23第三节木素的化学构造.pptVIP

第三节 木素的化学构造Chapter 3 Chemical structure of lignin 木素的功能基 木素的结构单元 木素结构单元间的联接 光谱的基本概念及其在木素结构研究上的应用 木素模型构造图 木素-碳水化合物复合体（LCC） 一、木素的功能基 主要包括甲氧基（-OCH3）、羟基（-OH）和羰基（-CO）。 （一）元素组成及甲氧基（methoxyl group） 甲氧基是木素最重要的特征基团，其含量为： 针叶木木素：14％－16％ 阔叶木木素：19％－22％ 草本类木素：14％－15％ 阔叶木木素中甲氧基含量比针叶木高,why? 木素中的甲氧基是联接在芳香环上的，而不 是联接在脂肪族侧链上。 甲氧基位置的确定 甲氧基所处的位置不同，裂开速度不同。 How to analyze the Methoxyl Groups? The methoxyl content is a widely used for characterization of lignins. It gives a measure of their purity and of their plant origin. The method most widely used is based on the formation of methyl iodide when the sample is treated with hydriodic acid at reflux temperature. 酚羟基（phenolic hydroxyl group）：存在于苯环上； 脂肪族羟基（aliphatic hydroxyl group）：存在于木素结构单元侧链上。 1.酚羟基 多数醚化，少数游离。 2.脂肪族羟基 使羟基甲基化的试剂 -碳原子上的－OH How to analyze the phenolic hydroxyl groups?  Common instrumental methods for the estimation of phenolic groups in lignin are potentiometric and conductormeric titration, ionization difference UV spectroscopy, and NMR spectroscopy Chemical methods include determination of the increase in methoxyl content after reaction with diazomethane, selective deacetylation of acetylated lignin with aminolysis（氨基水解）, and determination of the amount of methanol formed after oxidation with sodium periodate How to analyze the phenolic hydroxyl groups?（continued） A more indirect method is based on permangnate oxidation after alkylation of the phenolic groups The periodate method is based on the guaiacyl and syringyl structures with aqueous sodium periodate to o-quinone structures with the release of 1M methanol from each phenolic unit (Fig.4.27) Fig. 4.27 How to analyze the phenolic hydroxyl groups (continued)? The aminolysis is based on the finding that phenolic acetates are cleaved with pyrrolidine(吡咯烷）much faster than aliphatic acetates. The pyrrolidine acetates formed in the reaction of an acetylated lignin is determined by GC (gas chromatography) (Fig.4.28) Fig.4.28 How to analyze the aliphatic hydroxyl g