States. https://doi.org/10.1039/C5CP06505D
Copy to clipboard
Perras, Frédéric A., Reinig, Regina R., Slowing, Igor I., Sadow, Aaron D., and Pruski, Marek. Fri . "Effects of biradical deuteration on the performance of DNP: Towards better performing polarizing agents". United States. https://doi.org/10.1039/C5CP06505D. https://www.osti.gov/servlets/purl/1227445.
Copy to clipboard
@article{osti_1227445,
title = {Effects of biradical deuteration on the performance of DNP: Towards better performing polarizing agents},
author = {Perras, Frédéric A. and Reinig, Regina R. and Slowing, Igor I. and Sadow, Aaron D. and Pruski, Marek},
abstractNote = {We study the effects of the deuteration of biradical polarizing agents on the efficiency of dynamic nuclear polarization (DNP) via the cross-effect. To this end, we synthesized a series of bTbK and TOTAPol biradicals with systematically increased deuterium substitution. The deuteration increases the radicals' relaxation time, thus contributing to a higher saturation factor and larger DNP enhancement, and reduces the pool of protons within the so-called spin diffusion barrier. Notably, we report that full or partial deuteration leads to improved DNP enhancement factors in standard samples, but also slows down the build-up of hyperpolarization. Improvements in DNP enhancements factors of up to 70% and time savings of up to 38% are obtained upon full deuteration. As a result, it is foreseen that this approach may be applied to other DNP polarizing agents thus enabling further sensitivity improvements.},
doi = {10.1039/C5CP06505D},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 1,
volume = 18,
place = {United States},
year = {Fri Nov 20 00:00:00 EST 2015},
month = {Fri Nov 20 00:00:00 EST 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C5CP06505D
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Dynamic nuclear polarization at high magnetic fields
journal, February 2008

  • Maly, Thorsten; Debelouchina, Galia T.; Bajaj, Vikram S.
  • The Journal of Chemical Physics, Vol. 128, Issue 5
  • DOI: 10.1063/1.2833582

Phenomenological Model for the New Effect in Dynamic Polarization
journal, October 1967

Topical Developments in High-Field Dynamic Nuclear Polarization
journal, February 2014

  • Michaelis, Vladimir K.; Ong, Ta-Chung; Kiesewetter, Matthew K.
  • Israel Journal of Chemistry, Vol. 54, Issue 1-2
  • DOI: 10.1002/ijch.201300126

Dynamic nuclear polarization with a cyclotron resonance maser at 5 T
journal, November 1993

High-Frequency Dynamic Nuclear Polarization in MAS Spectra of Membrane and Soluble Proteins
journal, November 2003

  • Rosay, Melanie; Lansing, Jonathan C.; Haddad, Kristin C.
  • Journal of the American Chemical Society, Vol. 125, Issue 45
  • DOI: 10.1021/ja036898k

Cryogenic sample exchange NMR probe for magic angle spinning dynamic nuclear polarization
journal, June 2009

  • Barnes, Alexander B.; Mak-Jurkauskas, Melody L.; Matsuki, Yoh
  • Journal of Magnetic Resonance, Vol. 198, Issue 2
  • DOI: 10.1016/j.jmr.2009.03.003

Solid-state dynamic nuclear polarization at 263 GHz: spectrometer design and experimental results
journal, January 2010

  • Rosay, Melanie; Tometich, Leo; Pawsey, Shane
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 22
  • DOI: 10.1039/c003685b

Dynamic nuclear polarization experiments at 14.1 T for solid-state NMR
journal, January 2010

  • Matsuki, Yoh; Takahashi, Hiroki; Ueda, Keisuke
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 22
  • DOI: 10.1039/c002268c

Dynamic nuclear polarization at 700MHz/460GHz
journal, November 2012

  • Barnes, Alexander B.; Markhasin, Evgeny; Daviso, Eugenio
  • Journal of Magnetic Resonance, Vol. 224
  • DOI: 10.1016/j.jmr.2012.08.002

A spectrometer designed for 6.7 and 14.1T DNP-enhanced solid-state MAS NMR using quasi-optical microwave transmission
journal, February 2012

The Development of 460 GHz gyrotrons for 700 MHz DNP-NMR spectroscopy
journal, March 2015

