Improved NMR transfer of magnetization ...
Type de document :
Article dans une revue scientifique: Article original
DOI :
PMID :
URL permanente :
Titre :
Improved NMR transfer of magnetization from protons to half-integer spin quadrupolar nuclei at moderate and high magic-angle spinning frequencies.
Auteur(s) :
Gómez, Jennifer S. [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Rankin, Andrew G. M. [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Trebosc, Julien [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Pourpoint, Frederique [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Tsutsumi, Y. [Auteur]
Yokohama National University
Nagashima, H. [Auteur]
Lafon, Olivier [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Amoureux, Jean-Paul [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Rankin, Andrew G. M. [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Trebosc, Julien [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Pourpoint, Frederique [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Tsutsumi, Y. [Auteur]
Yokohama National University
Nagashima, H. [Auteur]
Lafon, Olivier [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Amoureux, Jean-Paul [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Titre de la revue :
Magn Reson (Gott)
Numéro :
2
Pagination :
447-464
Date de publication :
2023-11-02
ISSN :
2699-0016
Discipline(s) HAL :
Chimie/Chimie inorganique
Résumé en anglais : [en]
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 ...
Lire la suite >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, νR≈10–15 kHz, in order to transfer the DNP-enhanced 1H polarization to quadrupolar nuclei. Nevertheless, polarization transfers from protons to quadrupolar nuclei are also required at higher MAS frequencies in order to improve the 1H resolution. We investigate here how this transfer can be achieved at νR≈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 B0=18.8 T on γ-alumina and isopropylamine-templated microporous aluminophosphate (AlPO4-14), featuring low and significant 1H–1H dipolar interactions, respectively. These experiments demonstrate that the 1H magnetization can be efficiently transferred to 27Al nuclei using D-RINEPT with (270090180) recoupling and using PRESTO with (1800) or (270090180) schemes at νR=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 νR=62.5 kHz to acquire in 72 min 2D HETCOR (heteronuclear correlation) spectra between 1H and quadrupolar nuclei, with a non-uniform sampling (NUS).Lire moins >
Lire la suite >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, νR≈10–15 kHz, in order to transfer the DNP-enhanced 1H polarization to quadrupolar nuclei. Nevertheless, polarization transfers from protons to quadrupolar nuclei are also required at higher MAS frequencies in order to improve the 1H resolution. We investigate here how this transfer can be achieved at νR≈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 B0=18.8 T on γ-alumina and isopropylamine-templated microporous aluminophosphate (AlPO4-14), featuring low and significant 1H–1H dipolar interactions, respectively. These experiments demonstrate that the 1H magnetization can be efficiently transferred to 27Al nuclei using D-RINEPT with (270090180) recoupling and using PRESTO with (1800) or (270090180) schemes at νR=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 νR=62.5 kHz to acquire in 72 min 2D HETCOR (heteronuclear correlation) spectra between 1H and quadrupolar nuclei, with a non-uniform sampling (NUS).Lire moins >
Langue :
Anglais
Audience :
Internationale
Vulgarisation :
Non
Établissement(s) :
Université de Lille
CNRS
Centrale Lille
ENSCL
Univ. Artois
CNRS
Centrale Lille
ENSCL
Univ. Artois
Collections :
Équipe(s) de recherche :
RMN et matériaux inorganiques (RM2I)
Date de dépôt :
2023-11-09T01:25:56Z
2023-11-24T10:30:09Z
2023-11-24T10:30:09Z
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