Lignin Stabilization and Carbohydrate Nature in H-transfer Reductive Catalytic Fractionation: The Role of Solvent Fractionation of Lignin Oil in Structural Profiling.
Lignin Stabilization and Carbohydrate Nature in H-transfer Reductive Catalytic Fractionation: The Role of Solvent Fractionation of Lignin Oil in Structural Profiling.
复制标题
DOI：
10.1002/cssc.202201875
复制
发表时间：
2023-02-08
期刊：
影响因子：
8.4
通讯作者：
中科院分区：
文献类型：
--
作者：
木质纤维素材料的还原催化分馏（RCF）生产出富含单体产品的木质素油和高质量的纤维素纸浆。RCF木质素油还含有木质素低聚物/聚合物和半纤维素衍生的碳水化合物。组分的多样性使木质素油成为分析方法的复杂基质。因此，信号通常是复杂和重叠的，这使得检测和量化关键中间体具有挑战性。因此，为了研究木质素稳定的机制和阐明RCF木质素油中碳水化合物的结构特征，需要降低RCF木质素油复杂性的分馏方法。本报告探讨了溶剂分馏的RCF木质素油作为一种简便的方法，以生产木质素油馏分的高级表征。溶剂分馏使用小体积的环境友好型溶剂（甲醇、丙酮和乙酸乙酯）来生产包含不同分子量范围产品的多组分木质素馏分。该特性允许通过高分辨率HSQC核磁共振波谱法确定RCF木质素油的整个分子量分布的结构不均匀性。本研究详细介绍了加氢催化剂（Raney Ni）在稳定木质素碎片中的作用，并确定了氢转移RCF工艺获得的木质素油中半纤维素衍生碳水化合物的结构特征。简单是终极的成熟。发现β - O - 4键经过选择性氢氧还原形成β - O - 4键，在c - α位置有一个亚甲基。这个过程也稳定木质素碎片。此外，RCF木质素油中的碳水化合物被发现是低聚糖（阿拉伯）木聚糖醇，它不与木质素共价键合。
Reductive Catalytic Fractionation (RCF) of lignocellulosic materials produces lignin oil rich in monomer products and high‐quality cellulosic pulps. RCF lignin oil also contains lignin oligomers/polymers and hemicellulose‐derived carbohydrates. The variety of components makes lignin oil a complex matrix for analytical methods. As a result, the signals are often convoluted and overlapped, making detecting and quantifying key intermediates challenging. Therefore, to investigate the mechanisms underlining lignin stabilization and elucidate the structural features of carbohydrates occurring in the RCF lignin oil, fractionation methods reducing the RCF lignin oil complexity are required. This report examines the solvent fractionation of RCF lignin oil as a facile method for producing lignin oil fractions for advanced characterization. Solvent fractionation uses small volumes of environmentally benign solvents (methanol, acetone, and ethyl acetate) to produce multigram lignin fractions comprising products in different molecular weight ranges. This feature allows the determination of structural heterogeneity across the entire molecular weight distribution of the RCF lignin oil by high‐resolution HSQC NMR spectroscopy. This study provides detailed insight into the role of the hydrogenation catalyst (Raney Ni) in stabilizing lignin fragments and defining the structural features of hemicellulose‐derived carbohydrates in lignin oil obtained by the H‐transfer RCF process. Simplicity is the ultimate sophistication. β‐O‐4 linkages are found to undergo selective hydrodeoxygenation forming β‐O‐4 linkages bearing a methylene group at the Cα position. This process also stabilizes lignin fragments. In addition, carbohydrates in RCF lignin oil are found to be oligo(arabino)xylan alcohols, which are not covalently bonded to lignin.
登录
查看更多内容
影响因子：
39.8
作者：
Adler, Anneli;Kumaniaev, Ivan;Samec, Joseph S. M.
通讯作者：
Samec, Joseph S. M.
影响因子：
1.9
作者：
Donaldson, Lloyd
通讯作者：
Donaldson, Lloyd
影响因子：
9.8
作者：
Hang Dao Thi;Van Aelst, Korneel;Van Geem, Kevin M.
通讯作者：
Van Geem, Kevin M.
影响因子：
16.6
作者：
Ferrini, Paola;Rinaldi, Roberto
通讯作者：
Rinaldi, Roberto
影响因子：
8.4
作者：
Cui, Chengzhong;Sun, Runkun;Argyropoulos, Dimitris S.
通讯作者：
Argyropoulos, Dimitris S.