  • Idehara, T.; Tatematsu, Y.; Yamaguchi, Y.
  • Journal of Infrared, Millimeter, and Terahertz Waves, Vol. 36, Issue 7
  • DOI: 10.1007/s10762-015-0150-z

Dynamic Nuclear Polarization with Biradicals
journal, September 2004

  • Hu, Kan-Nian; Yu, Hsiao-hua; Swager, Timothy M.
  • Journal of the American Chemical Society, Vol. 126, Issue 35
  • DOI: 10.1021/ja039749a

TOTAPOL: A Biradical Polarizing Agent for Dynamic Nuclear Polarization Experiments in Aqueous Media
journal, September 2006

  • Song, Changsik; Hu, Kan-Nian; Joo, Chan-Gyu
  • Journal of the American Chemical Society, Vol. 128, Issue 35
  • DOI: 10.1021/ja061284b

Dynamic Nuclear Polarization with a Rigid Biradical
journal, June 2009

  • Matsuki, Yoh; Maly, Thorsten; Ouari, Olivier
  • Angewandte Chemie International Edition, Vol. 48, Issue 27
  • DOI: 10.1002/anie.200805940

Dynamic Nuclear Polarization with a Water-Soluble Rigid Biradical
journal, February 2012

  • Kiesewetter, Matthew K.; Corzilius, Björn; Smith, Albert A.
  • Journal of the American Chemical Society, Vol. 134, Issue 10
  • DOI: 10.1021/ja212054e

A Slowly Relaxing Rigid Biradical for Efficient Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy: Expeditious Characterization of Functional Group Manipulation in Hybrid Materials
journal, January 2012

  • Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier
  • Journal of the American Chemical Society, Vol. 134, Issue 4
  • DOI: 10.1021/ja210177v

Highly Efficient, Water-Soluble Polarizing Agents for Dynamic Nuclear Polarization at High Frequency
journal, August 2013

  • Sauvée, Claire; Rosay, Melanie; Casano, Gilles
  • Angewandte Chemie International Edition, Vol. 52, Issue 41
  • DOI: 10.1002/anie.201304657

Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K
journal, August 2013

  • Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier
  • Journal of the American Chemical Society, Vol. 135, Issue 34
  • DOI: 10.1021/ja405813t

Relaxation rates for spirocyclohexyl nitroxyl radicals are suitable for interspin distance measurements at temperatures up to about 125 K
journal, January 2009

  • Kathirvelu, Velavan; Smith, Christopher; Parks, Christopher
  • Chem. Commun., Issue 4
  • DOI: 10.1039/B817758A

Impact of Gd 3+ on DNP of [1- 13 C]Pyruvate Doped with Trityl OX063, BDPA, or 4-Oxo-TEMPO
journal, May 2012

  • Lumata, Lloyd; Merritt, Matthew E.; Malloy, Craig R.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 21
  • DOI: 10.1021/jp302399f

DNP with the free radicals deuterated TEMPO and deuterated oxo-TEMPO
journal, June 2004

  • van den Brandt, B.; Bunyatova, E. I.; Hautle, P.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 526, Issue 1-2
  • DOI: 10.1016/j.nima.2004.03.149

DNP by Thermal Mixing under Optimized Conditions Yields >60 000-fold Enhancement of 89 Y NMR Signal
journal, June 2011

  • Lumata, Lloyd; Jindal, Ashish K.; Merritt, Matthew E.
  • Journal of the American Chemical Society, Vol. 133, Issue 22
  • DOI: 10.1021/ja201880y

Dynamic Nuclear Polarization and Spin Diffusion in Nonconducting Solids
journal, August 2008

Solid effect dynamic nuclear polarization and polarization pathways
journal, January 2012

  • Smith, Albert A.; Corzilius, Björn; Barnes, Alexander B.
  • The Journal of Chemical Physics, Vol. 136, Issue 1
  • DOI: 10.1063/1.3670019

Optimization of 1H spin density for dynamic nuclear polarization using photo-excited triplet electron spins
journal, March 2009

  • Kagawa, Akinori; Murokawa, Yu; Takeda, Kazuyuki
  • Journal of Magnetic Resonance, Vol. 197, Issue 1
  • DOI: 10.1016/j.jmr.2008.11.009

Dynamic Nuclear Polarization of Deuterated Proteins
journal, August 2010

  • Akbey, Ümit; Franks, W. Trent; Linden, Arne
  • Angewandte Chemie International Edition, Vol. 49, Issue 42
  • DOI: 10.1002/anie.201002044

