Impact of Remote Protonation on 13C CPMAS NMR Quantitation of Charred and Uncharred Wood

Abstract

The impact of inefficient cross polarization (long T CH values), caused by long 13C– 1H internuclear distances, on 13C CPMAS NMR spectra of charred and uncharred woods is determined by simultaneously fitting data from complementary variable spin lock and variable contact time experiments. As expected, the impact is minimal for uncharred woods, but is very significant for the charred woods. Quantification of the decrease in CPMAS signal intensity caused by both inefficient cross polarization and rapid T 1 ρH relaxation is achieved using an advanced spin counting methodology, for which the term “spin accounting” is proposed. 13C CPMAS NMR observabilities determined using the spin accounting methodology were close to 100% for the uncharred samples, and 69–82% for the charred samples. This represents a large improvement on the 30–40% observabilities determined using other spin counting techniques. Furthermore, it is shown that remote protonation and rapid T 1 ρH relaxation are roughly equally responsible for the low signal intensity of standard (1 ms contact time) 13C CPMAS spectra of charcoal.