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In the cellulose scientific community, hydrogen bonding is often used as the explanation for a large variety of phenomena and properties related to cellulose and cellulose based materials. Yet, hydrogen bonding is just one of several molecular interactions and furthermore is both relatively weak and sensitive to the environment. In this review we present a comprehensive examination of the scientific literature in the area, with focus on theory and molecular simulation, and conclude that the relative importance of hydrogen bonding has been, and still is, frequently exaggerated.

The axial modulus of the cellulose Iβ crystal is as high as 120–160 GPa. The importance of hydrogen bonds is often emphasized in this context, although intrinsic stiffness of the hydrogen bonds is relatively low. Here, hydrogen bond–covalent bond synergies are investigated quantitatively using molecular mechanics and molecular dynamics simulations for the so-called leverage effect, a model introduced recently in which strains for intra-molecular hydrogen bonds are higher than for the cellulose chain as a whole, thereby amplifying their contribution to the total stiffness. The present work also includes simulation of the hydrogen bonding band shifts in vibrational spectra during cellulose deformation, which are compared with FT-IR data. The leverage effect hypothesis was supported by the results, although the total contribution to cellulose stiffness is only 12 %. Hydrogen bonding is still critically important and would lower the modulus much more than 12 %, if “artificially” removed in the model. The reason is that intra-molecular hydrogen bonding preserves the crystal structure and directs axial deformation mechanisms towards higher energy deformation and high stiffness.

An in-depth analysis was performed of the molecular deformation mechanisms in cellulose during axial stretching. For the first time, it was demonstrated that entropy affects the stiffness of cellulose nanocrystals significantly. This was achieved through Molecular Dynamics simulations of model nanocrystals subject to constant stress in the axial direction, for nanocrystals of varying lateral dimensions and at different temperatures. The simulations were analyzed in terms of Young’s modulus E , which is a measure of the elastic response to applied stress. A weak but significant temperature dependence was shown, with ∂ E /∂ T  =  −0.05 Gpa K −1 at room temperature, in agreement with experimental numbers. In order to analyze the respective contributions from internal energy and entropy, a decomposition of the total response of the free energy with respect to strain was made. It was shown that the decrease in E with increasing T is due to entropy, and that the magnitude of the decrease is 6–9 % at room temperature compared to the value at 0 K. This was also shown independently by a direct calculation of the vibrational entropy of the cellulose crystal. Finally, it was found that internal hydrogen bonds are contributing to the stiffness by 20 %, mainly by stabilizing the cellulose internal structure.

Alternative hydrogen-bond structures were found for cellulose II and IIIIbased on molecular dynamics simulations using four force fields and energy optimization based on density functional theory. All the modeling results were in support to the new hydrogen-bonding network. The revised structures of cellulose II and IIIIdiffer with the fiber diffraction models mainly in the orientation of two hydroxyl groups, namely, OH2 and OH6 forming hydrogen-bond chains perpendicular to the cellulose molecule. In the alternative structures, the sense of hydrogen bond is inversed but little difference can be seen in hydrogen bond geometries. The preference of these alternative hydrogen bond structures comes from the local stabilization of hydroxyl groups with respect to the β carbon. On the other hand when simulated fiber diffraction patterns were compared with experimental ones, the current structure of cellulose II with higher energy and the alternative structure of cellulose IIIIwith lower energy were in better agreement.

The solubility of cellulose in water-based media is promoted by low temperature, which may appear counter-intuitive. An explanation to this phenomenon has been proposed that is based on a temperature-dependent orientation of the hydroxymethyl group. In this paper, this hypothesis is investigated using molecular dynamics computer simulations and NMR spectroscopy, and is discussed in conjunction with alternative explanations based on solvent–solute and solvent–solvent hydrogen bond formation respectively. It is shown that neither simulations nor experiments lend support to the proposed mechanism based on the hydroxymethyl orientation, whereas the two alternative explanations give rise to two distinct contributions to the hydration free energy of cellooligomers.

A combined solid-state NMR and Molecular Dynamics simulation study of cellulose in urea aqueous solution and in pure water was conducted. It was found that the local concentration of urea is significantly enhanced at the cellulose/solution interface. There, urea molecules interact directly with the cellulose through both hydrogen bonds and favorable dispersion interactions, which seem to be the driving force behind the aggregation. The CP/MAS 13 C spectra was affected by the presence of urea at high concentrations, most notably the signal at 83.4 ppm, which has previously been assigned to C4 atoms in cellulose chains located at surfaces parallel to the (110) crystallographic plane of the cellulose Iβ crystal. Also dynamic properties of the cellulose surfaces, probed by spin-lattice relaxation time 13 C T 1 measurements of C4 atoms, are affected by the addition of urea. Molecular Dynamics simulations reproduce the trends of the T 1 measurements and lends new support to the assignment of signals from individual surfaces. That urea in solution is interacting directly with cellulose may have implications on our understanding of the mechanisms behind cellulose dissolution in alkali/urea aqueous solutions.

Softwood branches develop compression wood (CW) in the lower parts of the branch, while opposite wood (OW) develops on the upper. These wood types differ in structure at several length scales, among others in the chemical composition of their lignin matrix. While OW mostly contains guaiacyl (G) units, CW is known to contain a substantial fraction of 4-hydroxyphenyl (H) lignin. In this study, the impact this difference has on lignin hygroexpansion and interaction with water is studied by the means of atomistic models and molecular dynamics computer simulations of lignin systems at different levels of hydration. It was found that, despite the minor difference in chemical composition, there are differences in swelling, structure and water dynamics. CW lignin is found to have a higher uniaxial swelling coefficient, since the phase separation between lignin and water is more pronounced. This behavior is linked to structural differences, where intermolecular π - π stacking is more common in CW lignin and hydrogen bonding to water more pronounced in OW lignin. These findings are of interest for understanding the role of lignin in CW, and general understanding of moisture interaction with lignin inside wood cell walls.

The differential swelling seen between softwood opposite wood (OW) and its neighbouring compression wood (CW) developed in branches prompts several engineering issues such as dimensional instability and cracking. For a more efficient use of resources, the inevitable CW and OW should not be discarded or used as fuel, but incorporated into engineered wood products. Swelling is a hygroelastic phenomenon, where both the swelling and elastic properties of CW and OW are needed in order to make proper structural predictions. In this paper, swelling coefficients and moisture dependent elastic moduli for both CW and OW in the three principal material directions are provided along with measurements of moisture content, density, and microfibril angle. The small deformations necessitate the use of precise X-ray micro-computed tomography for measurements. The results indicate that CW and OW from Norway spruce branches differ in swelling, especially in longitudinal direction at low moisture content. It is noted that CW is a wood type with less pronounced anisotropic behaviour than both OW and normal wood from the stem, with the elastic moduli less sensitive to moisture changes in both longitudinal and transverse directions.