Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection
Abstract
Many transition metals commonly encountered in inorganic materials and organometallic compounds possess NMR-active nuclei with very low gyromagnetic ratios (γ) such as 89Y, 103Rh, 109Ag, and 183W. A low-γ leads to poor NMR sensitivity and other experimental challenges. Consequently, nuclei with low-γ are often impossible to study with conventional solid-state NMR methods. In this paper, we combine fast magic angle spinning (MAS) and proton detection to enhance the sensitivity of solid-state NMR experiments with very low-γ nuclei by 1–2 orders of magnitude. Coherence transfer between 1H and low-γ nuclei was performed with low-power double quantum (DQ) or zero quantum (ZQ) cross-polarization (CP) or dipolar refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT). Comparison of the absolute sensitivity of CP NMR experiments performed with proton detection with 1.3 mm rotors and direct detection with 4 mm rotors shows that proton detection with a 1.3 mm rotor provides a significant boost in absolute sensitivity, while requiring approximately 1/40th of the material required to fill a 4 mm rotor. Fast MAS and proton detection were applied to obtain 89Y and 103Rh solid-state NMR spectra of organometallic complexes. Finally, these results demonstrate that proton detection and fast MAS represents a general approach to enablemore »
- Authors:
-
[1];
[1];
[1]
- Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
- Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1459536
- Report Number(s):
- IS-J 9683
Journal ID: ISSN 1089-5639
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 25; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Venkatesh, Amrit, Ryan, Matthew J., Biswas, Abhranil, Boteju, Kasuni C., Sadow, Aaron D., and Rossini, Aaron J. Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection. United States: N. p., 2018.
Web. doi:10.1021/acs.jpca.8b05107.
Venkatesh, Amrit, Ryan, Matthew J., Biswas, Abhranil, Boteju, Kasuni C., Sadow, Aaron D., & Rossini, Aaron J. Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection. United States. doi:https://doi.org/10.1021/acs.jpca.8b05107
Venkatesh, Amrit, Ryan, Matthew J., Biswas, Abhranil, Boteju, Kasuni C., Sadow, Aaron D., and Rossini, Aaron J. Mon .
"Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection". United States. doi:https://doi.org/10.1021/acs.jpca.8b05107. https://www.osti.gov/servlets/purl/1459536.
@article{osti_1459536,
title = {Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection},
author = {Venkatesh, Amrit and Ryan, Matthew J. and Biswas, Abhranil and Boteju, Kasuni C. and Sadow, Aaron D. and Rossini, Aaron J.},
abstractNote = {Many transition metals commonly encountered in inorganic materials and organometallic compounds possess NMR-active nuclei with very low gyromagnetic ratios (γ) such as 89Y, 103Rh, 109Ag, and 183W. A low-γ leads to poor NMR sensitivity and other experimental challenges. Consequently, nuclei with low-γ are often impossible to study with conventional solid-state NMR methods. In this paper, we combine fast magic angle spinning (MAS) and proton detection to enhance the sensitivity of solid-state NMR experiments with very low-γ nuclei by 1–2 orders of magnitude. Coherence transfer between 1H and low-γ nuclei was performed with low-power double quantum (DQ) or zero quantum (ZQ) cross-polarization (CP) or dipolar refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT). Comparison of the absolute sensitivity of CP NMR experiments performed with proton detection with 1.3 mm rotors and direct detection with 4 mm rotors shows that proton detection with a 1.3 mm rotor provides a significant boost in absolute sensitivity, while requiring approximately 1/40th of the material required to fill a 4 mm rotor. Fast MAS and proton detection were applied to obtain 89Y and 103Rh solid-state NMR spectra of organometallic complexes. Finally, these results demonstrate that proton detection and fast MAS represents a general approach to enable and accelerate solid-state NMR experiments with very low-γ nuclei.},
doi = {10.1021/acs.jpca.8b05107},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 25,
volume = 122,
place = {United States},
year = {2018},
month = {6}
}
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Works referencing / citing this record:
New frontiers for solid-state NMR across the periodic table: a snapshot of modern techniques and instrumentation
journal, January 2019
- Bryce, David L.
- Dalton Transactions, Vol. 48, Issue 23