These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.


Pubmed for Handhelds

PUBMED FOR HANDHELDS

Search MEDLINE/PubMed

  • Title: On the use of radio-frequency offsets for improving double-quantum homonuclear dipolar recoupling of half-integer-spin quadrupolar nuclei.
    Author: Duong NT, Lee D, Mentink-Vigier F, Lafon O, De Paëpe G.
    Journal: Magn Reson Chem; 2021 Sep; 59(9-10):991-1008. PubMed ID: 33624858.
    Abstract:
    Detecting proximities between nuclei is crucial for atomic-scale structure determination with nuclear magnetic resonance (NMR) spectroscopy. Different from spin-1/2 nuclei, the methodology for quadrupolar nuclei is limited for solids due to the complex spin dynamics under simultaneous magic-angle spinning (MAS) and radio-frequency irradiation. Herein, the performances of several homonuclear rotary recoupling (HORROR)-based homonuclear dipolar recoupling sequences are evaluated for 27 Al (spin-5/2). It is shown numerically and experimentally on mesoporous alumina that BR 2 2 1 outperforms the supercycled S3 sequence and its pure double-quantum (DQ) (bracketed) version, [S3 ], both in terms of DQ transfer efficiency and bandwidth. This result is surprising since the S3 sequence is among the best low-power recoupling schemes for spin-1/2. The superiority of BR 2 2 1 is thoroughly explained, and the crucial role of radio-frequency offsets during its spin dynamics is highlighted. The analytical approximation of BR 2 2 1 , derived in an offset-toggling frame, clarifies the interplay between offset and DQ efficiency, namely, the benefits of off-resonance irradiation and the trough in DQ efficiency for BR 2 2 1 when the irradiation is central between two resonances, both for spin-1/2 and half-integer-spin quadrupolar nuclei. Additionally, density matrix propagations show that the BR 2 2 1 sequence, applied to quadrupolar nuclei subject to quadrupolar interaction much larger than radio-frequency frequency field, can create single- and multiple-quantum coherences for near on-resonance irradiation. This significantly perturbs the creation of DQ coherences between central transitions of neighboring quadrupolar nuclei. This effect explains the DQ efficiency trough for near on-resonance irradiation, in the case of both cross-correlation and autocorrelation peaks. Overall, this work aids experimental acquisition of homonuclear dipolar correlation spectra of half-integer-spin quadrupolar nuclei and provides theoretical insights towards improving recoupling schemes at high magnetic field and fast MAS.
    [Abstract] [Full Text] [Related] [New Search]