RT Journal Article T1 Differences in the content, composition and structure of the native-like lignins in leucaena and tagasaste shrubs for biorefinery applications A1 Rosado, Mario J. A1 Rencoret, Jorge A1 Gutiérrez, Ana A1 Díaz Blanco, Manuel Jesús A1 Río, José C. del AB Leucaena and tagasaste are fast-growing leguminous shrubs recognized for producing substantial amounts oflignocellulosic biomass, making them promising candidates as alternative feedstocks for biorefineries. However,despite extensive research into their chemical composition, a detailed understanding of their native ligninstructure remains limited, hindering their optimal use in lignocellulosic biorefineries. In this study, native-likelignins were isolated and thoroughly analyzed using a variety of analytical techniques, including gel permeationchromatography (GPC), analytical pyrolysis coupled to gas chromatography/mass spectrometry (Py-GC/MS), two-dimensional Nuclear Magnetic Resonance (2D NMR), and 31P NMR. The data revealed significantdifferences in the lignin composition of the two species. Leucaena lignin showed a strong predominance ofguaiacyl (G) units, with minor amounts of syringyl (S), and p-hydroxyphenyl (H) units (H:G:S ratio of 1:83:16; S/G 0.19). In contrast, tagasaste lignin exhibited a slight predominance of S units (H:G:S ratio of 2:46:52; S/G1.13). These compositional variations significantly influenced the distribution of the different lignin interunitlinkages. Hence, leucaena lignin was characterized by fewer of β–O–4′ alkyl-aryl ether linkages (66 % of alllinkages) and a higher proportion of condensed linkages, making it more resistant to delignification. In contrast,tagasaste lignin presented higher levels of β–O–4′ alkyl-aryl ether linkages (74 %) and fewer condensed linkages,rendering it more susceptible to delignification. The insights gained from this study are expected to enhance thevalorization of these lignocellulosic materials as feedstocks in future lignocellulosic biorefineries PB Elsevier SN 0926-6690 SN 1872-633X (electrónico) YR 2025 FD 2025-05 LK https://hdl.handle.net/10272/25712 UL https://hdl.handle.net/10272/25712 LA eng NO Rosado, M. J., Rencoret, J., Gutiérrez, A., Díaz, M. J., & del Río, J. C. (2025). Differences in the content, composition and structure of the native-like lignins in leucaena and tagasaste shrubs for biorefinery applications. Industrial Crops and Products, 231, 121195. https://doi.org/10.1016/j.indcrop.2025.121195 NO This work was financed by the Spanish Ministerio de Ciencia, Innovaci´on y Universidades/Agencia Estatal de Investigaci´on - MCIU/ AEI/10.13039/501100011033, projects PID2020-118968RB-I00 and PID2023-152543OB-I00, the latter co-financed by the European Regional Development Fund (ERDF) “A way to make Europe”. MJR acknowledges the Spanish Ministerio de Ciencia, Innovaci´on y Universidades (MICIU) for a FPI fellowship (PRE2018-083267). The authors extend their sincere thanks to Dr. Manuel Angulo (CITIUS, University of Seville) for his invaluable support in the acquisition of the NMR spectra DS Repositorio Institucional de la Universidad de Huelva RD 14 jul 2026