Cellulose crystalline polymorphs

For CTA, there are two crystalline polymorphs, CTA I originating from native cellulose, and CTA n obtained from Cellulose II or by complete dissolution of native Cellulose I. As for Cellulose II, an anti-parallel chain arrangement is observed for the CTA II crystal structure. Proceeding from a CTA II crystal structure proposed by Roche et al. [26], Zugenmaier [27] published the atomic coordinates of a refined orthorhombic model. The a - b projection of this model perpendicular to the chain direction is shown in Figure 3.6. 

X-ray diffraction analysis indicates that the cellulose fibers formed from this solvent system exist in the cellulose III polymorph conformation. This polymorph structure is revealed by X-ray diffraction peaks at circa 20.8°, which correspond to both the (002) and (101) planes and another at circa 12.1° which corresponds to the (101) plane. The intensity of these X-ray diffraction peaks of the fiber suggests that it consists of a crystalline structure, in this case cellulose III crystals. As displayed in Table 12.2, the d(oo2) and d(ioi) are similar to those of cellulose III. These interplanar spacings are the average distance between the crystalline unit planes, and they are different from one cellulose polymorph to another. This suggests that the CH2OH moiety of the cellulose polymers are in the gg conformation and are free of... 

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In the present work, we extend the method to compensate for the hydrogen bonds present in carbohydrates. The hydroxylated character of carbohydrate polymers influences between-chain interactions through networks of hydrogen bonds that occur during crystallization. Frequently, several possible attractive interactions exist that lead to different packing arrangements, and several allomorphic crystalline forms have been observed for polysaccharides such as cellulose, chitin, mannan and amylose. The situation is even more complex when water or other guest molecules are present in the crystalline domains. Another complication is that polysaccharide polymorphism includes different helix shapes as well. 

When crystalline cellulose I is treated with aqueous alkali solutions of sufficient strength, a process known as mercerization takes place. As a result of it, cellulose I is converted to cellulose II, the most stable or the four crystalline cellulose polymorphs. The conversion proceeds in the solid state, without apparent destruction or change in the fibrous morphology of the cellulose. As our diffraction analysis indicates, however, it is accompanied by a reversal of the chain packing polarity—from the parallel-chain cellulose I to the... 

Recent studies of the Raman spectra of Celluloses I, II, and IV have indicated that the different polymorphic forms involve two basically different molecular conformations in addition to the differences in crystalline packing (7,8,9). The conformation variations suggested by the Raman spectra are such that they could play an important role in determining the susceptibility of glycosidic linkages to attack by hydrolytic agents. The questions raised by this possibility will be addressed in this chapter. 

There are at least four crystalline forms of cellulose, based on different packing of the primary chain (Blackwell, 1982), and three forms of granular starch, based on the packing of double helices (Noel et al., 1993). The differences are largely in the unit-cell dimensions and the crystallization and precipitation temperatures. One form of starch, precipitated with alcohol, is in a symmetrical molecular arrangement and is readily dispersible in cold water (Kerr, 1950). Mannan and dextran yield different crystals at low and high temperatures, and there was not only a polymorphic difference, but a conformational difference in cellulose (Quenin and Chanzy, 1987). Curdlan appears to have three polymorphs—anhydrous, hydrated, and annealed. 

Detailed structures of many crystalline materials can be determined by diffraction methods. However, because of the complex hierarchy of the cotton fiber and its very small crystallites, diffraction experiments on cotton fibers cannot provide fine details of molecular structure. Instead, the best data on cellulose structure comes from other sources. One of the major points of interest is the finding that cellulose has many different crystalline forms, or polymorphs, depending on the sources and subsequent treatments. Historically, there are four polymorphs or allomorphs, I to IV, and subclasses have been identified for all but cellulose II. 

Cellulose I(S and cellulose II have monoclinic, two-chain unit cells. Cellulose IIIj has a monoclinic one-chain cell [227], and the one-chain unit cell of la is triclinic with no 2i symmetry. Still, all of the chain shapes are very similar to each other. It had been speculated that cellulose chain linkage geometries would alternate between the quite different linkages found in crystalline p-cellobiose and in methyl 3-cellobioside [196]. That idea is now obsolete. Such a departure from symmetry would be far greater than indicated by the above high-resolution studies. When molecules from the high-resolution structures for all of the polymorphs are superimposed, differences in their backbone structures are barely visible. 

Cellulose powders can be created by cutting fibers into small particles, perhaps with a Wiley mill (Arthur H. Thomas Company, Swedesboro, New Jersey). On a laboratory x-ray system, powder diffraction patterns take 30 min. The positions of the peaks indicate the polymorphic form (I-IV) the powder diffraction pattern is often used as a fingerprint for comparison with the known pattern for a given crystalline form [207]. The breadth of the peaks is related to the extent of crystallinity (Figure 5.17, bottom). Using the Scherrer formula [245,246] and assuming no other distortions, the crystallite size can be calculated. Values for cotton perpendicular to the molecular axis are around 40 A. That corresponds to a 6x6 array of... 

The surface of crystallites also represents a portion of the cellulose component readily accessible to chemical agents. Thus, the nature of crystallite surface along with crystallinity influences the apparent accessibility of cellulose, especially when measured by chemical reactions. Among major polymorphs, cellulose I and II are most important in cellulose reactions. 

Quite early in the x-ray diffractometric studies of cellulose it was recognized that its crystallinity is polymorphic. It was established that native cellulose, on the one hand, and both regenrated and mercerized celluloses, on the other, represent two distinct crystallographic allomorphs (14). Little has transpired... 

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