Through-space heteronuclear correlation (D-HETCOR) experiments based on heteronuclear multiple-quantum correlation (D-HMQC) and refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT) sequences have been proven to be useful approaches for the detection of the spatial proximity between half-integer quadrupolar nuclei in solids under magic-angle spinning (MAS) conditions. The corresponding pulse sequences employ coherence transfers mediated by heteronuclear dipolar interactions, which are reintroduced under MAS by radiofrequency irradiation of only one of the two correlated nuclei. We investigate herein using numerical simulations of spin dynamics and solid-state NMR experiments on magnesium aluminoborate glass how the choice of the channel to which the heteronuclear dipolar recoupling is applied affects the transfer efficiency of D-HMQC and D-RINEPT sequences between B and Al nuclei. Experimental results show that maximum transfer efficiency is achieved when the recoupling scheme is applied to the channel, for which the spin magnetization is parallel to the B axis in average.
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http://dx.doi.org/10.1002/mrc.5163 | DOI Listing |
J Phys Chem Lett
September 2021
Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario K7L 3N6, Canada.
We report two- and three-dimensional (2D and 3D) C-O heteronuclear correlation solid-state NMR experiments under magic-angle spinning (MAS) conditions. These experiments utilize the D-RINEPT (Dipolar-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer) scheme with symmetry-based SR4 recoupling blocks for coherence transfer between C and O nuclei. First, a 2D O → C correlation experiment was performed for the [1-C,O]-Gly/Gly·HCl cocrystal and [U-C, 1-O]-α/β-d-glucose samples.
View Article and Find Full Text PDFMagn Reson (Gott)
June 2021
Univ. Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, Lille, 59000, France.
Half-integer spin quadrupolar nuclei are the only magnetic isotopes for the majority of the chemical elements. Therefore, the transfer of polarization from protons to these isotopes under magic-angle spinning (MAS) can provide precious insights into the interatomic proximities in hydrogen-containing solids, including organic, hybrid, nanostructured and biological solids. This transfer has recently been combined with dynamic nuclear polarization (DNP) in order to enhance the NMR signal of half-integer quadrupolar isotopes.
View Article and Find Full Text PDFMagn Reson Chem
September 2021
State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Centre for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, 430071, China.
Through-space heteronuclear correlation (D-HETCOR) experiments based on heteronuclear multiple-quantum correlation (D-HMQC) and refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT) sequences have been proven to be useful approaches for the detection of the spatial proximity between half-integer quadrupolar nuclei in solids under magic-angle spinning (MAS) conditions. The corresponding pulse sequences employ coherence transfers mediated by heteronuclear dipolar interactions, which are reintroduced under MAS by radiofrequency irradiation of only one of the two correlated nuclei. We investigate herein using numerical simulations of spin dynamics and solid-state NMR experiments on magnesium aluminoborate glass how the choice of the channel to which the heteronuclear dipolar recoupling is applied affects the transfer efficiency of D-HMQC and D-RINEPT sequences between B and Al nuclei.
View Article and Find Full Text PDFSolid State Nucl Magn Reson
February 2020
US DOE Ames Laboratory, Ames, IA, USA, 50011; Iowa State University, Department of Chemistry, Ames, IA, USA, 50011. Electronic address:
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 H spin diffusion during the back X→H CP transfer step may result in relayed correlations. This problem is particularly pronounced for the indirect detection of very low-γ nuclei such as Y, Rh, Ag and W where long contact times on the order of 10-30 ms are necessary for optimal CP transfer.
View Article and Find Full Text PDFJ Magn Reson
February 2019
Univ. Lille, CNRS-8181, UCCS: Unit of Catalysis and Chemistry of Solids, F-59000 Lille, France; Bruker France, 34 rue de l'Industrie, F-67166 Wissembourg, France. Electronic address:
In solid-state NMR spectroscopy, the through-space transfer of magnetization from protons to quadrupolar nuclei is employed to probe proximities between those isotopes. Furthermore, such transfer, in conjunction with Dynamic Nuclear Polarization (DNP), can enhance the NMR sensitivity of quadrupolar nuclei, as it allows the transfer of DNP-enhanced H polarization to surrounding nuclei. We compare here the performances of two approaches to achieve such transfer: PRESTO (Phase-shifted Recoupling Effects a Smooth Transfer of Order), which is currently the method of choice to achieve the magnetization transfer from protons to quadrupolar nuclei and which has been shown to supersede Cross-Polarization under Magic-Angle Spinning (MAS) for quadrupolar nuclei and D-RINEPT (Dipolar-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer) using symmetry-based SR4 recoupling, which has already been employed to transfer the magnetization in the reverse way from half-integer quadrupolar spin to protons.
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