Influence of deuteration in the glassing matrix on 13C dynamic nuclear polarization
journal, January 2013

  • Lumata, Lloyd; Merritt, Matthew E.; Kovacs, Zoltan
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 19
  • DOI: 10.1039/c3cp50750e

Amplifying Dynamic Nuclear Polarization of Frozen Solutions by Incorporating Dielectric Particles
journal, October 2014

  • Kubicki, Dominik J.; Rossini, Aaron J.; Purea, Armin
  • Journal of the American Chemical Society, Vol. 136, Issue 44
  • DOI: 10.1021/ja5088453

High frequency (140 GHz) dynamic nuclear polarization: Polarization transfer to a solute in frozen aqueous solution
journal, June 1995

  • Gerfen, G. J.; Becerra, L. R.; Hall, D. A.
  • The Journal of Chemical Physics, Vol. 102, Issue 24
  • DOI: 10.1063/1.468818

The magnetic field dependence of cross-effect dynamic nuclear polarization under magic angle spinning
journal, June 2015

  • Mance, Deni; Gast, Peter; Huber, Martina
  • The Journal of Chemical Physics, Vol. 142, Issue 23
  • DOI: 10.1063/1.4922219

Theoretical aspects of Magic Angle Spinning - Dynamic Nuclear Polarization
journal, September 2015

  • Mentink-Vigier, Frederic; Akbey, Ümit; Oschkinat, Hartmut
  • Journal of Magnetic Resonance, Vol. 258
  • DOI: 10.1016/j.jmr.2015.07.001

Pulsed EPR Determination of Water Accessibility to Spin-Labeled Amino Acid Residues in LHCIIb
journal, February 2009

Dynamic nuclear polarization assisted spin diffusion for the solid effect case
journal, February 2011

  • Hovav, Yonatan; Feintuch, Akiva; Vega, Shimon
  • The Journal of Chemical Physics, Vol. 134, Issue 7
  • DOI: 10.1063/1.3526486
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    19 F Magic Angle Spinning Dynamic Nuclear Polarization Enhanced NMR Spectroscopy
    journal, April 2019

    • Viger‐Gravel, Jasmine; Avalos, Claudia E.; Kubicki, Dominik J.
    • Angewandte Chemie, Vol. 131, Issue 22
    • DOI: 10.1002/ange.201814416

    Efficiency of Water-Soluble Nitroxide Biradicals for Dynamic Nuclear Polarization in Rotating Solids at 9.4 T: bcTol-M and cyolyl-TOTAPOL as New Polarizing Agents
    journal, August 2018

    • Geiger, Michel-Andreas; Jagtap, Anil P.; Kaushik, Monu
    • Chemistry - A European Journal, Vol. 24, Issue 51
    • DOI: 10.1002/chem.201801251

    De novo prediction of cross-effect efficiency for magic angle spinning dynamic nuclear polarization
    journal, January 2019

    • Mentink-Vigier, Frédéric; Barra, Anne-Laure; van Tol, Johan
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 4
    • DOI: 10.1039/c8cp06819d

    Optimizing nitroxide biradicals for cross-effect MAS-DNP: the role of g -tensors’ distance
    journal, January 2020

    • Mentink-Vigier, Frédéric
    • Physical Chemistry Chemical Physics, Vol. 22, Issue 6
    • DOI: 10.1039/c9cp06201g

    First α-deuterium nitroxides; synthesis and EPR study
    journal, January 2019

    • Toledo, Hila; Tumanskii, Boris; Sabirov, Denis Sh.
    • Organic & Biomolecular Chemistry, Vol. 17, Issue 34
    • DOI: 10.1039/c9ob01127g

    Large-scale ab initio simulations of MAS DNP enhancements using a Monte Carlo optimization strategy
    journal, October 2018

    • Perras, Frédéric A.; Pruski, Marek
    • The Journal of Chemical Physics, Vol. 149, Issue 15
    • DOI: 10.1063/1.5042651

    19 F Magic Angle Spinning Dynamic Nuclear Polarization Enhanced NMR Spectroscopy
    journal, May 2019

    • Viger‐Gravel, Jasmine; Avalos, Claudia E.; Kubicki, Dominik J.
    • Angewandte Chemie International Edition, Vol. 58, Issue 22
    • DOI: 10.1002/anie.201814416
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: