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:
-
- Ames Lab., Ames, IA (United States)
- 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.
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
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.
@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}
}
Web of Science
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
Phenomenological Model for the New Effect in Dynamic Polarization
journal, October 1967
- Hwang, Chester F.; Hill, Daniel A.
- Physical Review Letters, Vol. 19, Issue 18
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
Dynamic nuclear polarization with a cyclotron resonance maser at 5 T
journal, November 1993
- Becerra, Lino R.; Gerfen, Gary J.; Temkin, Richard J.
- Physical Review Letters, Vol. 71, Issue 21
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
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
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
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
Dynamic nuclear polarization at 700MHz/460GHz
journal, November 2012
- Barnes, Alexander B.; Markhasin, Evgeny; Daviso, Eugenio
- Journal of Magnetic Resonance, Vol. 224
A spectrometer designed for 6.7 and 14.1T DNP-enhanced solid-state MAS NMR using quasi-optical microwave transmission
journal, February 2012
- Pike, Kevin J.; Kemp, Thomas F.; Takahashi, Hiroki
- Journal of Magnetic Resonance, Vol. 215
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
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
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
Dynamic Nuclear Polarization with a Rigid Biradical
journal, June 2009
- Matsuki, Yoh; Maly, Thorsten; Ouari, Olivier
- Angewandte Chemie International Edition, Vol. 48, Issue 27
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
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
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
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
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
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
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
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
Dynamic Nuclear Polarization and Spin Diffusion in Nonconducting Solids
journal, August 2008
- Ramanathan, C.
- Applied Magnetic Resonance, Vol. 34, Issue 3-4
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
Theory for cross effect dynamic nuclear polarization under magic-angle spinning in solid state nuclear magnetic resonance: The importance of level crossings
journal, August 2012
- Thurber, Kent R.; Tycko, Robert
- The Journal of Chemical Physics, Vol. 137, Issue 8
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
Dynamic Nuclear Polarization of Deuterated Proteins
journal, August 2010
- Akbey, Ümit; Franks, W. Trent; Linden, Arne
- Angewandte Chemie International Edition, Vol. 49, Issue 42
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
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
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
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
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
Pulsed EPR Determination of Water Accessibility to Spin-Labeled Amino Acid Residues in LHCIIb
journal, February 2009
- Volkov, A.; Dockter, C.; Bund, T.
- Biophysical Journal, Vol. 96, Issue 3
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
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
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
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
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
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
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
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