Influence of hemicellulose and lignin on intermolecular interaction between quinacridone and lignocellulosic fibers revealed by gel-state NMR and color measurements

Abstract

Quinacridone, a π-conjugated planar molecule, and common red pigment in industrial and painting applications, easily aggregates to form large clusters of pigment particles, resulting in a reduction in color strength. Cotton-derived cellulose nanofiber (NF), which almost consists of cellulose without hemicellulose and lignin, has been found to adsorb quinacridone on the surface, which inhibits pigment aggregation. The aggregation inhibition property of cellulose NF was induced by the strong intermolecular interactions between cellulose and quinacridone. In this study, the properties of lignocellulosic fibers for suppressing the aggregation of quinacridone pigments were investigated to reveal the influence of hemicellulose and lignin on the intermolecular interactions between quinacridone and fibers. Two lignocellulosic fibers with different degrees of fibrillation were used as dispersants of the pigment. In the scanning electron microscopy (SEM) images of the quinacridone–lignocellulose mixture, quinacridone particles were observed along the lignocellulose fiber, indicating that the quinacridone particles were well-adsorbed on the fiber surface. Consequently, the color of the aqueous suspension of quinacridone–lignocellulose mixture became increasingly vivid as the weight ratio of the lignocellulose fibers increased and as the fiber was fibrillated. The nuclear Overhauser effect spectroscopy (NOESY)–nuclear magnetic resonance (NMR) spectrum for quinacridone–lignocellulose suspension in d-dimethyl sulfoxide showed several NOE cross-peaks between quinacridone and cellulose/hemicellulose, whereas no cross-peaks between quinacridone and lignin were observed. It can be concluded that cellulose and hemicellulose promote the adsorption of quinacridone on the fiber surface, whereas lignin does not interact with quinacridone, even though both are aromatic molecules. This suggests that the intermolecular interactions based on hydrogen bonding and CH–π attraction are more dominant than the π–π attraction between quinacridone and lignocellulosic fibers.