Carbon-13 NMR Spectroscopic Studies on Chemically Modified and Unmodified Synthetic and Natural Humic Acids

Carbon-13 cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy (13C-CP/MAS-NMR) was applied to study the chemical modification process of humic acids (HA) with diazomethane and the subsequent alkaline hydrolysis of the methylated HA, which results in HA with blocked phenolic OH groups. We investigated different chemically modified and unmodified natural and synthetic HA with carbon-13 of natural abundance. In addition, we studied carbon-13 labeled modified synthetic HA, that were synthesized with [13C]diazomethane as methylation reagent, to confirm the assumed modification process and to determine the type of functional groups that have the highest affinity for methylation.
The results of the NMR studies with carbon-13 labeled HA show that carboxyl and acidic (phenolic) OH groups are methylated with diazomethane. Due to the alkaline saponification of the methylated HA, methyl esters of carboxyl groups are hydrolyzed, whereas phenolic OH groups remain methylated. Carboxyl groups show the highest affinity for methylation.
From the spectra of the modified and unmodified HA with carbon-13 of natural abundance it can be concluded that the applied modification procedure causes only the desired structural changes in HA.