Improved NMR transfer of magnetization from protons to half-integer spin quadrupolar nuclei at moderate and high magic-angle spinning frequencies

Jennifer S Gómez; Andrew G M Rankin; Julien Trébosc; Frédérique Pourpoint; Yu Tsutsumi; Hiroki Nagashima; Olivier Lafon; Jean-Paul Amoureux

doi:10.5194/mr-2-447-2021

Improved NMR transfer of magnetization from protons to half-integer spin quadrupolar nuclei at moderate and high magic-angle spinning frequencies

Magn Reson (Gott). 2021 Jun 17;2(1):447-464. doi: 10.5194/mr-2-447-2021. eCollection 2021.

Authors

Jennifer S Gómez¹, Andrew G M Rankin^{1

2}, Julien Trébosc³, Frédérique Pourpoint¹, Yu Tsutsumi⁴, Hiroki Nagashima⁵, Olivier Lafon^{1

6}, Jean-Paul Amoureux^{1

7

8}

Affiliations

¹ Univ. Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, Lille, 59000, France.
² present address: Sorbonne Université, CNRS, Collège de France, Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), 4 place Jussieu, Paris, 75005, France.
³ Univ. Lille, CNRS, INRAE, Centrale Lille, Univ. Artois, FR 2638 - IMEC - Fédération Chevreul, Lille, 59000, France.
⁴ Bruker Japan, 3-9 Moriya, Kanagawa, Yokohama, Kanagawa, 221-0022, Japan.
⁵ Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan.
⁶ Institut Universitaire de France, 1 rue Descartes, Paris, 75231, France.
⁷ Riken NMR Science and Development Division, Yokohama, Kanagawa, 230-0045, Japan.
⁸ Bruker Biospin, 34 rue de l'industrie, Wissembourg, 67166, France.

Abstract

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. However, the cross-polarization transfer lacks robustness in the case of quadrupolar nuclei, and we have recently introduced as an alternative technique a $D$ -RINEPT (through-space refocused insensitive nuclei enhancement by polarization transfer) scheme combining a heteronuclear dipolar recoupling built from adiabatic pulses and a continuous-wave decoupling. This technique has been demonstrated at 9.4 T with moderate MAS frequencies, $ν_{R} \approx 10$ -15 kHz, in order to transfer the DNP-enhanced $^{1}$ H polarization to quadrupolar nuclei. Nevertheless, polarization transfers from protons to quadrupolar nuclei are also required at higher MAS frequencies in order to improve the $^{1}$ H resolution. We investigate here how this transfer can be achieved at $ν_{R} \approx 20$ and 60 kHz. We demonstrate that the $D$ -RINEPT sequence using adiabatic pulses still produces efficient and robust transfers but requires large radio-frequency (rf) fields, which may not be compatible with the specifications of most MAS probes. As an alternative, we introduce robust and efficient variants of the $D$ -RINEPT and PRESTO (phase-shifted recoupling effects a smooth transfer of order) sequences using symmetry-based recoupling schemes built from single and composite $π$ pulses. Their performances are compared using the average Hamiltonian theory and experiments at $B_{0} = 18.8$ T on $γ$ -alumina and isopropylamine-templated microporous aluminophosphate (AlPO $_{4}$ -14), featuring low and significant $^{1}$ H- $^{1}$ H dipolar interactions, respectively. These experiments demonstrate that the $^{1}$ H magnetization can be efficiently transferred to $^{27}$ Al nuclei using $D$ -RINEPT with $SR 4_{1}^{2}$ (270 $_{0}$ 90 $_{180}$ ) recoupling and using PRESTO with $R 22_{2}^{7}$ (180 $_{0}$ ) or $R 16_{7}^{6}$ (270 $_{0}$ 90 $_{180}$ ) schemes at $ν_{R} = 20$ or 62.5 kHz, respectively. The $D$ -RINEPT and PRESTO recoupling schemes complement each other since the latter is affected by dipolar truncation, whereas the former is not. We also analyze the losses during these recoupling schemes, and we show how these magnetization transfers can be used at $ν_{R} = 62.5$ kHz to acquire in 72 min 2D HETCOR (heteronuclear correlation) spectra between $^{1}$ H and quadrupolar nuclei, with a non-uniform sampling (NUS).