TY - JOUR
T1 - Broadband adiabatic inversion cross-polarization phenomena in the NMR of rotating solids
AU - Wi, Sungsool
AU - Schurko, Robert W.
AU - Frydman, Lucio
N1 - This work was supported by the NHMFL through the National Science Foundation Cooperative Agreement (DMR-1157490 and 1644779) and by the State of Florida. L.F. acknowledges support from the Israel Science Foundation grant 795/13, the Kimmel Institute for Magnetic Resonance (Weizmann Institute), and the generosity of the Perlman Family Foundation. R.W.S. thanks NSERC for funding this research in the form of a Discovery Grant and Discovery Accelerator Supplement, and is also grateful for a 50th Anniversary Golden Jubilee Chair from the University of Windsor.
PY - 2018/10
Y1 - 2018/10
N2 - We explore the use of cross-polarization magic-angle spinning (CPMAS) methods incorporating an adiabatic frequency sweep in a standard Hartman-Hahn CPMAS pulse scheme, to achieve signal enhancements in solid-state NMR spectra of rare spins under fast MAS spinning rates, including spin-1/2, integer spin, and half-integer spin nuclides. These experiments, dubbed Broadband Adiabatic INversion Cross-Polarization Magic-Angle Spinning (BRAIN-CPMAS) experiments, involve an adiabatic inversion pulse on the S-channel of a rare spin nuclide while simultaneously applying a conventional spin-locking pulse on the I-channel (1H). The signal enhancement imparted by this CP scheme on the S-spin is broadbanded, while employing low RF field strengths on both I- and S-channels. A feature demanded by these BRAIN-CPMAS methods is to impose a selective adiabatic frequency sweep over a single MAS spinning centerband or sideband, to avoid interference between the MAS modulation and sweeps over multiple sidebands. Upon implementing this swept-CP method, a number of MAS-driven processes happen, including broadband zero- and double-quantum CP transfers, and MAS-driven rotary-resonance phenomena. When this CP method is applied to integer and half-integer quadrupolar nuclei at very fast MAS spinning rates, a favorable double-quantum CP condition is found that can be easily achieved, and avoids the level-crossings among various ms energy levels that complicate quadrupolar CPMAS NMR experiments along lines first shown by Alex Vega. An additional CP mechanism was found in the 1H-2H case, involving static-like zero-quantum CP modes driven by a quadrupole-modulated RF-dipolar zero-order recoupling under MAS. All these phenomena were examined using average Hamiltonian theory, numerical simulations, and experiments on model compounds. Sensitivity-enhanced, distortion-free CP over wide bandwidths were predicted and observed for S = 1/2 and for S = 1 (2H) under fast MAS rates. BRAIN-CPMAS also delivered undistorted central transition NMR spectra of half-integer quadrupolar nuclei, while utilizing low RF field strengths that avoid complex level-crossing effects under high MAS rates.
AB - We explore the use of cross-polarization magic-angle spinning (CPMAS) methods incorporating an adiabatic frequency sweep in a standard Hartman-Hahn CPMAS pulse scheme, to achieve signal enhancements in solid-state NMR spectra of rare spins under fast MAS spinning rates, including spin-1/2, integer spin, and half-integer spin nuclides. These experiments, dubbed Broadband Adiabatic INversion Cross-Polarization Magic-Angle Spinning (BRAIN-CPMAS) experiments, involve an adiabatic inversion pulse on the S-channel of a rare spin nuclide while simultaneously applying a conventional spin-locking pulse on the I-channel (1H). The signal enhancement imparted by this CP scheme on the S-spin is broadbanded, while employing low RF field strengths on both I- and S-channels. A feature demanded by these BRAIN-CPMAS methods is to impose a selective adiabatic frequency sweep over a single MAS spinning centerband or sideband, to avoid interference between the MAS modulation and sweeps over multiple sidebands. Upon implementing this swept-CP method, a number of MAS-driven processes happen, including broadband zero- and double-quantum CP transfers, and MAS-driven rotary-resonance phenomena. When this CP method is applied to integer and half-integer quadrupolar nuclei at very fast MAS spinning rates, a favorable double-quantum CP condition is found that can be easily achieved, and avoids the level-crossings among various ms energy levels that complicate quadrupolar CPMAS NMR experiments along lines first shown by Alex Vega. An additional CP mechanism was found in the 1H-2H case, involving static-like zero-quantum CP modes driven by a quadrupole-modulated RF-dipolar zero-order recoupling under MAS. All these phenomena were examined using average Hamiltonian theory, numerical simulations, and experiments on model compounds. Sensitivity-enhanced, distortion-free CP over wide bandwidths were predicted and observed for S = 1/2 and for S = 1 (2H) under fast MAS rates. BRAIN-CPMAS also delivered undistorted central transition NMR spectra of half-integer quadrupolar nuclei, while utilizing low RF field strengths that avoid complex level-crossing effects under high MAS rates.
U2 - https://doi.org/10.1016/j.ssnmr.2018.08.003
DO - https://doi.org/10.1016/j.ssnmr.2018.08.003
M3 - مقالة مرجعية
SN - 0926-2040
VL - 94
SP - 31
EP - 53
JO - Solid State Nuclear Magnetic Resonance
JF - Solid State Nuclear Magnetic Resonance
ER -