Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection
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 1/40 th 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 tomore »
- Authors:
-
[1]
; [2]
; [2]
; [2]
; [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:
- Report Number(s):
- IS-J 9683
Journal ID: ISSN 1089-5639
- Grant/Contract Number:
- AC02-07CH11358
- 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
- Research Org:
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Sponsoring Org:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
- OSTI Identifier:
- 1459536
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.,
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:10.1021/acs.jpca.8b05107.
Venkatesh, Amrit, Ryan, Matthew J., Biswas, Abhranil, Boteju, Kasuni C., Sadow, Aaron D., and Rossini, Aaron J.. 2018.
"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:10.1021/acs.jpca.8b05107.
@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}
}