Structural Characterization of the Milled-Wood Lignin Isolated from Sweet Orange Tree (Citrus sinensis) Pruning Residue

Abstract

The pruning of sweet orange trees (Citrus sinensis) generates large amounts of lignocellulosic residue. Orange tree pruning (OTP) residue presents a significant lignin content (21.2%). However, there are no previous studies describing the structure of the native lignin in OTPs. In the present work, the “milled-wood lignin” (MWL) was extracted from OTPs and examined in detail via gel permeation chromatography (GPC), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and two-dimensional nuclear magnetic resonance (2D-NMR). The results indicated that the OTP-MWL was mainly composed of guaiacyl (G) units, followed by syringyl (S) units and minor amounts of p-hydroxyphenyl (H) units (H:G:S composition of 1:62:37). The predominance of G-units had a strong influence on the abundance of the different linkages; therefore, although the most abundant linkages were β–O–4′ alkyl–aryl ethers (70% of total lignin linkages), the lignin also contained significant amounts of phenylcoumarans (15%) and resinols (9%), as well as other condensed linkages such as dibenzodioxocins (3%) and spirodienones (3%). The significant content of condensed linkages will make this lignocellulosic residue more recalcitrant to delignification than other hardwoods with lower content of these linkages.