Amorphous hemicelluloses

The chemical degradation of amorphous hemicelluloses is similar to that of cellulose (Sect. II. C.), but it proceeds much more readily and extensively because of their relatively high accessibilities. 

Fibers. The morphology of a wood fiber is represented schematically in Figure 1. It consists of several layers of cell walls which contain aggregates of cellulosic chains called microfibrils which are embedded in a polymeric matrix composed of amorphous hemicelluloses, i.e. all types of polysaccharides other than cellulose, and of lignins 11 which are phenolic compounds acting as a glue between the wood components. The primary wall (PW) of the cell contains randomly organized cellulose... 

The case of contradictory findings for the analysis of dietary fiber are due to differences among analytical methods employed. The AO AC total dietary fiber method measures all compounds not digested by amylase and protease and insoluble in 80% aqueous ethanol. While cellulose, pectin, hemicelluloses, gums and lignin do meet these criteria, extrusion-modified starches and proteins could also be measured as fiber. Sites formerly accessible to digestion by enzymes may be involved in new bonds or physically-hindered. Many materials used to add dietary fiber to foods contain far less than 100% fiber. Artz and co-workers (1990) found no difference in X-ray diffraction patterns of corn fiber-corn starch blends after extrusion, which was expected since very little crystalline cellulose was present. The com bran isolate used as a fiber source actually contained only 16.6% cellulose. Amorphous hemicelluloses comprised the remainder of the dietary fiber fraction. 

Lu and Pizzi [83] showed that lignocellulosic substrates have a distinct influence on the hardening behavior of PF-resins, whereby the activation energy of the hardening process is much lower than for the resin alone [84]. The reason is a catalytic activation of the PF-condensation by carbohydrates like crystalline and amorphous cellulose and hemicellulose. Covalent bonding between the PF-resin and the wood, especially lignin, does not play any role [84]. 

We have seen that lignin is a highly branched amorphous pol3rmer containing an extremely complex array of structures and that when in situ in the wood, it is a graft polymer with cellulose and hemicellulose to boot. Characterization of lignins thus becomes a problem. 

Unlike cellulose, hemicelluloses consist of different monosaccharide units. In addition, the polymer chains of hemicelluloses have short branches and are amorphous. Because of the amorphous morphology, hemicelluloses are partially soluble... 

In contrast to cellulose, which is crystalline, strong, and resistant to hydrolysis, hemicellulose has a random, amorphous structure with little strength. It is easily hydrolyzed by dilute acid or base, but nature provides an arsenal of hemicellulase enzymes for its hydrolysis. Hemicellulases are commercially important because they open the structure of wood for easier bleaching and thus support the introduction of ECF or TCF methods. Many different pentoses are usually present in hemicellulose. Xylose, however, is always the predominating sugar. The pentoses are also present in rings (not shown) that can be five- or six-membered. 

Disordered cellulose molecules as well as hemicelluloses and lignin are located in the spaces between the microfibrils. The hemicelluloses are considered to be amorphous although they apparently are oriented in the same direction as the cellulose microfibrils. Lignin is both amorphous and isotropic. 

Although hemicelluloses occurring in plant tissues are likely to be amorphous [18, 19], they, like cellulose, are capable of forming strong hydrogen bonds... 

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