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.

Modern technology has enabled the isolation of nanocellulose from plant-based fibers, and the current trend focuses on utilizing nanocellulose in a broad range of sustainable materials applications. Water is generally seen as a detrimental component when in contact with nanocellulose-based materials, just like it is harmful for traditional cellulosic materials such as paper or cardboard. However, water is an integral component in plants, and many applications of nanocellulose already accept the presence of water or make use of it. This review gives a comprehensive account of nanocellulose-water interactions and their repercussions in all key areas of contemporary research: fundamental physical chemistry, chemical modification of nanocellulose, materials applications, and analytical methods to map the water interactions and the effect of water on a nanocellulose matrix.

Xylan is tightly associated with cellulose and lignin in secondary plant cell walls, contributing to its rigidity and structural integrity in vascular plants. However, the molecular features and the nanoscale forces that control the interactions among cellulose microfibrils, hemicelluloses, and lignin are still not well understood. Here, we combine comprehensive mass spectrometric glycan sequencing and molecular dynamics simulations to elucidate the substitution pattern in softwood xylans and to investigate the effect of distinct intramolecular motifs on xylan conformation and on the interaction with cellulose surfaces in Norway spruce (Picea abies). We confirm the presence of motifs with evenly spaced glycosyl decorations on the xylan backbone, together with minor motifs with consecutive glucuronation. These domains are differently enriched in xylan fractions extracted by alkali and subcritical water, which indicates their preferential positioning in the secondary plant cell wall ultrastructure. The flexibility of the 3-fold screw conformation of xylan in solution is enhanced by the presence of arabinofuranosyl decorations. Additionally, molecular dynamic simulations suggest that the glycosyl substitutions in xylan are not only sterically tolerated by the cellulose surfaces but that they increase the affinity for cellulose and favor the stabilization of the 2-fold screw conformation. This effect is more significant for the hydrophobic surface compared with the hydrophilic ones, which demonstrates the importance of nonpolar driving forces on the structural integrity of secondary plant cell walls. These novel molecular insights contribute to an improved understanding of the supramolecular architecture of plant secondary cell walls and have fundamental implications for overcoming lignocellulose recalcitrance and for the design of advanced wood-based materials.

Wood, with its constituent building block cellulose, is by far the most common biomaterial on the planet and has been the most important material used by humans to establish civilization. If there is one single biomaterial that should be studied and used by materials scientists across disciplines to achieve a sustainable future, it is cellulose. This perspective provides insights for the general materials science community about the unique properties of wood and cellulose and how they may be used in advanced sustainable materials to make a substantial societal impact. The focus is on sawn wood or cellulose fibers produced at scale by industry and the more recent cellulosic nanomaterials, highlighting the areas where these cellulose‐based materials can be valorized into higher‐order functions. Numerous articles have comprehensively reviewed different areas where cellulose is currently used in advanced materials science. The objective here is to provide general insight for all material scientists and to provide the opinions about the areas in which cellulose and wood have the largest potential to make a significant societal impact, especially to realize next‐generation sustainable materials for construction, food, water, energy, and information. Discussing key areas where future research is needed to open avenues toward a more sustainable future is ended.

The adsorption of nonionic polymers to cellulose is of large importance both in the plant cell wall during synthesis and for the development of sustainable materials from wood. Here, the thermodynamics of adsorption of the polysaccharide xyloglucan (XG) to both native and chemically modified cellulose with carboxyl groups was investigated using molecular dynamics simulations. The free energy of adsorption was calculated as the potential of mean force between an XG oligomer and model cellulose surfaces in a range of temperatures from 298 K to 360 K. It was found that the adsorption near room temperature is an endothermic process dominated by the entropy of released interfacial water molecules. This was corroborated by quantitative assessment of the absolute entropy per water molecule both at the interface and in the bulk. In the case of native cellulose, the adsorption became exothermic at higher temperatures, while the relatively strong interactions between water and the charged groups of the oxidized cellulose impede such a transition. The results also indicate that the extraction of strongly associated hemicelluloses would be facilitated by low temperature.