Cellulose diffraction

FIGURE 5.17 Cellulose diffraction patterns. Top left synchrotron radiation x-ray diffraction pattern for cotton fiber bundle. The fiber was vertical and the white circle and line correspond to a shadow from the main beam catcher and its support. (Credit to Zakhia Ford.) Top right electron diffraction pattern of fragments of cotton secondary wall. The much shorter arcs in the top right figure are due to the good alignment and small number of crystallites in the electron beam. (Credit to Richard J. Schmidt.) Bottom a synthesized powder pattern for cellulose, based on the unit cell dimensions and crystalline coordinates of Nishiyama et al. [209]. (Credit to Zakhia Ford.) Also shown are the hkl values for the Miller indices. The 2-theta values are for molybdenum radiation instead of the more commonly used copper radiation. 

Cellulose is the main component of the wood cell wall, typically 40—50% by weight of the dry wood. Pure cellulose is a polymer of glucose residues joined by 1,4-P-glucosidic bonds. The degree of polymerization (DP) is variable and may range from 700 to 10,000 DP or more. Wood cellulose is more resistant to dilute acid hydrolysis than hemiceUulose. X-ray diffraction indicates a partial crystalline stmcture for wood cellulose. The crystalline regions are more difficult to hydrolyze than the amorphous regions because removal of the easily hydrolyzed material has Htde effect on the diffraction pattern. 

The superimposition of diffraction spots from both phases gives the previously reported pattern that was thought to require an eight-chain unit cell. In the la stmcture, because of its one-chain unit cell, all chains must have parallel packing. Since the la and ip stmctures exist in the same microfibril of cellulose, the chains in the ip stmcture should also be parallel. 

The dimensions of the unit cells deduced for Cellulose I seem to depend on the kind of plant that is the source of the cellulose wide ranges are reported (64). Since most Cellulose I s are mixtures of two or more stmctures, with mostiy overlapping diffraction spots, the various observed dimensions could result from different amounts of the la, ip, and possibly other forms. 

Similar models for the crystal stmcture of Fortisan Cellulose II came from two separate studies despite quite different measured values of the diffraction intensities (66,70). Both studies concluded that the two chains in the unit cell were packed antiparallel. Hydrogen bonding between chains at the corners and the centers of the unit cells, not found in Cellulose I, was proposed to account for the increased stabiUty of Cellulose II. The same model, with... 

Cellulose III. Cellulose III results from treatment of cellulose with Hquid ammonia (ammonia mercerization) or amines. Cellulose III can be made from either Cellulose I or II. When treated with water. Cellulose III can revert to its parent stmcture. Some cellulose III preparations are much more stable than other preparations. The intensities on diffraction patterns from Cellulose III differ slightly depending on whether the Cellulose III was made from Cellulose I or II, and thus these allomorphs are called IIIj or IHjj- Workers studying III concluded, based partiy on the results of I and II, that the packings of IIIj and IIIjj are parallel and antiparallel, respectively (67). IIIjj also is thought to have hydrogen bonds between the corner and center chains. 

Treatment of the algal cellulose (mixture of la—IP) from Valonia in ethylenediamine to give Cellulose IIIj simultaneously induced sub fibrillation in the initial microfihril (75). Thus crystallites 20 nm wide were spHt into subunits only 3—5 nm wide, even though the length was retained. Conversion of this IIIj back to I gave a material with an electron diffraction pattern and nmr spectmm similar to that of cotton Cellulose ip. 

Those containing less than 7.5% N show a fiber character and give no X-ray diffraction indicating nitration, but only the pattern of mercerized cellulose... 

N are more or less disintegrated, yielding very diffuse diffractions, apparently due in part to very small crystalline elements of mercerized cellulose... 

Five articles on polysaccharide helices solved prior to 1979 have appeared in the volumes published between 1967 and 1982.2-6 The first was a review on X-ray fiber diffraction and its application to cellulose, chitin, amylose, and related structures, and the rest were bibliographic accounts. Since then, X-ray structures of several new polysaccharides composed of simple to complex repeating units have been successfully determined, thanks to technological advances in fiber-diffraction techniques, the availability of fast and powerful computers, and the development of sophisticated software. Also, some old models have been either re-... 

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. 

The phase composition of glycine crystal forms during the drying step of a wet granulation process has been studied, and a model developed for the phase conversion reactions [88], X-ray powder diffraction was used for qualitative analysis, and near-infrared spectroscopy for quantitative analysis. It was shown that when glycine was wet granulated with microcrystalline cellulose, the more rapidly the granulation... 

Fig. 3 (a) The powder x-ray diffraction patterns of microcrystalline cellulose milled... 

Lamellar, single crystals of cellulose triacetate, precipitated from nitromethane with butyl alcohol, were studied by X-ray and electron diffraction. Only the crystals containing the mother liquor, or moistened with nitromethane, showed rich diffraction details. From stretched and annealed fibers, it was found that the unit cell is tetragonal, with a = fe = 21.15A (2.115 nm), and c = 41.36 A (4.136 nm). 

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