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Improved strategies for DNP-enhanced 2D 1 H-X heteronuclear correlation spectroscopy of surfaces

Journal Article · · Solid State Nuclear Magnetic Resonance
 [1];  [1];  [2];  [3];  [3];  [3];  [3]
  1. Ames Lab., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
  3. Ames Lab. and Iowa State Univ., Ames, IA (United States)

We demonstrate that dynamic nuclear polarization (DNP)-enhanced 1H-X heteronuclear correlation (HETCOR) measurements of hydrogen-rich surface species are better accomplished by using proton-free solvents. This approach notably prevents HETCOR spectra from being obfuscated by the solvent-derived signals otherwise present in DNP measurements. Additionally, in the hydrogen-rich materials studied here, which included functionalized mesoporous silica nanoparticles and metal organic frameworks, the use of proton-free solvents afforded higher sensitivity gains than the commonly used solvents containing protons. Here, we also explored the possibility of using a solvent-free sample formulation and the feasibility of indirect detection in DNP-enhanced HETCOR experiments.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1399263
Alternate ID(s):
OSTI ID: 1495835
Report Number(s):
IS-J--9361; PII: S0926204017300644
Journal Information:
Solid State Nuclear Magnetic Resonance, Journal Name: Solid State Nuclear Magnetic Resonance Journal Issue: C Vol. 87; ISSN 0926-2040
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (45)

Proton-Detected Solid-State NMR Spectroscopy of Natural-Abundance Peptide and Protein Pharmaceuticals journal January 2009
Dynamic Nuclear Polarization with a Rigid Biradical journal June 2009
Dynamic Nuclear Polarization of Deuterated Proteins journal August 2010
Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy of Functionalized Metal-Organic Frameworks journal November 2011
Highly Efficient, Water-Soluble Polarizing Agents for Dynamic Nuclear Polarization at High Frequency journal August 2013
Natural Abundance 17 O DNP NMR Provides Precise O−H Distances and Insights into the Brønsted Acidity of Heterogeneous Catalysts journal June 2017
Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy journal October 2014
A Spectrometer for Dynamic Nuclear Polarization and Electron Paramagnetic Resonance at High Frequencies journal November 1995
An Improved Broadband Decoupling Sequence for Liquid Crystals and Solids journal January 2000
Sensitivity Enhancement in Solid State 15N NMR by Indirect Detection with High-Speed Magic Angle Spinning journal January 2000
Natural abundance nitrogen-15 NMR by enhanced heteronuclear spectroscopy journal January 1980
Frequency-switched pulse sequences: Homonuclear decoupling and dilute spin NMR in solids journal March 1989
Substrate inhibition in the heterogeneous catalyzed aldol condensation: A mechanistic study of supported organocatalysts journal July 2012
Cryogenic sample exchange NMR probe for magic angle spinning dynamic nuclear polarization journal June 2009
Proton-detected heteronuclear single quantum correlation NMR spectroscopy in rigid solids with ultra-fast MAS journal January 2010
The effect of biradical concentration on the performance of DNP-MAS-NMR journal March 2012
Indirect detection of infinite-speed MAS solid-state NMR spectra journal March 2017
Solvent suppression in DNP enhanced solid state NMR journal April 2017
Solvent signal suppression for high-resolution MAS-DNP journal May 2017
Indirectly detected heteronuclear correlation solid-state NMR spectroscopy of naturally abundant 15N nuclei journal February 2014
Water and the silica surface as studied by variable-temperature high-resolution proton NMR journal July 1993
Sensitivity enhanced detection of weak nuclei using heteronuclear multiple quantum coherence journal August 1979
High-Frequency Dynamic Nuclear Polarization in MAS Spectra of Membrane and Soluble Proteins journal November 2003
Dynamic Nuclear Polarization with Biradicals journal September 2004
Solid-State NMR Study of MCM-41-type Mesoporous Silica Nanoparticles journal March 2005
TOTAPOL: A Biradical Polarizing Agent for Dynamic Nuclear Polarization Experiments in Aqueous Media journal September 2006
Chemical Shift Correlation NMR Spectroscopy with Indirect Detection in Fast Rotating Solids:  Studies of Organically Functionalized Mesoporous Silicas
  • Wiench, Jerzy W.; Bronnimann, Charles E.; Lin, Victor S. -Y
  • Journal of the American Chemical Society, Vol. 129, Issue 40, p. 12076-12077 https://doi.org/10.1021/ja074746+
journal September 2007
Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization journal November 2010
Conformations of Silica-Bound (Pentafluorophenyl)propyl Groups Determined by Solid-State NMR Spectroscopy and Theoretical Calculations journal September 2010
Fast Characterization of Functionalized Silica Materials by Silicon-29 Surface-Enhanced NMR Spectroscopy Using Dynamic Nuclear Polarization journal February 2011
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
Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K journal August 2013
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953
journal October 2008
Mesoporous Silica Nanoparticles Loaded with Surfactant: Low Temperature Magic Angle Spinning 13 C and 29 Si NMR Enhanced by Dynamic Nuclear Polarization journal January 2013
Optimizing Sample Preparation Methods for Dynamic Nuclear Polarization Solid-state NMR of Synthetic Polymers journal June 2014
Non-aqueous solvents for DNP surface enhanced NMR spectroscopy journal January 2012
Pushing NMR sensitivity limits using dynamic nuclear polarization with closed-loop cryogenic helium sample spinning journal January 2015
Dynamic nuclear polarization at 40 kHz magic angle spinning journal January 2016
Matrix-free dynamic nuclear polarization enables solid-state NMR 13C–13C correlation spectroscopy of proteins at natural isotopic abundance journal January 2013
Analysis of sensitivity enhancement by dynamic nuclear polarization in solid-state NMR: a case study of functionalized mesoporous materials journal January 2013
An improved NMR technique for homonuclear dipolar decoupling in solids: Application to polycrystalline ice journal April 1979
Dynamic nuclear polarization of small labelled molecules in frozen water–alcohol solutions journal July 2008
Polarization of Nuclear Spins in Metals journal October 1953
Polarization of Nuclei in Metals journal October 1953
Operational characteristics of a 14-W 140-GHz gyrotron for dynamic nuclear polarization journal June 2006

Cited By (4)

Structural Insights into Peptides Bound to the Surface of Silica Nanopores journal March 2019
Direct 17 O dynamic nuclear polarization of single-site heterogeneous catalysts journal January 2018
Probing the surface of γ-Al 2 O 3 by oxygen-17 dynamic nuclear polarization enhanced solid-state NMR spectroscopy journal January 2018
Large-scale ab initio simulations of MAS DNP enhancements using a Monte Carlo optimization strategy journal October 2018

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