Determination of T1ρH relaxation rates in charred and uncharred wood and consequences for NMR quantitation

Abstract

The performance of three different techniques for determining proton rotating frame relaxation rates (T1rhoH) in charred and uncharred woods is compared. The variable contact time (VCT) experiment is shown to over-estimate T1rhoH. particularly for the charred samples, due to the presence of slowly cross-polarizing 13C nuclei. The variable spin (VSL) or delayed contact experiment is shown to overcome these problems; however, care is needed in the analysis to ensure rapidly relaxing components are not overlooked. T1rhoH is shown to be non-uniform for both charred and uncharred wood samples; a rapidly relaxing component (T1rhoH = 0.46-1.07 ms) and a slowly relaxing component (T1rhoH = 3.58-7.49) is detected in each sample. T1rhoH for each component generally decreases with heating temperature (degree of charring) and the proportion of rapidly relaxing component increases. Direct T1rhoH determination (via 1H detection) shows that all samples contain an even faster relaxing component (0.09-0.24 ms) that is virtually undetectable by the indirect (VCT and VSL) techniques. A new method for correcting for T1rhoH signal losses in spin counting experiments is developed to deal with the rapidly relaxing component detected in the VSL experiment. Implementation of this correction increased the proportion of potential 13C CPMAS NMR signal that can be accounted for by up to 50% for the charred samples. An even greater proportion of potential signal can be accounted for if the very rapidly relaxing component detected in the direct T1rhoH determination is included; however, it must be kept in mind that this experiment also detects 1H pools which may not be involved in 1H-13C cross-polarization.