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Chapter 5 Hemicellulose. 5.1 Introduction. 1. Difination Except pectin and starch, those non-cellulose polysaccharides are called hemicellulose. Hemicellulose could be extracted by alkaline solution. Softwood: poly gluco mannose Hardwood: xylan Grass and straw: xylan. 5.1 Introduction.
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5.1 Introduction 1. Difination Except pectin and starch, those non-cellulose polysaccharides are called hemicellulose. Hemicellulose could be extracted by alkaline solution. Softwood: poly gluco mannose Hardwood: xylan Grass and straw: xylan
5.1 Introduction • 2. Units • (1) Hexose: D-glucose, D-mannose, D-galactose • (2) Pentose: D-xylose, L-arabinose • (3) Uronic acid: D-glucronic acid • (4) Deoxy-hexose: L-rhamnose, L-fucose
5.1 Introduction Haworth structures
5.2 Isolation and purification 1.Pretreatment (1)Benzene-alcohol(or acetone)extraction: remove terpenoids, fats, waxes, and tannins. (2)Water extraction( or 70% ethanol): remove monosaccharides and water soluble oligosaccharides (3)Ammonium oxalate extraction: remove pectin (4)Holocellulose preparation: remove lignin
5.2 Isolation and purification 2.Preparation (1)Alkaline extraction: 17.5% NaOH , 24% KOH (2)Precipitation: ethanol (3)Chelate dissolution: Na2B4O7 polyglucomannose (4)Chelate precipitation: Ba(OH)2polyglucomannose (5)Retaining acetyl groups: DMSO
5.3 Chemical Structure • 1. Study methods • Acid hydrolysis • Periodate oxidation: ethylene glycol structure • Smith degradation • Methanolysis
5.3 Chemical Structure • Periodate oxidation
5.3 Chemical Structure Smith degradation
→4βDXp1→4βDXp1→4(βDXp)n1→4βDXp1→4βXp1→4βDXp→4βDXp1→4βDXp1→4(βDXp)n1→4βDXp1→4βXp1→4βDXp 2 3 ∣ ∣ 1 1 4-O-Me-αGlupA L-Araf Poly arabinose-4-O-methyl glucronic acid xylose βDXp: β-D-xylose, pyran-type 4-O-Me-α-GlupA: 4-O-methyl-α-glucronic acid, pyran-type L-Araf: L-arabinose, furan-type 5.3 Hemicelluloses & structures
→[4βDXp1]7-8→4βDXp1→4βDXp1→4βDXp1→ 3or2 2 ↑ ↑ 1 1 Acetyl (MeO)4-αD-GlupA →4βDMp1→4βDGp1→4βDMp1→4βDMp1→4βDGp1→ 5.3 Hemicelluloses & structures
5.4 physical structure With branches: less ordered Mostly amorphous regions Rare crystalline regions Comparation: cellulose and hemicellulose Homopolysaccharide, straight chains, no branches, composed of β-D-glucopyranose units, crystalline and amorphous regions, swelling and dissolution, degradation and derivatives
5.4 Chemical Structure Pentose ≻ Hexose β ≻ α Furan-type ≻ Pyran-type Non acidic saccharides ≻ Acidic saccharides (Arabinose ≻galactose ≻xylose ≻mannose ≻glucose)
5.5 Chemical Properties Alkaline degradation: peeling reaction
5.6 Industrial utilization • 1. Hexose • Ethanol • 2. Petose • Furfural • Xylose and xylitol
半纤维素复习题 一、答下列各题 1.依据纤维素与半纤维素在化学结构和超分子结构的区别,比较二者在化学反应能力上的不同? 2.在针叶木、阔叶木和禾本科三类植物原料的半纤维素分离时,哪类原料不可以直接用碱提取?哪类原料可以直接用碱提取?为什么? 二、写或简述下列各题 1 简写针、阔叶材木材主要半纤维素的化学结构简式(各两种简式) 2.半纤维素高聚糖在100oC NaOH溶液中发生哪些化学反应? 写出一例反应式。 3. 论述木材聚戊糖测定原理和方法,有何注意事项。
补充 • 1.半纤维素的含义 • 2.半纤维素在植物界的分布 • 3.针、阔叶木的半纤维素组成的区别 • 4.从植物体中分离半纤维素的基本方法 • 5.Smith降解 • 6.阔叶木主要半纤维素的化学结构与纤维素比较有何区别? • 7.半纤维素在酸、碱蒸煮中行为是什么?