Detailed analysis of the TIMES and TIMES0 high-resolution MAS methods for high-resolution proton NMR.

We analyze and compare the specifications of TIMES and TIMES(0) proton high-resolution NMR methods for solid-state samples. This comparison is performed in terms of resolution versus magic-angle spinning (MAS) spinning speed, ν(R), rf-field amplitude, ν(1), and tilt-angle for the effective rf-field, θ(p). The chemical-shift and homo-nuclear dipolar scaling factors are calculated for both methods. For all MAS speeds, the best resolution is always observed with rf-field of ν(1)≈120-130 kHz. At slow MAS speed (ν(R)≤10 kHz), the best resolution is observed for a tilt-angle of θ(P)≈90°. At moderate spinning speed (15≤ν(R)≤35 kHz), θ(P)≈55° gives the best resolution. At higher MAS speed (ν(R)≥60 kHz), with TIMES and TIMES(0) the best resolution is obtained for θ(P)≤40°; but we then recommend TIMES(0), owing to its simpler set-up. We also show that in addition to the usual high rf-field regime (ν(1)≈120-130 kHz), another low rf-regime (ν(1)≈40-50 kHz) exists at MAS speed higher than ν(R)≥60 kHz, which also gives a good (1)H resolution. This low rf-regime should be useful for multi-dimensional analyses of bio-molecules with (1)H detection under high-resolution, in order to limit the heating of the sample.