Abstract
We review the recent progress in homonuclear correlation NMR spectroscopy on half-integer spin quadrupolar nuclei undergoing magic-angle spinning (MAS). The most central component of such experimentation is a dipolar recoupling stage, during which the through-space interactions are reactivated and used for retrieving information about interatomic proximities and NMR interaction tensor parameters. Yet, while several homonuclear correlation techniques for half-integer spin applications exist and their usage has accelerated over the past few years, they are not as versatile and reliable as analogous spin-1/2 implementations. This stems mainly from the insufficient resolution and sensitivity of NMR spectra from quadrupolar nuclei, coupled with the challenges to achieve efficient dipolar recoupling by radio-frequency fields in the presence of MAS. Herein, we contrast various two/three-dimensional homonuclear correlation NMR protocols for establishing internuclear connectivities/proximities from the viewpoints of spectral resolution and sensitivity, with particular emphasis on experimentation involving two-spin double-quantum (2Q) coherences that has emerged as the most popular correlation technique. We discuss the relative merits of currently proposed 2Q-recoupling options for half-integer spins. The most promising recent methods for extracting structural information are reviewed, encompassing the estimation of internuclear distances and electric-field gradient tensor orientations, and the probing of cluster-sizes of (re)coupled quadrupolar nuclei. We also review recent advances in utilizing homonuclear J interactions among quadrupolar nuclei, which until recently was an essentially untapped area of solid-state NMR. The contents are organized to convey the current state-of-the-art techniques and their limitations, where we also identify the needs for further developments and suggest potentially fruitful future research directions.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Dusold S, Sebald A. Dipolar recoupling under magic-angle-spinning conditions. Annu Rep NMR Spectrosc. 2000;41:185–264.
Schnell I. Dipolar recoupling in fast-MAS solid-state NMR spectroscopy. Prog NMR Spectrosc. 2004;45:145–207.
Edén M. Advances in symmetry-based pulse sequences in magic-angle spinning solid-state NMR. eMagRes. 2013;2:351–64.
Saalwächter K, Robust NMR. Approaches for the determination of homonuclear dipole-dipole coupling constants in studies of solid materials and biomolecules. ChemPhysChem. 2013;14:3000–14.
Edén M. Homonuclear dipolar recoupling of half-integer spin quadrupolar nuclei: techniques and applications. Solid State Nucl Magn Reson. 2009;36:1–10.
Fernandez C, Pruski M. Probing quadrupolar nuclei by solid-state NMR spectroscopy: recent advances. Top Curr Chem. 2012;306:119–88.
Nielsen NC, Bildsøe H, Jakobsen HJ, Levitt MH. Double-quantum homonuclear rotary resonance: efficient dipolar recovery in magic-angle-spinning nuclear magnetic resonance. J Chem Phys. 1994;101:1805–12.
Mali G, Fink G, Taulelle F. Double-quantum homonuclear correlation magic angle sample spinning nuclear magnetic resonance spectroscopy of dipolar-coupled quadrupolar nuclei. J Chem Phys. 2004;120:2835–45.
Edén M, Lo AYH. Supercycled symmetry-based double-quantum dipolar recoupling of quadrupolar spins: I. Theory J Magn Reson. 2009;200:267–79.
Edén M, Zhou D, Yu J. Improved double-quantum NMR correlation spectroscopy of dipolar-coupled quadrupolar spins. Chem Phys Lett. 2006;431:397–403.
Lee D, Takahashi H, Thankamony ASL, Dacquin JP, Bardet M, Lafon O, et al. Enhanced solid-state NMR correlation spectroscopy of quadrupolar nuclei using dynamic nuclear polarization. J Am Chem Soc. 2012;134:11766–9.
Edén M, Two-Dimensional MAS NMR correlation protocols involving double-quantum filtering of quadrupolar spin-pairs. J Magn Reson. 2010;204:99–110.
Lo AYH, Edén M. Efficient symmetry-based homonuclear dipolar recoupling of quadrupolar spins: double-quantum NMR correlations in amorphous solids. Phys Chem Chem Phys. 2008;10:6635–64.
