We report novel symmetry-based pulse sequences for exciting double-quantum (2Q) coherences between the central transitions of half-integer spin quadrupolar nuclei in the NMR of rotating solids. Compared to previous 2Q-recoupling techniques, numerical simulations and 23Na and 27Al NMR experiments on Na2SO4 and the open-framework aluminophosphate AlPO-CJ19 verify that the new dipolar recoupling schemes display higher robustness to both radio-frequency field inhomogeneity and to spreads in resonance frequencies. These advances allowed for the first demonstration of 2Q-recoupling in an amorphous solid for revealing its intermediate-range structural features, in the context of mapping 27Al-27Al connectivities between the aluminium polyhedra (AlO4, AlO5 and AlO6) of a lanthanum aluminate glass (La0.18Al0.82O1.5).
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http://dx.doi.org/10.1039/b808295b | DOI Listing |
J Phys Chem A
January 2025
Department of NMR based Structural Biology, Max Planck Institute for Multidisciplinary Sciences, Am Faßberg 11, Göttingen 37077, Germany.
Theoretical and simulated analyses of selective homonuclear dipolar recoupling sequences serve as primary tools for understanding and determining the robustness of these sequences under various conditions. In this article, we investigate the recently proposed first-order dipolar recoupling sequence known as MODIST (Modest Offset Difference Internuclear Selective Transfer). We evaluate the MODIST transfer efficiency, assessing its dependence on rf-field strengths and the number of simulated spins, extending up to 10 spins.
View Article and Find Full Text PDFChem Rev
November 2024
Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Magic angle spinning (MAS) nuclear magnetic resonance (NMR) has evolved significantly over the past three decades and established itself as a vital tool for the structural analysis of biological macromolecules and materials. This review delves into the development and application of dipolar recoupling techniques in MAS NMR, which are crucial for obtaining detailed structural and dynamic information. We discuss a variety of homonuclear and heteronuclear recoupling methods which are essential for measuring spatial restraints and explain in detail the spin dynamics that these sequences generate.
View Article and Find Full Text PDFJ Magn Reson
November 2024
Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, Cambridge, MA 02139, United States. Electronic address:
In magic angle spinning (MAS) experiments involving uniformly C/N labeled proteins, C-C and C-N dipolar recoupling experiments are now routinely used to measure direct dipole-dipole couplings that constrain distances and torsion angles and determine molecular structures. When the distances are short (<4 Å), the direct couplings dominate the evolution of the spin system, and the C-C and C-N J-couplings (scalar couplings) are ignored. However, for structurally interesting >4 Å distances, the dipolar and J-couplings are generally of comparable magnitude, and the variation in J must be included in order to optimize the precision of the experiment.
View Article and Find Full Text PDFJACS Au
September 2024
School of Chemistry, Faculty of Exact sciences, Tel Aviv University, Tel Aviv 6997801, Israel.
The development of robust NMR methodologies to probe dynamics on the atomic scale is vital to elucidate the close relations between structure, motion, and function in biological systems. Here, we present an automated protocol to measure, using magic-angle spinning NMR, the effective C-N dipolar coupling constants between multiple spin pairs simultaneously with high accuracy. We use the experimental dipolar coupling constants to quantify the order parameters of multiple C-N bonds in the thousands of identical copies of the coat protein in intact fd-Y21M filamentous bacteriophage virus and describe its overall dynamics on the submillisecond time scale.
View Article and Find Full Text PDFChemphyschem
December 2024
Polymer Science and Technology, CSIR-Central Leather Research Institute, Adyar, Chennai, 600020, India.
A Model mesogen and its symmetrical Dimer made up of phenyl benzoate core unit are investigated by C NMR spectroscopy. The existence of layer order in smectic A and smectic C phases of Dimer mesogen is established by powder X-ray diffraction. The chemical shift anisotropy (CSA) tensors of Model mesogen are determined by 2D separation of undistorted powder patterns by effortless recoupling (SUPER) experiment and are utilized for calculating the order parameters employing the alignment-induced chemical shifts (AIS).
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