Broadband adiabatic inversion experiments for the measurement of longitudinal relaxation time constants

摘要

Accurate measurements of longitudinal relaxation time constants (T-1) in solid-state nuclear magnetic resonance (SSNMR) experiments are important for the study of molecular-level structure and dynamics. Such measurements are often made under magic-angle spinning conditions; however, there are numerous instances where they must be made on stationary samples, which often give rise to broad powder patterns arising from large anisotropic NMR interactions. In this work, we explore the use of wideband uniform-rate smooth-truncation pulses for the measurement of T-1 constants. Two experiments are introduced: (i) BRAIN-CPT1, a modification of the BRAIN-CP (BRoadband Adiabatic-INversion-Cross Polarization) sequence, for broadband CP-based T-1 measurements and (ii) WCPMG-IR, a modification of the WURST-CPMG sequence, for direct-excitation (DE) inversion-recovery experiments. A series of T-1 constants are measured for spin-1/2 and quadrupolar nuclei with broad powder patterns, such as Sn-119 (I = 1/2), Cl-35 (I = 3/2), H-2 (I = 1), and Pt-195 (I = 1/2). High signal-to-noise spectra with uniform patterns can be obtained due to signal enhancements from T-2(eff)-weighted echo trains, and in favorable cases, BRAIN-CPT1 allows for the rapid measurement of T-1 in comparison to DE experiments. Protocols for spectral acquisition, processing, and analysis of relaxation data are discussed. In most cases, relaxation behavior can be modeled with either monoexponential or biexponential functions based upon measurements of integrated powder pattern intensity; however, it is also demonstrated that one must interpret such T-1 values with caution, as demonstrated by measurements of T-1 anisotropy in Sn-119, H-2, and Pt-195 NMR spectra.