Hygroexpansion, CP/MAS 13C-NMR, WAXS and SAXS measurements were carried out on sheets made from four different commercial pulps of varying lignin content. Non-directional laboratory sheets were made at different press levels from the pulps following different degrees of beating. The sheets were dried both freely and with restraints. Measurements were made on sheets before and after moisture cycling to determine hygroexpansion coefficients, changes in cellulose average lateral fibril dimensions and average cellulose crystallite sizes, with the aim of understanding macroscale and nanoscale changes as the result of moisture cycling. Within the sheets consistent and statistically significant structural changes were observed on both macro and nanoscale. On the macroscale, moisture cycling consistently induced irreversible shrinkage in sheets dried with restraints, but less so in the case of sheets dried freely. The hygroexpansion coefficients were typically higher for freely dried sheets compared with sheets dried with constraints. On the nanoscale, moisture cycling consistently caused an increase in the average crystallite sizes (WAXS) and the average lateral fibril dimensions (CP/MAS 13C-NMR), though the latter occurred with poor statistical significance. These changes were interpreted as an increase in the degree of order in the cellulose fibril interior/cellulose crystallite. There were no profound differences in the nanoscale changes observed for sheets dried with restraints and for sheets dried freely. Changes in the fibre wall nanostructure were of similar magnitudes when comparing results from freely dried low grammage sheets (less abundant inter-fibre joints) with freely dried sheets of higher grammage (more abundant inter-fibre joints). No obvious correlations were found between the macroscale and nanoscale measurements. The proposed explanation for this was that the nanoscale structural changes occurred similarly throughout the entirety of the fibre wall, independent of the proximity to an inter-fibre joint, and that the nanoscale structural changes were mainly the result of water penetrating into the interior of cellulose fibril aggregates. By using the same fibril model for evaluation of CP/MAS 13C-NMR and WAXS data, good-to-reasonable agreement were found for estimates of the degree of cellulose crystallinity. 

The high structural anisotropy and colloidal stability of cellulose nanofibrils’ enable the creation of self-standing fibrillar hydrogel networks at very low solid contents. Adding methacrylate moieties on the surface of TEMPO oxidized CNFs allows the formation of more robust covalently crosslinked networks by free radical polymerization of acrylic monomers, exploiting the mechanical properties of these networks more efficiently. This technique yields strong and elastic networks but with an undefined network structure. In this work, we use acrylate-capped telechelic polymers derived from the step-growth polymerization of PEG diacrylate and dithiothreitol to crosslink methacrylated TEMPO-oxidized cellulose nanofibrils (MATO CNF). This combination resulted in flexible and strong hydrogels, as observed through rheological studies, compression and tensile loading. The structure and mechanical properties of these hydrogel networks were found to depend on the dimensions of the CNFs and polymer crosslinkers. The structure of the networks and the role of individual components were evaluated with SAXS (Small-Angle X-ray Scattering) and photo-rheology. A thorough understanding of hybrid CNF/polymer networks and how to best exploit the capacity of these networks enable further advancement of cellulose-based materials for applications in packaging, soft robotics, and biomedical engineering.

Large amounts of cellulose-based waste textiles are generated every year, yet little is done to recycle this waste. Alternatives such as fiber-to-fiber recycling, where a significant part of the value of the waste textiles is recovered, are attractive possibilities. In this study, we have investigated the viability of using hydrated zinc chloride (ZnCl2·4H2O) as a solvent and swelling agent to convert cotton waste textiles (the most abundant cellulose-based waste textile) into a dissolving pulp that can be used as raw material for the production and spinning of viscose fibers. The solvent produced an accessible dissolving pulp and exhibited excellent recyclability, maintaining good dissolving power even after repeated recycling. The dissolving pulp was subsequently used to produce viscose dope, a spinning solution which was spun and cut into viscose staple fibers. The viscose dope exhibited good properties (moderate filter clogging value and gamma number), and the resulting staple fibers were strong and of good quality (high linear density, elongation, and tenacity). These results illustrate the potential of using hydrated zinc chloride for the production of viscose grade dissolving pulp from cotton waste textiles. 

