Primary hemicelluloses

Hemicelluloses and Related Polysaccharides. HemiceUuloses [9034-32-6] are a large group of polysaccharides that are associated with ceUulose in the primary and secondary ceU waUs of aU higher plants, but otherwise have no relationship to ceUulose (2). They are also present in some other plants. 

Glucomannans (GM) and galactoglucomannans (GGM), common constituents of plant cell walls, are the major hemicellulosic components of the secondary cell walls of softwoods, whereas in the secondary cell walls of hardwoods they occur in minor amounts. They are suggested to be present together with xylan and fucogalactoxyloglucan in the primary cell walls of higher plants [192]. These polysaccharides were extensively studied in the 1960s [6,193]. 

The number of reports about hemicelluloses that have been covered by this review indicates the significantly increased importance of all types of hemicelluloses as plant constituents and isolated polymers during the last decade. Attention has been paid not only to known hemicelluloses but also to the primary structure, physicochemical, physical, and various functional properties of hemicelluloses isolated from hitherto uninvestigated plants. The efforts to exploit a variety of plant as potential sources of hemicelluloses were pointed out particularly for agricultural crops, wood wastes, as well as for by-products of pulp and rayon fiber technologies. Many studies were devoted to characterize seed-storage hemicelluloses from plants that have been traditionally applied in food and medicine of many underdeveloped countries to find substitutes for imported commercial food giuns. 

The structural varieties of hemicelluloses offer a number of possibilities for specific chemical, physical, and enzymic modifications. Future advancements will be based on the synthesis of hemicellulose-based polymers with new functionalities and with a well-defined and preset primary structure both on the level of the repeating imit and the polymer chain. Hemicelluloses have also started to be attractive to synthetic polymer chemists as... 

The pectin network.-The second polysaccharide network present in primary cell walls is composed of pectic polysaccharides. The pectin network appears to coexist with the cellulose/hemicellulose network, that is, both networks appear to be able to share the same space [16-19]. However, the proportions of the two networks appear to vary from location to location within a single cell wall as well as from the primary wall of one type of cell to the primary wall of a another type of cell [9,20-22]. 

Our two network model of the primary wall receives support from a variety of indirect observations. For example it has been shown Aat when a cell wall is regenerated by a carrot protoplast a homogalacturonan/ rhamnogalacturonan shell is laid down first, through which the cellulose/ hemicellulose network is later intercalated (8). Further evidence that pectin may form an independent network is seen in the fact that walls from suspension-cultured cells of tofnato Lycopersicon esculentum VF 36),... 

The primary walls of growing plant cells are composed of 90% carbohydrate and 10% protein (51). Carbohydrate in the primary wall is present predominantly as cellulose, hemicellulose, and pectin. The pectic polysaccharides, are defined as a group of cell wall polymers containing a-l,4-linked D-galactosyluronic acid residues (62,76). Pectic polysaccharides are a major component of the primary cell waU of dicots (22-35%), arc abundant in gymnosperms and non-graminaceous monocots, and are present in reduced amounts (-10%) in the primary walls of the graminaceae (27,62). 

The components of the plant cell wall (8-21) are the middle lamella (intercellular substance), the primary wall, and the secondary wall. The middle lamella is the pectic layer between cells and holds adjoining cells together as do membrane carbohydrates. The primary wall is thin (1-3 pm) and flexible containing cellulose, hemicelluloses, pectins, and glycoproteins. This wall provides mechanical strength, maintains cell shape,... 

The primary structural component of paper is cellulose but non-structural polysaccharides (hemicelluloses) and sometimes lignin may also be present in paper. The physical and mechanical properties of a sheet are, however, in large measure due to the cellulosic fibres. 

The surface wettability of heat-treated wood decreases due to a reduction in the hydroxyl content of the modified wood (Pdtrissans etal., 2003). There is a reduction in the water-sorption capacity, which is related to a reduction in the number of primary sorption sites (OH groups) within the wood cell wall, largely as a result of the removal/degradation of the hemicellulosic component. As remarked upon earlier, hygroscopic properties are strongly influenced by the treatment method employed. Podgorski etal. (2000) heated... 

Biorefinery includes fractionation for separation of primary refinery products. The fractionation refers to the conversion of wood into its constituent components (cellulose, hemicelluloses and lignin). Processes include steam explosion, aqueous separation and hot water systems. Commercial products of biomass fractionation include levulinic acid, xylitol and alcohols. Figure 3.3 shows the fractionation of wood and chemicals from wood. 

Cellulose microfibrils make up the basic framework of the primary wall of young plant cells (3), where they form a complex network with other polysaccharides. The linking polysaccharides include hemicellulose, which is a mixture of predominantly neutral heterogly-cans (xylans, xyloglucans, arabinogalactans, etc.). Hemicellulose associates with the cellulose fibrils via noncovalent interactions. These complexes are connected by neutral and acidic pectins, which typically contain galac-turonic acid. Finally, a collagen-related protein, extensin, is also involved in the formation of primary walls. 

The major polymers that make up the wall are polysaccharides and lignin. These occur together with more minor but very important constituents such as protein and lipid. Water constitutes a major and very important material of young, primary walls (2). The lignin is transported in the form of its building units (these may be present as glucosides) and is polymerized within the wall. Those polysaccharides which make up the matrix of the wall (hemicelluloses and pectin material) are polymerized in the endomembrane system and are secreted in a preformed condition to the outside of the cell. Further modifications of the polysaccharides (such as acetylation) may occur within the wall after deposition. Cellulose is polymerized at the cell surface by a complex enzyme system transported to the plasma membrane (3). 

Darvill, J. E., McNeil, M., Darvill, A. G., Albersheim, P. (1980). Structure of plant cell walls XL Glucuronoarabi-noxylan. A second hemicellulose in the primary cell walls of suspension-cultured sycamore cells. Plant Physiol, 66,1135-1139. 

The cellulose fibrils of secondary cell-walls have a considerably greater cross-sectional area than those of primary walls,4,223 It is possible that primary microfibrils aggregate to form secondary-wall fibrils. Hemicelluloses trapped between aggregating primary, cellulose microfibrils may constitute the origin of a major proportion of the non-D-glu-cosyl residues of cellulose obtained from secondary walls. 

Fig. 8. — Partial Model of Primary Cell-Wall in Lupin Hypocotyl, Proposed by Monro and Coworkers.49 [The half of the Figure labeled (A) represents the extensin-hemicellulose network, and the half labeled (B) represents the separate, pectic network, which is believed not to involve the wall glycoprotein (extensin). Thus, the cellulose microfibrils (M) are separately cross-linked by two networks of polymers, the first (A) being composed of the wall glycoprotein and polysaccharide (probably hemicelluloses), and the second (B) being composed of the pectic polymers. These two networks have been separated in the Figure for clarity. This model is tentative and incomplete, as the nature of the linkages between the polymers in these two networks has not yet been identified. The...

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