Dissolution of cellulose into supercritical water and its dissolving state followed by structure formation from the solution system.

Cellulose was treated with supercritical water at 668 K and 25 MPa for 0.04 s in this study. The cellulose/water system was transparent at room temperature for a while after supercritical water treatment before a precipitate gradually appeared over several hours. The precipitation process was monitored by synchrotron X-ray scattering. The scattering functions of fractal systems and flat-like structures were utilized to explain the experimentally observed small-angle scattering profiles. Immediately after supercritical water treatment, the cellulose appeared to dissolve with a fractal dimension D of approximately 1, indicating that the cellulose molecules were rigid, followed by aggregation into a 5-nm-thick flat-like structure. The flat-like structure was determined to be similar to the molecular sheets observed during the early stages of precipitation in the cellulose/aqueous sodium hydroxide and cellulose/aqueous lithium hydroxide/urea systems. Resultant regenerated cellulose had high crystallinity, large crystal size, and a low degree of polymerization.

Cellulose/glucomannan blends prepared from aqueous sodium hydroxide solution and their practical use as food materials.

Aqueous sodium hydroxide solution is one of the simplest and most environmentally friendly solvents of cellulose. Regenerated cellulose/glucomannan blends were prepared from an aqueous sodium hydroxide solution, and the mechanical properties and structure of the blends were investigated. In addition, the noodle-shaped blends were sensory evaluated as food materials. The blends exhibited porous structures, which corresponded with high water and oil absorption. The strength and modulus of the blends were markedly low, probably due to the highly porous structure. The viscoelastic measurement indicated that cellulose and glucomannan existed in a rubbery state under wet conditions. The blends had a good oral sensation, probably derived from the remarkable porous structure, high water content, low strength and modulus, and rubbery state in wet conditions. The sensory evaluation suggested that the noodle-shaped blends can be used as a food material with a texture similar to capellini pasta.

Comparison of the simulations of cellulosic crystals with three carbohydrate force fields.

Three independently developed molecular mechanics force fields for carbohydrates have been used to simulate a suite of small molecule analogs of cellulose for which crystal structures have been reported, as a test to determine which might be best for simulations of cellulose itself. Such evaluation is necessary since the reported cellulose crystal structure is not stable in molecular dynamics simulations with any available force field. The present simulations found that all three resulted in small deviations from the reported crystal structures, but that all were reasonably accurate and none was clearly superior to the others for the entire suite of structures examined.

Ab initio studies on the structure of and atomic interactions in cellulose III(I) crystals.

The crystal structure of cellulose III(I)was analyzed using first-principles density functional theory (DFT). The geometry was optimized using variable-cell relaxation, as implemented in Quantum ESPRESSO. The Perdew-Burke-Ernzerhof (PBE) functional with a correction term for long-range van der Waals interactions (PBE-D) reproduced the experimental structure well. By using the optimized crystal structure, the interactions existed among the cellulose chains in the crystal were precisely investigated using the NBO analysis. The results showed that the weak bonding nature of CH/O and the hydrogen bonding occur among glucose molecules in the optimized crystal structure. To investigate the strength of interaction, dimeric and trimeric glucose units were extracted from the crystal, and analyzed using MP2 ab initio counterpoise methods with BSSE correction. The results estimated the strength of the interactions. That is, the packed chains along with a-axis interacts with weak bonding nature of CH/O and dispersion interactions by -7.50 kcal/mol, and two hydrogen bonds of O2HO2…O6 and O6HO6…O2 connect the neighboring packed chains with -11.9 kcal/mol. Moreover, FMO4 calculation was also applied to the optimized crystal structure to estimate the strength of the interactions. These methods can well estimate the interactions existed in the crystal structure of cellulose III(I).

Water structuring over the hydrophobic surface of cellulose.

Many important biological solutes possess not only polar and hydrogen-bonding functionalities but also weakly hydrating, or hydrophobic, surfaces. While the aggregation of these hydrophobic surfaces has been shown to play an important role in the aggregation of individual chains of cellulose, it is not known whether the water structuring imposed by these hydrophobic surfaces more closely resembles that associated with small hydrophobic solutes like methane and fats or more closely resembles that associated with extended hydrophobic surfaces like mica or waxy planes. By using molecular dynamics simulations to characterize the water molecule orientations over different regions of the 100 surface of cellulose in contact with water, it was found that the hydrophobic strips of the cellulose crystal are sufficiently narrow that they hydrate like a fatty acid chain, rather than like a more extended surface, suggesting that their aggregation would be dominated by entropy rather than enthalpy.

