title: Performance of RINEPT is amplified by dipolar couplings under ultrafast MAS conditions.
abstract: The refocused insensitive nuclei enhanced by polarization transfer (RINEPT) technique is commonly used for heteronuclear polarization transfer in solution and solid-state NMR spectroscopy. Suppression of dipolar couplings, either by fast molecular motions in solution or by a combination of MAS and multiple pulse sequences in solids, enables the polarization transfer via scalar couplings. However, the presence of unsuppressed dipolar couplings could alter the functioning of RINEPT, particularly under fast/ultrafast MAS conditions. In this study, we demonstrate, through experiments on rigid solids complemented by numerical simulations, that the polarization transfer efficiency of RINEPT is dependent on the MAS frequency. In addition, we show that heteronuclear dipolar coupling is the dominant factor in the polarization transfer, which is strengthened by the presence of (1)H-(1)H dipolar couplings. In fact, the simultaneous presence of homonuclear and heteronuclear dipolar couplings is the premise for the polarization transfer by RINEPT, whereas the scalar coupling plays an insignificant role under ultrafast MAS conditions on rigid solids. Our results additionally reveal that the polarization transfer efficiency decreases with the increasing duration of RF pulses used in the RINEPT sequence.
authors.affiliation: Biophysics and Department of Chemistry, The University of Michigan, Ann Arbor, MI 48109-1055, USA; School of Physics, Nankai University, Tianjin 300071, PR China.
authors.forename: Rongchun
authors.initials: R
authors.lastname: Zhang
authors.affiliation: Biophysics and Department of Chemistry, The University of Michigan, Ann Arbor, MI 48109-1055, USA. Electronic address: ramamoor@umich.edu.
authors.forename: Ayyalusamy
authors.initials: A
authors.lastname: Ramamoorthy
mesh_terms: D000465:Algorithms; D000596:Amino Acids / Q000032:analysis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D012815:Signal Processing, Computer-Assisted
chemical_list: D000596:Amino Acids
keywords: Dipolar couplings; Polarization transfer; RINEPT; Solid-state NMR; Ultrafast MAS