Mali G, Kaucic V, Taulelle F. Measuring distances between half-integer quadrupolar nuclei and detecting relative orientations of quadrupolar and dipolar tensors by double-quantum homonuclear recoupling nuclear magnetic resonance experiments. J Chem Phys. 2008;128:204503.
Wang Q, Hu B, Lafon O, Trébosc J, Deng F, Amoureux JP. Double-quantum homonuclear NMR correlation spectroscopy of quadrupolar nuclei subjected to magic-angle spinning and high magnetic field. J Magn Reson. 2009;200:251–60.
Yu Z, Zheng A, Wang Q, Chen L, Xu J, Amoureux JP, et al. Insights into the dealumination of zeolite HY revealed by sensitivity-enhanced 27Al DQ-MAS NMR spectroscopy at high field. Angew Chem Int Ed. 2010;49:8657–61.
Brinkmann A, Edén M. Estimating internuclear distances between half-integer quadrupolar nuclei by central-transition double-quantum sideband NMR spectropscopy. Can J Chem. 2011;89:892–9.
Brinkmann A, Edén M. Central-transition double-quantum sideband NMR spectroscopy of half-integer quadrupolar nuclei: estimating internuclear distances and probing clusters within multi-spin networks. Phys Chem Chem Phys. 2014;16:7037–50.
Brus J, Czernek J, Urbanova M, Kobera L, Jegorov J. An efficient 11B-11B solid-state NMR spectroscopy strategy for monitoring covalent self-assembly of boronic acid-derived compounds: the transformation and unique architecture of bortezomib molecules in the solid state. Phys Chem Chem Phys. 2017;19:487–95.
van Wüllen L, Sabarinathan V. Structure and high temperature behaviour of sodium aluminophosphate glasses. Phys Chem Glasses: Eur J Glass Sci Technol, Part B. 2016;57:173–82.
Jaworski A, Stevensson B, Pahari B, Okhotnikov K, Edén M. Local structures and Al/Si ordering in lanthanum aluminosilicate glasses explored by advanced 27Al NMR experiments and molecular dynamics simulations. Phys Chem Chem Phys. 2012;14:15866–78.
Ren J, Zhang L, Eckert H. Medium-range order in sol–gel prepared Al2O3–SiO2 glasses: new results from solid-state NMR. J Phys Chem C. 2014;118:4906–17.
Lee SK, Deschamps M, Hiet J, Massiot D, Park SY. Connectivity and proximity between quadrupolar nuclides in oxide glasses: insights from through-bond and through-space solid-state NMR. J Phys Chem B. 2009;113:5162–7.
Tricot G, Saitoh A, Takebe H. Intermediate length scale organisation in tin borophosphate glasses: new insights from high field correlation NMR. Phys Chem Chem Phys. 2015;17:29531–40.
Tricot G. The structure of Pyrex® glass investigated by correlation NMR spectroscopy. Phys Chem Chem Phys. 2016;18:26764–70.
Baldus M, Rovnyak D, Griffin RG. Radio-frequency-mediated dipolar recoupling among half-integer quadrupolar spins. J Chem Phys. 2000;112:5902–9.
Wi S, Logan JW, Sakellariou D, Walls JD, Pines A. Rotary resonance recoupling for half-integer quadrupolar nuclei in solid-state nuclear magnetic resonance. J Chem Phys. 2002;117:7024–33.
Teymoori G, Pahari B, Stevensson B, Edén M. Low-power broadband homonuclear dipolar recoupling without decoupling: double-quantum 13C NMR correlations at very fast magic-angle spinning. Chem Phys Lett. 2012;547:103–9.
Brinkmann A, Kentgens APM, Anupold T, Samoson A. Symmetry-based recoupling in double rotation solid-state NMR spectroscopy. J Chem Phys. 2008;129:174507.
Perras FA, Bryce DL. Symmetry-amplified J splittings for quadrupolar spin pairs: a solid-state NMR probe of homoatomic covalent bonds. J Am Chem Soc. 2013;135:12596–9.
Ding S, McDowell CA. Spectral spin diffusion of a spin-3/2 system in rotating solids. Mol Phys. 1995;85:283–98.
Gan Z, Robyr P. Deuterium polarization transfer in rotating solids and its application in structural investigation. Mol Phys. 1998;95:1143–52.