Folded-chain structure of cellulose II suggested by molecular dynamics simulation.

We investigated the possibility of a folded-chain crystal of the cellulose II polymorph by molecular dynamics (MD) simulation. The molecular direction of cellulose chains in cellulose II is anti-parallel, which allows the crystal to have folded-chain packing. It is impossible for cellulose I to form such a structure due to its parallel up assembly. The folded-chain crystal of the cellulose II polymorph was suggested based on the following results: (1) the glucose residue with boat and skew boat ring conformations enabled the cellulose chain to form a hairpin turn; (2) the lattice parameters of the folded-chain crystal and original crystal were almost the same (deviations in the a, b, and γ parameters of both crystals were within 3%); (3) the folded-chain molecular sheet was as stable in a water medium as the extended-chain molecular sheet, and structural parameters such as the hydrogen bonding system and side chain conformation of both molecular sheets were almost the same, indicating that the folded-chain molecular sheet is an initial structure during crystallization of the folded-chain crystal.

Molecular dynamics simulation of the dissolution process of a cellulose triacetate-II nano-sized crystal in DMSO.

An understanding of the dissolution process of cellulose derivatives is important not only for basic research but also for industrial purposes. We investigated the dissolution process of cellulose triacetate II (CTA II) nano-sized crystal in DMSO solvent using molecular dynamics simulations. The nano-sized crystal consists of 18 CTA chains. During the 9 ns simulation, it was observed that one chain (C01) located at the corner of the lozenge crystal was solvated by the DMSO molecules and moved away from the remaining cluster into the DMSO solvent. The analysis showed that the breakage of the interaction between the H1, H3, and H5 hydrogens of the pyranose ring and the acetyl carbonyl oxygen in the C01 and C02 adjacent chains would be crucial for the dissolution of CTA. The DMSO molecules solvating around these atoms would prevent the re-crystallization of the CTA molecules and facilitate further dissolution.

Supermolecular structure of cellulose/amylose blends prepared from aqueous NaOH solutions and effects of amylose on structural formation of cellulose from its solution.

We previously proposed a mechanism for the structural formation of cellulose from its solution using a molecular dynamics (MD) simulation and suggested that the initial structure from its solution plays a critical role in determining its final structure. Structural changes in the van der Waals-associated cellulose molecular sheet as the initial structure were examined by MD simulation; the molecular sheet was found to be disordered due to maltohexaoses as an amylose model in terms of the hydrogen bonding system of cellulose. The structure and properties of cellulose/amylose blends prepared from an aqueous NaOH solution were examined experimentally by wide-angle X-ray diffraction and dynamic viscoelasticity measurements. The crystallinity of cellulose in the cellulose/amylose blend films was lower than that of cellulose film. The diffraction peaks of the cellulose/amylose blends were slightly shifted; specifically, (1 1 0) was shifted to a higher angle, and (1 1 0) and (0 2 0) were shifted to lower angles. These experimental results probably resulted from the disordered molecular sheet, as revealed by MD simulations.

Structural reorganization of molecular sheets derived from cellulose II by molecular dynamics simulations.

We investigated structural reorganization of two different kinds of molecular sheets derived from the cellulose II crystal using molecular dynamics (MD) simulations, in order to identify the initial structure of the cellulose crystal in the course of its regeneration process from solution. After a one-nanosecond simulation, the molecular sheet formed by van der Waals forces along the (11 0) crystal plane did not change its structure in an aqueous environment, while the other one formed by hydrogen bonds along the (110) crystal plane changed into a van der Waals-associated molecular sheet, such as the former. The two structures that were calculated showed substantial similarities such as the high occupancy of intramolecular hydrogen bonds between O3(H) and O5 of over 0.75, few intermolecular hydrogen bonds, and the high occurrence of hydrogen bonding with water. The convergence of the two structures into one denotes that the van der Waals-associated molecular sheet can be the initial structure of the cellulose crystal formed in solution. The main chain conformations were almost the same as those in the cellulose II crystal except for a -16 degrees shift of phi (dihedral angle of O5-C1-O1-C4) and the gauche-gauche conformation of the hydroxymethyl side group appears probably due to its hydrogen bonding with water. These results suggest that the van der Waals-associated molecular sheet becomes stable in an aqueous environment with its hydrophobic inside and hydrophilic periphery. Contrary to this, a benzene environment preferred a hydrogen-bonded molecular sheet, which is expected to be the initial structure formed in benzene.