Parallel model cellulose

As the above results show, the gross features of the cellulose I crystal structure predicted by various methods do not differ appreciably, but the accompanying deviations in the R -factors are significant. When these predictions are used to assess, for example, whether the cellulose I crystal structure is based on parallel- or antmarallel-chains, the range in the R"-factors seen for the parallel models (cf. Table II) is comparable to that between the two different polarity models. As shown in Fig. 5, the most probable parallel- and antiparallel-chain structures of cellulose I, refined by minimizing the function O, differ in R -factors by approximately the same extent as the three predictions for the parallel model shown in Fig. 4 and Table II. 

This paper is a review of x-ray diffraction work in the authors laboratory to refine the structures of cellulose I and II, and a- and B-chitin, concentrating on the methods used to select between alternate models. Cellulose I is shown to consist of an array of parallel chains, and this conclusion is supported by a separate refinement based on electron diffraction data. In the case of cellulose II, both parallel and antiparallel chain... 

The crystal structure of native ramie cellulose was shown to be similar to that recently reported for Valonia cellulose. The earlier conclusion that the ramie diffraction data could not be satisfied by a conventional cellulose model is refuted. R (an indication of diffraction error) values of 0.158, 0.185, and 0.175 were obtained for anti-parallel, parallel up, and parallel down alignments respectively. The author considers that the anti-parallel model provides the best accounting for the ramie data and is therefore probably the correct model for both cotton and ramie cellulose. The changes in crystallinity and physical characteristics of microcrystalline cellulose which occur on grinding have been studied. Under one set of grinding conditions, the specific surface area rose... 

Ghosh [548] used cellulose nitrate microporous filters (500 pm thick) as scaffold material to deposit octanol into the pores and then under controlled pressure conditions, displace some of the oil in the pores with water, creating a membrane with parallel oil and water pathways. This was thought to serve as a possible model for some of the properties of the outermost layer of skin, the stratum comeum. The relative proportions of the two types of channel could be controlled, and the properties of 5-10% water pore content were studied. Ibuprofen (lipophilic) and antipyr-ine (hydrophilic) were model drugs used. When the filter was filled entirely with water, the measured permeability of antipyrine was 69 (in 10 6 cm/s) when 90% of the pores were filled with octanol, the permeability decreased to 33 95% octanol content further decreased permeability to 23, and fully octanol-filled filters indicated 0.9 as the permeability. 

Figure 5. Most probable parallel (left) and antiparallel (right) cellulose I models.

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... 

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. 

The favored models are anti-parallel or parallel-up. In both models, one chain has two intramolecular inter-residue hydrogen bonds as in cellulose I, while the other chain has only the 0(3)H- 0(5 ) observed in cellobiose. All hydroxyls are utilized. The parallel-down models appear to be inconsistent with this criterion however, this does not necessarily exclude them from consideration [515]. 

The pyrolysis of wheat straw could be expected to be described by a superposition model, i.e. described by a number of parallel first order reactions, representing the decomposition of the biomass constituents (cellulose, hemicellulose and lignin) [4,5]. In this work, a superposition model has been used, in which the pyrolysis is assumed to be described by N independent first order reactions (for i=l, 2,..., N) ... 

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