Crystal microfibrils

Fig. 3. A cross-section of a nearly square cellulose microfibril, with the individual molecular chains shown as rectangles. Also shown are the one- and two-chain unit cells of la and ip. This view of the microfibril is parallel to the long axis. The chains are arranged so that the edges of the crystal correspond...

The mesomorphous phase, also called an intermediate phase or a mesophase, is formed by molecules occurring in surface layers of the crystallites. It can be assumed that the mesophase is made up largely by regularly adjacent reentry folds. However, it cannot be excluded that the mesophase is also composed of some irregular chain folds, which are characterized by a long length and run near the crystal face in the direction perpendicular to the microfibril axis. 

From the foregoing it is clear that indentation anisotropy is a consequence of high molecular orientation within highly oriented fibrils and microfibrils coupled with a preferential local elastic recovery of these rigid structures. We wish to show next that the influence of crystal thickness on AMH is negligible. The latter quantity is independent on 1 and is only correlated to the number of tie molecules and inter-crystalline bridges of the oriented molecular network. 

Except for biopolymers, most polymer materials are polydisperse and heterogeneous. This is already the case for the length distribution of the chain molecules (molecular mass distribution). It is continued in the polydispersity of crystalline domains (crystal size distribution), and in the heterogeneity of structural entities made from such domains (lamellar stacks, microfibrils). Although this fact is known for long time, its implications on the interpretation and analysis of scattering data are, in general, not adequately considered. 

Microencapsulation technique, 13 276-277 Microetching techniques, 19 167 Microextraction, solid-phase, 11 518 Microfermenters, 11 14 Microfibers, 11 186, 240 24 613 Microfibrils, 10 283 11 171 Microfilaments, liquid crystal properties in, 15 111-112... 

We suggest that both the lamellar and the microfibrillar morphologies are formed by a nucleation and growth process. A low nucleation density of crystal solvates results in a lamellar morphology, whereas a high nucleation density of the crystalline PBT results in formation of microfibrils. 

Attempts to examine the process of cellulose crystallization have frequently involved culturing Acetobacter in the presence of fluorescent brighteners, direct dyes, carboxy-methyl-cellulose, or other agents which compete for interchain hydrogen bond sites, thereby disrupting microfibril formation... 

Lamellar, single crystals of ivory-nut mannan were studied by electron diffraction. The base-plane dimensions of the unit cell are a = 0.722 nm and b = 0.892 nm. The systematic absences confirmed the space group P212121. The diffraction pattern did not change with the crystallization temperature. Oriented crystallization ofD-mannan with its chain axis parallel to the microfibril substrates, Valonia ventricosa and bacterial cellulose, was discovered ( hetero-shish-kebabs ). 

The finished cellulose is in the form of crystalline microfibrils (Fig. 20-29), each consisting of 36 separate cellulose chains lying side by side, all with the same (parallel) orientation of nonreducing and reducing ends. It seems likely that each particle in the rosette synthesizes six separate cellulose chains simultaneously and in parallel with the chains made by the other five particles, so that 36 polymers arrive together on the outer surface of the cell, already aligned and ready to crystallize as a microfibril of the cell wall. When the 36 polymers reach some critical length, their synthesis is terminated by an unknown mechanism crystallization into a microfibril follows. 

FIGURE 20-32 A plausible model for the structure of cellulose synthase. The enzyme complex includes a catalytic subunit with eight transmembrane segments and several other subunits that are presumed to act in threading cellulose chains through the catalytic site and out of the cell, and in the crystallization of 36 cellulose strands into the paracrystalline microfibrils shown in Figure 20-29. 

Cellulose synthesis takes place in terminal complexes (rosettes) in the plasma membrane. Each cellulose chain begins as a sitosterol dextrin formed inside the cell. It then flips to the outside, where the oligosaccharide portion is transferred to cellulose synthase in the rosette and is then extended. Each rosette produces 36 separate cellulose chains simultaneously and in parallel. The chains crystallize into one of the microfibrils that form the cell wall. 

The same authors 369,3701 also obtained similar results if the liquid crystal solvent was aligned by flow during the polymerization. They showed that the polymerization conditions lead to alignment of the fibrils within the polymer mass and of the chains within the fibrils polymers produced in this way could also be doped to a conductivity of 104 S cm-1 371). The morphology of polyacetylene produced by polymerization in a liquid crystal solvent, aligned both magnetically and by flow, has been studied by Montaner et al. 371). They show that the polymer film is made up of very long fibrils built from microfibrils. In one fibril, the orientation of microcrystalline domains with respect to the fibril axis is very well defined, whilst the orientation of the different fibrils in the sample spreads over 20°. 

Baldock, C., Sherrat, M. J., Shuttleworth, C. A., and Kielty, C. M. (2003). The super-molecular organisation of collagen VI microfibrils. J. Mol. Biol. 330, 297-307. Bogin, O., Kvansakul, M., Rom, E., Singer, J., Yayon, A., and Hohenester, E. (2002). Insight into Schmid metaphyseal chondrodysplasia from the crystal structure of the collagen X NCI domain trimer. Structure 10, 165-173. 

The refinement (2) proceeded in the same way as for the x-ray work, except that o and S q were refined as additional variables. We assumed that the scattering was kinematic. The cross sectional dimensions of the microfibrils are 200xl0C)X and our previous work on synthetic polymer single crystals showed that the kinematic approximation was adequate for such small crystallites. Intensity measurement presented considerable difficulty in that multiple film exposures could not be obtained. Sequential exposures of the same area of the specimen led to problems of beam damage, and patterns from different areas were not comparable due to differences in the preferred orientation. As a result, only the 28 strongest non-meridional intensities could be measured. These were all for reflections which could be indexed by the Meyer and Misch unit cell, and thus the two chain unit cell was used for the refinement. 

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