Quantitative phosphorus-31 NMR analysis of lignins, a new tool for the lignin chemist

TLDR: In this paper, a quantitative method for the determination of the various types of hydroxyl groups present in lignins was developed for determining the syringyl, guaiacyl and p-hydroxyphenyl free phenolic groups.

Abstract: A novel quantitative method has been developed for the determination of the various types of hydroxyl groups present in lignins. The syringyl, guaiacyl and p-hydroxyphenyl free phenolic groups, as well as the primary, and the secondary hydroxyl groups (belonging to individual erythro and threo forms of the aryl-glycerol β-O-4 ether strctures) can be quantitatively determined from a 31P NMR experiment. This is made possible by phosphitylating lignins with 1,3,2 dioxaphospholanyl chloride, followed by 31P NMR spectroscopy, in the presence of a relaxation reagent (chromium acetylacetonate) and an internal standard. The various aspects leading to the development of this technique are discussed together with relevant statistical information pertaining to the reproducibility and quantitative validity of the method. This simple and novel form of spectroscopy may become a valuable resource to the lignin chemist, because it can supply detailed quantitative information about the structure of a soluble lign...