Dowell NG, Ashbrook SE, McManus J, Wimperis S. Relative orientation of quadrupole tensors from two-dimensional multiple-quantum MAS NMR. J Am Chem Soc. 2001;123:8135–6.
Dowell NG, Ashbrook SE, Wimperis S. Relative orientation of quadrupole tensors from high-resolution NMR of powdered solids. J Phys Chem A. 2002;106:9470–8.
Edén M, Annersten H, Zazzi Å. Pulse-assisted homonuclear dipolar recoupling of half-integer quadrupolar spins in magic-angle spinning NMR. Chem Phys Lett. 2005;410:24–30.
Edén M, Frydman L. Homonuclear NMR correlations between half-integer quadrupolar nuclei undergoing magic-angle spinning. J Phys Chem B. 2003;107:14598–611.
Edén M, Frydman L. Quadrupolar-driven recoupling of homonuclear dipolar interactions in the nuclear magnetic resonance of rotating solids. J Chem Phys. 2001;114:4116–23.
Barrow NS, Yates JR, Feller SA, Holland D, Ashbrook SE, Hodgkinson P, et al. Towards homonuclear J solid-state NMR correlation experiments for half-integer quadrupolar nuclei: experimental and simulated 2Jbb coupling constants for lithium diborate. Phys Chem Chem Phys. 2011;13:5778–89.
Edén M, Grinshtein J, Frydman L. High resolution 3D exchange NMR spectroscopy and the mapping of connectivities between half-integer quadrupolar nuclei. J Am Chem Soc. 2002;124:9708–9.
Wi S, Heise H, Pines A. Reintroducing anisotropic interactions in magic-angle spinning NMR of half-integer quadrupolar nuclei: 3D MQMAS. J Am Chem Soc. 2002;124:10652–3.
Iuga D, Holland D, Dupree R. A 3D experiment that provides isotropic homonuclear correlations of half-integer quadrupolar nuclei. J Magn Reson. 2014;246:122–9.
Mali G, Kaucic V. Enhancing sensitivity or resolution of homonuclear correlation experiment for half-integer quadrupolar nuclei. J Magn Reson. 2004;171:48–56.
Painter AJ, Duer MJ. Double-quantum-filtered nuclear magnetic resonance spectroscopy applied to quadrupolar nuclei in solids. J Chem Phys. 2002;116:710–22.
Edén M. Determination of absolute quadrupolar tensor orientations by double-quantum NMR on powders. Chem Phys Lett. 2009;470:318–24.
Duer MJ, Painter AJ. Correlating quadrupolar nuclear spins: a multiple-quantum NMR approach. Chem Phys Lett. 1999;313:763–70.
Hughes CE. Spin counting. Prog Nucl Magn Reson Spectrosc. 2004;45:301–13.
Massiot D, Fayon F, Deschamps M, Cadars S, Florian P, Montouillout V, et al. Detection and use of small J couplings in solid state NMR experiments. Comptes Rendus Chim. 2010;13:117–29.
Perras FA, Bryce DL. Measuring dipolar and J coupling between quadrupolar nuclei using double-rotation NMR. J Chem Phys. 2013;138:174202.
Perras FA, Bryce DL. Boron-Boron J coupling constants are unique probes of electronic structure: a solid-state NMR and molecular orbital study. Chem Sci. 2014;5:2428–37.
Perras FA, Bryce DL. Theoretical study of homonuclear J coupling between quadrupolar spins: single-crystal, DOR, and J-resolved solid-state NMR. J Magn Reson. 2014;242:23–32.
Perras FA. Quantitative structure parameters from the NMR spectroscopy of quadrupolar nuclei. Pure Appl Chem. 2016;88:95–111.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2018 Springer International Publishing AG, part of Springer Nature
About this entry
Cite this entry
Edén, M. (2018). Recent Progress in Homonuclear Correlation Spectroscopy of Quadrupolar Nuclei. In: Webb, G. (eds) Modern Magnetic Resonance. Springer, Cham. https://doi.org/10.1007/978-3-319-28388-3_104
Download citation
DOI: https://doi.org/10.1007/978-3-319-28388-3_104
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-28387-6
Online ISBN: 978-3-319-28388-3
eBook Packages: Chemistry and Materials ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics