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从蓖麻(Ricinus communis L.)植物各部位提取的木质素:结构表征与催化解聚

Lignin Extracted from Various Parts of Castor ( L.) Plant: Structural Characterization and Catalytic Depolymerization.

作者信息

Wang Yihan, Su Shihao, Song Guoyong

机构信息

Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China.

Engineering Research Center of Forestry Biomass Materials and Energy, Ministry of Education, Beijing Forestry University, Beijing 100083, China.

出版信息

Polymers (Basel). 2023 Jun 19;15(12):2732. doi: 10.3390/polym15122732.

Abstract

Castor is an important non-edible oilseed crop used in the production of high-quality bio-oil. In this process, the leftover tissues rich in cellulose, hemicellulose and lignin are regarded as by-products and remain underutilized. Lignin is a crucial recalcitrance component, and its composition and structure strongly limit the high-value utilization of raw materials, but there is a lack of detailed studies relating to castor lignin chemistry. In this study, lignins were isolated from various parts of the castor plant, namely, stalk, root, leaf, petiole, seed endocarp and epicarp, using the dilute HCl/dioxane method, and the structural features of the as-obtained six lignins were investigated. The analyses indicated that endocarp lignin contained catechyl (C), guaiacyl (G) and syringyl (S) units, with a predominance of C unit [C/(G+S) = 6.9:1], in which the coexisted C-lignin and G/S-lignin could be disassembled completely. The isolated dioxane lignin (DL) from endocarp had a high abundance of benzodioxane linkages (85%) and a low level of β-β linkages (15%). The other lignins were enriched in G and S units with moderate amounts of β-O-4 and β-β linkages, being significantly different from endocarp lignin. Moreover, only -coumarate (CA) incorporated into the epicarp lignin was observed, with higher relative content, being rarely reported in previous studies. The catalytic depolymerization of isolated DL generated 1.4-35.6 wt% of aromatic monomers, among which DL from endocarp and epicarp have high yields and excellent selectivity. This work highlights the differences in lignins from various parts of the castor plant, providing a solid theory for the high-value utilization of the whole castor plant.

摘要

蓖麻是一种重要的非食用油料作物,用于生产高品质生物油。在此过程中,富含纤维素、半纤维素和木质素的剩余组织被视为副产品,尚未得到充分利用。木质素是关键的难降解成分,其组成和结构严重限制了原材料的高值利用,但目前缺乏关于蓖麻木质素化学的详细研究。本研究采用稀盐酸/二氧六环法从蓖麻植株的各个部位,即茎、根、叶、叶柄、种子内果皮和外果皮中分离木质素,并对所得六种木质素的结构特征进行了研究。分析表明,内果皮木质素含有儿茶酚基(C)、愈创木基(G)和紫丁香基(S)单元,其中C单元占主导地位[C/(G+S)=6.9:1],共存的C-木质素和G/S-木质素可以完全拆解。从内果皮中分离得到的二氧六环木质素(DL)具有高丰度的苯并二氧六环键(85%)和低水平的β-β键(15%)。其他木质素富含G和S单元,含有适量的β-O-4和β-β键,与内果皮木质素显著不同。此外,仅观察到外果皮木质素中掺入了对香豆酸(CA),其相对含量较高,此前的研究中鲜有报道。分离得到的DL的催化解聚产生了1.4-35.6 wt%的芳香族单体,其中内果皮和外果皮的DL产率高且选择性好。这项工作突出了蓖麻植株不同部位木质素的差异,为蓖麻全株的高值利用提供了坚实的理论依据。

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