Parallel packing cellulose

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. 

Fig. 3.—Parallel packing arrangement of the 2-fold helices of cellulose I (1). (a) Stereo view of two unit cells approximately normal to the ac-plane. The two comer chains (open bonds) in the back, separated by a, form a hydrogen-bonded sheet. The center chain is drawn in filled bonds. All hydrogen bonds are drawn in dashed lines in this and the remaining diagrams, (b) Projection of the unit cell along the c-axis, with a down and b across the page. No hydrogen bonds are present between the comer and center chains.

The cellulose oligomers, beginning with methyl cellotrioside, yield powder diffraction patterns that are very similar to those of cellulose II. The NMR studies of the cellulose oligomers further establish the extensive analogy between cellotetraose and cellulose II. Work by both Gessler et al. [222] and Raymond et al. [223] has shown that the 06 atoms in cellotetraose and methyl cellotrioside [224] all take the gt position, consistent with the diffraction and NMR results for cellulose II. Because the chains in the methyl cellotrioside and cellotetraose are antiparallel, this work adds support to the above results on cellulose II. On the other hand, molecules in crystalline a-lactose, a related disaccharide, have parallel packing [225]. 

One of the most special aspects of cellulose polymorphy is the transformation from I to II. The conversion of the parallel-packed cellulose I structures to an antiparallel cellulose II structure is interesting because it can occur without loss of the fibrous form. This transformation is widely thought to be irreversible, although there are several reports [231-233] of regenerated cellulose I. The observation that there are two different forms of cellulose III and of IV is also remarkable. The two subforms of each allomorph have essentially identical lattice dimensions and at least similar equatorial intensities. Other intensities are different, particularly the meridional intensities, depending on whether the structures were prepared initially from cellulose I or II. The formation of the III and IV structures is reversible and the preceding polymorph (I or II) results. 

Valonia cellulose I was peracetylated under nonswelling conditions. The observations made by electron microscopy and electron diffraction on the fibrous tri-O-acetylcellulose I (CTA I) and the cellulose I obtained by deacetylation thereof led to the conclusion that the chains in CTA I are parallel-packed, as in cellulose I. Similar experiments showed that CTA II and cellulose II have the same antiparallel polarity of the chains in the lattice. 

Atalla and Van der Hart (11, 12) concluded, based on their Raman and NMR spectra, that the molecules in cellulose I and II have different conformations. Based on x-ray analyses, Sarko et al. (13i H) and Blackwell et al. (15, 16) both concluded that crystal structures of cellulose I and II were based on parallel and antiparallel packing, respectively, of chains that have similar backbone conformations. Sarko (17) concluded that the allomorphs in the I and II families were based on parallel and antiparallel chains, respectively. The irreversibility may arise from the increase in entropy when parallel packing is converted to antiparallel packing. 

A prerequisite for this model of stmetural interconversion is the existence of arrays of parallel-packed chains in a single microfibril, the arrays being oriented in up and down directions. The occurrence of such an arrangement was demonstrated in the highly crystalline and well-organized cell-wall of Valonia. Cellulose microfibrils are statistically distributed in opposite polarities wifltin given arrays, where they are packed side by... 

Cellulose, the most abundant renewable organic material produced in the biosphere, is extracted from plants, bacteria, algae, fungi, and tunicates [28]. The structure of nature-derived cellulosic materials is hierarchical. The primary building unit of cellulose is p-l,4,-linked-anhydro-D-glucose. A discrete number of cellulose molecules pack in a parallel fashion to form elementary fibrils, also known as... 

One of the first structures to be determined was the natural polysaccharide cellulose. In this case the repeat unit is cellobiose, composed of two glucoside rings. In the 1980s, NMR experiments established that native cellulose is actually a composite of a triclinic parallel-packed unit cell called cellulose / , and a monoclinic parallel-packed unit cell called cellulose I. Experimentally, the structures are only difficultly distinguishable via X-ray analysis (7a, 7b). Figure 6.1 (3) illustrates the general form of the cellulose unit cell. 

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. 

The major structural characteristics of cellulose I, determined in this and other studies, include extended chains stabilized alorig their lengths W two intramolecular hydrogen bonds per glucose residue (0(3)- 0(5) and 0(6)—0(2) ), the arrangement of the chains into sheets stabilized by one intermolecular hydrogen bond per residue (0(3)—0(6)), and the packing of the sheets into a three-dimensional structure marked by a parallel-chain arrai ement. These structural characteristics are illustrated in Fig. 2. 

The question of parallel vs. antiparallel chain packing in cellulose I has been a controversial one practically since the first cellulose structure was proposed. A consensus appears to be forming, however, based on both diffraction analysis and other experimental evidence, that one of two possible... 

Finally, the question of the ability of the modeling methods to predict the crystal lattice (i.e., the unit cell) from the conformation of the chain should be addressed, despite the expected computational difficulties. Based on previous work, in which the prediction of the unit cells of all four cellulose polymorphs in both parallel and antiparallel chain packing polarities was... 

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... 

Using the two-chain unit-cell,3 with a = 0.817 nm, b = 0.785 nm, c = 1.034 nm, andy = 96.38°, the modified intensity-data of Mann and coworkers,37 and several residue-geometries, the structure of native ramie cellulose was refined. The resulting R factors were 15.8%, 18.5%, and 17.5% for, the antiparallel, parallel-up, and parallel-down models, respectively. A temperature factor of 0.23 nm2 was necessary in order to obtain a good fit with the observed data. It was suggested that the antiparallel packing of the chains cannot be discounted for cotton and ramie celluloses. 

Combined X-ray and electron diffraction analysis led to an orthorhombic unit-cell, with a = 2.468 mn, 1) = 1.152 nm, and c = 1.054 nm. The space group is P2,2,21. Two parallel chains are related, pairwise, by a two-fold screw-axis parallel to the chain axis, and pairs of chains pack in an antiparallel array. The (110) growth planes ol the crystal are parallel to the direction of highest atomic densities. The transformation CTA II cellulose II was discussed. The R factor is 30% with the X-ray diffraction data, and 26% with the electron diffraction data. 

Cellulose fibres are probably packed parallel to one another lengthwise along the axis to form bundles, so called micelles, which are highly oriented along the fibre axis, thus giving cellulose its characteristic mechanical properties. 

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