Converting omnipresent environmental energy through the assistance of spontaneous water evaporation is an emerging technology for sustainable energy systems. Developing bio-based hydrovoltaic materials further pushes the sustainability, where wood is a prospect due to its native hydrophilic and anisotropic structure. However, current wood-based water evaporation-assisted power generators are facing the challenge of low power density. Here, an efficient hydrovoltaic wood power generator is reported based on wood cell wall nanoengineering. A highly porous wood with cellulosic network filling the lumen is fabricated through a green, one-step treatment using sodium hydroxide to maximize the wood surface area, introduce chemical functionality, and enhance the cell wall permeability of water. An open-circuit potential of ≈140 mV in deionized water is realized, over ten times higher than native wood. Further tuning the pH difference between wood and water, due to an ion concentration gradient, a potential up to 1 V and a remarkable power output of 1.35 µW cm−2 is achieved. The findings in this study provide a new strategy for efficient wood power generators. © 2022 The Authors. 

The fundamental understanding concerning cellulose-cellulose interactions under wet and dry conditions remains unclear. This is especially true regarding the drying-induced association of cellulose, commonly described as an irreversible phenomenon called hornification. A fundamental understanding of the mechanisms behind hornification would contribute to new drying techniques for cellulose-based materials in the pulp and paper industry while at the same time enhancing material properties and facilitating the recyclability of cellulose-rich materials. In the present work, the irreversible joining of cellulose-rich surfaces has been studied by subjecting cellulose nanofibril (CNF) films to different heat treatments to establish a link between reswelling properties, structural characteristics as well as chemical and mechanical analyses. A heating time/temperature dependence was observed for the reswelling of the CNF films, which is related to the extent of hornification and is different for different chemical compositions of the fibrils. Further, the results indicate that hornification is related to a diffusion process and that the reswellability increases very slowly over long time, indicating that equilibrium is not reached. Hence, hornification is suggested to be a kinetically limited phenomenon governed by non-covalent reversible interactions and a time/temperature dependence on their forming and breaking. © 2023 The Authors

The effect on softwood fiber wall nanostructure of kraft cooking, oxygen delignification and refining was evaluated by X-ray scattering. A recently developed simulation method for modelling small angle X-ray scattering (SAXS) data was used to estimate the apparent average sizes of solids (AAPS) and interstitial spaces in the fiber wall (AACS). Fiber saturation point and wide angle X-ray scattering were also used to calculate the pore volume in the fiber wall and the crystallite size of the fibril, respectively. The experimental modelled SAXS data was able to give consistent values for each kraft-cooked and oxygen-delignified pulp. Kraft delignification seems to have the major influence on the fiber nanostructure modification, while oxygen delignification has little or no significant impact even for different kappa numbers. The particle sizes values were more stable than the cavities sizes and no significant differences were seen between different delignification processes, refining or delignification degree. Pulps evaluated after PFI-refining, showed an increase in the fiber wall porosity evaluated by FSP and an increase in the interstitial spaces in the fiber wall, while the crystallite size and the particle sizes were very little or not affected at all. 

Cellulose rich and cellulose enriched pulps are com. important and scientifically interesting materials with a complex hierarchical fiber wall nanostructure which change with moisture sorption and swelling in water. The fiber wall building blocks and cavities are in size ranges addressable by small angle x-ray scattering (SAXS) but due to large variability in sizes and shapes, extracting quant. data about the fiber wall nanostructure from SAXS data can be challenging. For this purpose, a simulation method was developed for modeling SAXS data recorded on cellulose rich pulps. The modeling method is independent of the establishments of sep. form factors and structure factors and was used to model SAXS data recorded on dense samples. An advantage of the modeling method was that it made it possible to connect exptl. SAXS data to apparent average sizes of particles and cavities at different sample solid contents. Exptl. SAXS data could be modelled as a superposition of a limited number of simulated intensity components and gave results in qual. agreement with CP/MAS 13C-NMR data recorded on the same samples. For the water swollen samples, results obtained by the SAXS modeling method and results obtained from CP/MAS 13C-NMR measurements, agreed on the ranking of particle sizes in the different samples. The SAXS modeling method is dependent on simulations of autocorrelation functions. The time needed for simulations could be reduced by rescaling of simulated correlation functions, due to their independence of the choice of step size in real space. This way an autocorrelation function simulated for a specific sample could be used to generate SAXS intensity profiles corresponding to all length scales for that sample and used for efficient modeling of the exptl. data recorded on that sample.

