Polysaccharides xylans

The origin and function of xylan in the cell wall are also not explained. Postulations that it is a plasticizer or is a reserve food are not fully substantiated. Its derivation from cellulose through the decarboxylation of an intermediary polyglucuronic acid seems very unlikely. There is evidence from a number of sources to indicate that the xylan polysaccharide is deposited along with cellulose in cell wall elaboration. 

Other workers140 have also examined the products derived by hydrolysis of periodate-oxidized xylan. Both wheat straw and com cob xylan, after oxidation and hydrolysis, yield small amounts of L-arabinose and D-xylose. These sugars are obtained even after the xylans have been subjected to extended periods of oxidation. It is concluded that the D-xylose constituted branch points in the xylan. Likewise, the L-arabi-nose molecules must not have been terminal units in a xylan chain but must have been either interior units in the xylan molecule or have constituted an araban-like polysaccharide which is in combination or admixture with the xylan polysaccharide. 

Scheme 3 Acidic Xylan (polysaccharide fraction D4) -methylation analysis, partial fragmentation to methylated aldobiouronic acid derivatives (j ), and general structure ( )...

Birch contains a higher amoxmt of xylan polysaccharides in its cell wall, so xylose sugar is found in higher concentrations in birch tree hydrolyzates as compared to other tree biomass. Relatively low levels of maimose were reported from birch tree (Keranen et al., 2013). Furfural and HMF concentrations were foxmd to be low in birch tree when compared to aspen. Hence partially fermentable sugars can be obtained from birch wood biomass (Tables 16.1 and 16.2). 

The pentosan polysaccharides, xylan and arabinan, commonly known as hemiceUulose, are the principal precursors of furfural and are always found together with lignin and cellulose in plant materials. 

The common hemiceUulose components of arborescent plants are listed in Table 3. Xylans, arabinogalactans, and pectic substances are common to all while only traces (if at all) of glucomaimans are found in the cell walls of bamboo. Other polysaccharides are found in trace amounts in wood as well as in bark, growing tissues, and other specialized parts of trees. 

Note. The name ending in -an refers to the unsubstituted polysaccharide. Thus xylan occurs in nature in unacetylated and partially acetylated forms. Xylan designates the unacetylated material, and xylan acetate an acetylated derivative. 

A similar molecular structure is also proposed82 for the gummy polysaccharide from corm sacs of Watsonia pyramidata in which the (1— 4)-xylan backbone is highly substituted with 2- as well as 3-linked L-arabinofuranosyl side... 

Xylan-type polysaccharides are the main hemicellulose components of secondary cell walls constituting about 20-30% of the biomass of dicotyl plants (hardwoods and herbaceous plants). In some tissues of monocotyl plants (grasses and cereals) xylans occur up to 50% [6j. Xylans are thus available in huge and replenishable amoimts as by-products from forestry, the agriculture, wood, and pulp and paper industries. Nowadays, xylans of some seaweed represent a novel biopolymer resource [4j. The diversity and complexity of xylans suggest that many useful by-products can be potentially produced and, therefore, these polysaccharides are considered as possible biopolymer raw materials for various exploitations. As a renewable resource, xylans are... 

Most frequently, SEC with dextran-, pullulan-, or polystyrene calibration standards has been used to characterize the molecular properties of xylans. However, as for viscometric studies [108], a sufficient solvent ionic strength is a prerequisite for useful SEC measurements of charged polysaccharides, including glucuronoxylans [111-113]. An advantage of the SEC technique is that the presence of protein and phenolic components or oxidative changes can be detected by simultaneous ultraviolet (UV) detection. 

Interactions with xanthan were investigated for some GAX fractions of wheat bran [109]. Whereas, for lowly substituted GaMs a synergy in viscosity was observed at low total polymer concentrations, yielding a maximum of the relative viscosity at nearly equal proportions of both polysaccharides [124], the xanthan/xylan mixtures at the same experimental conditions showed no synergy. The observed decrease in the relative viscosity values upon addition of the xylan indicates that a certain interaction with xanthan takes place, but that it leads to a contraction in the hydrodynamic volume. The authors suggested that structural and conformational differences between GaM and GAX might be the reason for this observation. 

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]. 

During the past decade, MALDI-TOF MS has proven to be an effective tool for the analysis of oligo- and polymeric mannoglucans (for extensive reviews see [222,223]). SEC/MALDI mass spectrometry was employed in the analysis of hemicelluloses isolated by microwave heat-fractionation from spruce and aspen wood [94]. These methods allowed the separation and characterization of the oligo- and polysaccharide fractions derived from the xylan and mannan components of both woods [224]. 

Due to the lack of a commercial supply, as well as their usually low molecular weight and poor solubility, xylans have found little industrial utility and interest in their modification has been rather low in comparison to commercially available polysaccharides such as cellulose or starch. With the aim of improving the functional properties of xylans and/or imparting new functionalities to them, various chemical modifications have been investigated during the past decade. Most of them were presented in recent reviews [3,399]. 

For thousands of years, nature has provided humankind with a large variety of materials for the most diversified applications for its survival, such as food, energy, medicinal products, protection and defense tools, and others. The pharmaceutical industry has benefitted from such diversity of biomaterials and has exploited the use of natural products as sources of both drugs and excipients. One example of a promising biomaterial for pharmaceutical use is xylan, a hemicellulose largely found in nature, being considered the second most abundant polysaccharide after cellulose. 

The floss silk from Chorisia speciosa furnished a polysaccharide with a main chain of (1 -> 4) linked P-Xylp substituted at 0-2 by 5 % of uronic acid. The xylan structure also was interposed with a-Rhap units in small amounts. The defatted seeds furnished on aqueous extraction a major fraction, ((9-acetyl, 10 % and protein, 45 %) wich was hydrolysed and analysed by p.c. and GLC, showing Rha (20 %), Ara (16 %), Gal (64 %) and also uronic acids (45 %). Partial hydrolysis gave rise to a polysaccharide free of arabinose, with 46 % of uronic acids. Methylation analysis (GLC -MS) indicated a chain of (1 4) - linked Gal/ (42 % of 2,3,6-Me3-Gal). 

---