Polysaccharides crystallinity

The authors of [57, 58] got a linear eorrelations between the values of Am,xH of cellulose with water. They earned out the experiment using an adiabatic calorimeter [13, 70, 71] at 298 K with an error of 1.5 % and foimd out that for entirely crystalline cellulose A ,ixH with water is close to zero, whereas for entirely amorphous cellulose it makes -27.1 kJ/mol. Equation (1) relating the enthalpy of cellulose mixing with water and the degree of polysaccharide crystallinity (X, %) was proposed ... 

Several physicochemical properties of dietary fiber contribute to its physiological role. Water-holding capacity, ion-exchange capacity, solution viscosity, density, and molecular kiteractions are characteristics determined by the chemical stmcture of the component polysaccharides, thek crystallinity, and surface area. 

Water-Holding Capacity (WHC). AU polysaccharides are hydrophilic and hydrogen bond to variable amounts of water. HydratabUity is a function of the three-dimensional stmcture of the polymer (11) and is kifluenced by other components ki the solvent. Fibrous polymers and porous fiber preparations also absorb water by entrapment. The more highly crystalline fiber components are more difficult to hydrate and have less tendency to sweU. Stmctural features and other factors, including grinding, that decrease crystallinity or alter stmcture, may iacrease hydratioa capacity and solubUity. 

Hence polysaccharides have been viewed as a potential renewable source of nanosized reinforcement. Being naturally found in a semicrystalline state, aqueous acids can be employed to hydrolyze the amorphous sections of the polymer. As a result the crystalline sections of these polysaccharides are released, resulting in individual monocrystalline nanoparticles [13]. The concept of reinforced polymer materials with polysaccharide nanofillers has known rapid advances leading to development of a new class of materials called Bionanocomposites, which successfully integrates the two concepts of biocomposites and nanometer sized materials. The first part of the chapter deals with the synthesis of polysaccharide nanoparticles and their performance as reinforcing agents in bionanocomposites. 

A similar procedure was adopted for synthesis of nanoparticles of cellulose (CelNPs). The polysaccharide nanoparticles were derivatised under ambient conditions to obtain nanosized hydrophobic derivatives. The challenge here is to maintain the nanosize even after derivatisation due to which less vigorous conditions are preferred. A schematic synthesis of acetyl and isocyanate modified derivatives of starch nanoparticles (SNPs) is shown in scheme 3. The organic modification was confirmed from X-ray diffraction (XRD) pattern which revealed that A- style crystallinity of starch nanoparticles (SNPs) was destroyed and new peaks emerged on derivatisation. FT-IR spectra of acetylated derivatives however showed the presence of peak at 3400 cm- due to -OH stretching indicating that the substitution is not complete. 

Naturally, very long T,c values are expected for solids as viewed from the expected correlation time at the low temperature side of the T c minimum (0.1-0.2 s) as shown in Figure 1. Indeed, their values turns out to be the order of 10-30 s for carbon sites in the absence of internal fluctuations as in polysaccharides such as (1 — 3)-p-D-glucan and (1 —> 3)-p-D-xylan,46 8 fibrous proteins such as collagen49 and silk fibroin,50 free and metal-complexed ionophores,51 or in some instances up to 1000 s as in crystalline polyethylene.52... 

It is of interest to note that the crystalline barium heparinate, which is an acid salt, tends to lose its anticoagulant powers very readily and that the authors consider that sulfur content gives no indication of heparin activity.93 Some polysaccharide sulfuric esters from marine algae possess anticoagulant activity. 

The marked advances made in the study of bacterial polysaccharides serve only to emphasize the vast amount of work still to be carried out in this field. The recent remarkable achievements in enzymic chemical synthesis (starch, crystalline sucrose, etc.) indicate the growing necessity for greater cooperation11 between enzymologist and chemist in the solution of many biological phenomena. 

Dermatan sulfate, also termed chondroitin sulfate B, a related glycosaminoglycan constituent of connective tissue, was known to be composed of galactosamine and a uronic acid, originally believed to be glucuronic acid but then claimed to be iduronic acid based largely on color reactions and paper chromatography. However, the d or L-enantiomer status of the latter monosaccharide was not clear. Jeanloz and Stoffyn unequivocally characterized the monosaccharide as L-iduronic acid by consecutive desulfation, reduction, and hydrolysis of the polysaccharide, followed by isolation of the crystalline 2,3,4-tri-0-acetyl-l,6-anhydro-/ -L-idopyranose, which was shown to be identical to an authentic specimen synthesized from 1,2-0-isopropylidene-/ -L-idofuranose.34... 

The liquid was then evaporated in vacuo to a small volume and two volumes of 95% ethanol were added. A small amount of flocculent precipitate, probably consisting of yeast polysaccharides, was removed by centrifugation, and the solution was concentrated to a sirup in a vacuum oven at 40°. This colorless sirup, when treated with hot absolute alcohol and stirred, set to a crystalline mass. The crystals were filtered, washed with alcohol and ether and dried in vacuo at 70°. The yield was 2.8 g. 

It is noteworthy that D-fructose, which has a pyranose structure in the free crystalline state, assumes a furanose configuration whenever it combines with another sugar to form an oligosaccharide or polysaccharide. Apparently the ketohexose L-sorbose shows the same behavior. 

Catalytic reduction and methanolysis of the methylated capsular polysaccharide of Type III pneumococcus gives a mixture of methyl 2,3,6-trimethyl- and 2,4-dimethyl-a/3-D-glucopyranosides. The latter, which arises from glucuronic acid units in the polysaccharide, can be separated into crystalline a- and 6-isomers identical with synthetic specimens.84,88... 

Like most polysaccharides it is polydisperse with a high molecular weight. Its degree of polymerisation is typically between 10000 and 15000 glucose residues depending upon source and it is never found in a completely crystalline form, but occurs as a partly crystalline... 

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