Molecular Weight Distributions and Linkages in Lignocellulosic Materials Derivatized from Ionic Liquid Media

A novel and reproducible method is described for accurately determining the molecular weight distribution by size exclusion chromatography (SEC) of whole lignocellulosic materials. This approach offers the opportunity to compare the molecular weight distributions of intact milled woods and its component fractions, lignins and holocelluloses, all from the same source, thus highlighting the potential of the technique and the contributions of the individual components to the chromatogram. The method is based on the dissolution of the ball-milled samples in the ionic liquid 1-allyl-3- methylimidazolium chloride ([amim]Cl). Under these homogeneous ionic liquid media, a derivatization reaction was performed with benzoyl chloride in the presence of pyridine. The thoroughly benzoylated wood with its associated carbohydrate and lignin components was found to be completely soluble in the THF SEC eluent with marked UV detector sensitivity. This methodology, when applied to the individually isolated holocellulose and lignin (enzymatic mild acidolysis lignin; EMAL) materials from Norway spruce (Eucalyptus grandis) wood and corn stover, offered a better understanding as to the possible ways the lignin and the carbohydrates may interact within these three different species. Finally, the applicability of the methodology is shown for a series of pure cellulosic samples under intense mechanical defibration conditions, offering a visualization of the molecular weight distribution changes induced during the production of nanofibrillated cellulose. © 2011 American Chemical Society.