Dynamics of cross polarization in solid state nuclear magnetic resonance experiments of amorphous and heterogeneous natural organic substances

Nuclear magnetic resonance (NMR) experiments on carbon-13 in the solid state were done with cross polarization (CP) and magic angle spinning (MAS) in order to overcome the low NMR sensitivity of (13)C and the chemical shift anisotropy, respectively. In the present research, CPMAS (13)C-NMR spectra were collected by modulating the contact time needed for cross polarization (variable contact times experiments, VCT) on two different humic acids (a soil-HA and a coal-HA). VCT data were fitted by a model containing either a monotonic or a non-monotonic cross polarization term. The non-monotonic model, which fitted the experimental results better than the monotonic one, provided two cross-polarization rates, thereby suggesting that two different mechanisms for the energy transfer from protons to carbons arise in amorphous and heterogeneous humic substances. The first mechanism was a fast proton-to-carbon energy transfer due to protons directly bound to carbons. The second mechanism was related to a slow transfer mediated by local segmental motions. Different domains in the humic acids were identified. Soil-HA was made of rigid domains, containing mainly aromatic and carboxylic moieties, and fast moving domains, containing alkyl, C-O and C-N groups. Coal-HA showed a rigid aromatic domain that was differentiated from a very mobile domain made of alkyl and COOH groups.