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Title: Suppressing 1H Spin Diffusion in Fast MAS Proton Detected Heteronuclear Correlation Solid-State NMR Experiments

Abstract

Fast magic angle spinning (MAS) and indirect detection by high gyromagnetic ratio (γ) nuclei such as proton or fluorine are increasingly utilized to obtain 2D heteronuclear correlation (HETCOR) solid-state NMR spectra of spin-1/2 nuclei by using cross polarization (CP) for coherence transfer. However, one major drawback of CP HETCOR pulse sequences is that 1H spin diffusion during the back X→1H CP transfer step results in relayed correlations. This problem is particularly pronounced for the indirect detection of very low-γ nuclei such as 89Y, 103Rh, 109Ag and 183W where long contact times on the order of 10 to 30 ms are necessary for optimal CP transfer. In this work, we propose two methods that eliminate relayed correlations and allow more reliable distance information to be obtained from 2D HETCOR NMR spectra. The first method uses Lee-Goldburg (LG) CP during the X→1H back-transfer step to suppress 1H spin diffusion. We determine LG conditions compatible with fast MAS frequencies (νrot) of 40- 95 kHz and show that 1H spin diffusion can be efficiently suppressed at low effective radiofrequency (RF) fields (ν1,eff << 0.5νrot) and also at high effective RF fields (ν1,eff >> 2νrot). We describe modified Hartmann-Hahn LG-CP match conditions compatible with fastmore » MAS and suitable for indirect detection of moderate-γ nuclei such as 13C, and low-γ nuclei such as 89Y. The second method uses D-RINEPT (dipolar refocused insensitive nuclei enhanced by polarization transfer) during the X→1H back-transfer step of the HETCOR pulse sequence. The effectiveness of these methods for acquiring HETCOR spectra with reduced relayed signal intensities is demonstrated with 1H{13C} HETCOR NMR experiments on L-histidine•HCl•H2O and 1H{89Y} HETCOR NMR experiments on an organometallic yttrium complex.« less

Authors:
 [1];  [2];  [1];  [1];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  2. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
OSTI Identifier:
1668265
Alternate Identifier(s):
OSTI ID: 1693889
Report Number(s):
IS-J-10,108
Journal ID: ISSN 0926-2040; DE-AC02-07CH11358; DE-AC02-07CH11358; DE-AC02-07CH11358; DE-AC02-07CH11358; DE-AC02-07CH11358; DE-AC02-07CH11358; DE-AC02-07CH11358
Grant/Contract Number:  
AC02-07CH11358; DMR-1644779
Resource Type:
Accepted Manuscript
Journal Name:
Solid State Nuclear Magnetic Resonance
Additional Journal Information:
Journal Volume: 105; Journal ID: ISSN 0926-2040
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Citation Formats

Venkatesh, Amrit, Hung, Ivan, Boteju, Kasuni C., Sadow, Aaron D., Gor’kov, Peter L., Gan, Zhehong, and Rossini, Aaron J. Suppressing 1H Spin Diffusion in Fast MAS Proton Detected Heteronuclear Correlation Solid-State NMR Experiments. United States: N. p., 2019. Web. doi:10.1016/j.ssnmr.2019.101636.
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Venkatesh, Amrit, Hung, Ivan, Boteju, Kasuni C., Sadow, Aaron D., Gor’kov, Peter L., Gan, Zhehong, & Rossini, Aaron J. Suppressing 1H Spin Diffusion in Fast MAS Proton Detected Heteronuclear Correlation Solid-State NMR Experiments. United States. https://doi.org/10.1016/j.ssnmr.2019.101636
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Venkatesh, Amrit, Hung, Ivan, Boteju, Kasuni C., Sadow, Aaron D., Gor’kov, Peter L., Gan, Zhehong, and Rossini, Aaron J. Wed . "Suppressing 1H Spin Diffusion in Fast MAS Proton Detected Heteronuclear Correlation Solid-State NMR Experiments". United States. https://doi.org/10.1016/j.ssnmr.2019.101636. https://www.osti.gov/servlets/purl/1668265.
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@article{osti_1668265,
title = {Suppressing 1H Spin Diffusion in Fast MAS Proton Detected Heteronuclear Correlation Solid-State NMR Experiments},
author = {Venkatesh, Amrit and Hung, Ivan and Boteju, Kasuni C. and Sadow, Aaron D. and Gor’kov, Peter L. and Gan, Zhehong and Rossini, Aaron J.},
abstractNote = {Fast magic angle spinning (MAS) and indirect detection by high gyromagnetic ratio (γ) nuclei such as proton or fluorine are increasingly utilized to obtain 2D heteronuclear correlation (HETCOR) solid-state NMR spectra of spin-1/2 nuclei by using cross polarization (CP) for coherence transfer. However, one major drawback of CP HETCOR pulse sequences is that 1H spin diffusion during the back X→1H CP transfer step results in relayed correlations. This problem is particularly pronounced for the indirect detection of very low-γ nuclei such as 89Y, 103Rh, 109Ag and 183W where long contact times on the order of 10 to 30 ms are necessary for optimal CP transfer. In this work, we propose two methods that eliminate relayed correlations and allow more reliable distance information to be obtained from 2D HETCOR NMR spectra. The first method uses Lee-Goldburg (LG) CP during the X→1H back-transfer step to suppress 1H spin diffusion. We determine LG conditions compatible with fast MAS frequencies (νrot) of 40- 95 kHz and show that 1H spin diffusion can be efficiently suppressed at low effective radiofrequency (RF) fields (ν1,eff << 0.5νrot) and also at high effective RF fields (ν1,eff >> 2νrot). We describe modified Hartmann-Hahn LG-CP match conditions compatible with fast MAS and suitable for indirect detection of moderate-γ nuclei such as 13C, and low-γ nuclei such as 89Y. The second method uses D-RINEPT (dipolar refocused insensitive nuclei enhanced by polarization transfer) during the X→1H back-transfer step of the HETCOR pulse sequence. The effectiveness of these methods for acquiring HETCOR spectra with reduced relayed signal intensities is demonstrated with 1H{13C} HETCOR NMR experiments on L-histidine•HCl•H2O and 1H{89Y} HETCOR NMR experiments on an organometallic yttrium complex.},
doi = {10.1016/j.ssnmr.2019.101636},
journal = {Solid State Nuclear Magnetic Resonance},
number = ,
volume = 105,
place = {United States},
year = {Wed Nov 13 00:00:00 EST 2019},
month = {Wed Nov 13 00:00:00 EST 2019}
}
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