The fashion industry is becoming one of the largest emitters worldwide due to its high consumption of raw materials, its effluents, and the fact that every garment will eventually contribute to the vast amount of waste being incinerated or accumulating in landfills. Although fiber-to-fiber recycling processes are being developed, the mechanical properties of the textile fibers are typically degraded with each such recycle. Thus, tertiary recycling alternatives where textiles are depolymerized to convert them into valuable products are needed to provide end-of-life alternatives and to achieve circularity in the fashion industry. We have developed a method whereby cotton waste textiles are depolymerized to form a glucose solution, using sulfuric acid as the sole catalyst, with a high yield (>70%). The glucose solution produced in this process has a high concentration (>100 g/L), which reduces the purification cost and makes the process industrially relevant. This method can be applied regardless of the quality of the fibers and could therefore process other cellulosic fibers such as viscose. The glucose produced could subsequently be fermented into butanediol or caprolactam, precursors for the production of synthetic textile fibers, thus retaining the value of the waste textiles within the textile value chain. © 2022 by the authors.

Cellulose-rich never-dried acetate grade Eucalyptus dissolving pulp was used to study the effects on the supramolecular structure of cellulose due to the addition of AlCl3 during drying from acidic conditions (pH 3.5). CP/MAS 13C-NMR was the analytical technique used for taking measures of the cellulose supramolecular structure. In this study AlCl3 was used as source of Al3+, but Al2(SO4)3 has been shown to give the same effect and it is believed that any salt of Al3+ will give the same effect. The presence of AlCl3 increased the average lateral fibril aggregate dimensions some 25% above that reached by the pulp dried without addition of AlCl3. The observed changes in cellulose supramolecular structure due to the addition of AlCl3 are large considering the low AlCl3 concentration that was used. No change in degree of crystallinity was observed as the result of drying, either with or without AlCl3 addition. Although the mechanism of action for AlCl3, causing the observed effects on the cellulose supramolecular structure, is currently not fully understood, the interpretation made was that the presence of AlCl3 increased the agglomeration of the cellulose that always take place during the first drying of cellulosic fibres. This can be seen as an increased degree of physical cross-linking in the cellulose network. 

In this study, the use of cubosomes for topical delivery of the antimicrobial peptide (AMP) LL-37 was investigated. Topical delivery of AMPs is of great interest for treatment of skin infections caused by bacteria, such as Staphylococcus aureus. AMP containing cubosomes were produced by three different preparation protocols and compared: (i) pre-loading, where LL-37 was incorporated into a liquid crystalline gel, which thereafter was dispersed into nanoparticles, (ii) post-loading, where LL-37 was let to adsorb onto pre-formed cubosomes, and (iii) hydrotrope-loading, where LL-37 was incorporated during the spontaneously formed cubosomes in an ethanol/glycerol monooleate mixture. Particle size and size distribution were analyzed using dynamic light scattering (DLS), liquid crystalline structure by small angle x-ray scattering (SAXS) and release of LL-37 by a fluorescamine assay. Proteolytic protection of LL-37 as well as bactericidal effect after enzyme exposure was investigated. The skin irritation potential of cubosomes was examined by an in vitro epidermis model. Finally, the bacterial killing property of the cubosomes was examined by an ex vivo pig skin wound infection model with Staphylococcus aureus. Data showed that a high loading of LL-37 induced formation of vesicles in case of cubosomes prepared by sonication (pre-loading). No release of LL-37 was observed from the cubosomes, indicating strong association of the peptide to the particles. Proteolysis studies showed that LL-37 was fully protected against enzymatic attacks while associated with the cubosomes, also denoting strong association of the peptide to the particles. As a consequence, bactericidal effect after enzyme exposure remained, compared to pure LL-37 which was subjected to proteolysis. No skin irritation potential of the cubosomes was found, thus enabling for topical administration. The ex vivo wound infection model showed that LL-37 in pre-loaded cubosomes killed bacteria most efficient.