Biobased cellulose nanofibrils (CNFs) constitute important building blocks for biomimetic, nanostructured materials, and considerable potential exists in their hybridization with tailorable polymeric nanoparticles. CNFs naturally assemble into oriented, fibrillar structures in their cross-section. This work shows that polymeric nanoparticle additives have the potential to increase or decrease orientation of these cellulose structures, which allows the control of bulk mechanical properties. Small amounts of these additives (<1 wt%) are shown to promote the alignment of CNFs, and the particle size is found to determine a tailorable maximum feature size which can be modified. Herein, X-ray scattering allows for the quantification of orientation at different length scales. This newly developed method of measuring cross-sectional orientation allows for understanding the influence of nanoparticle characteristics on the CNF network structure at different length scales in hybrid cellulose-nanoparticle materials, where previously quantitative description has been lacking. It thus constitutes an important foundation for further development and understanding of nanocellulose materials on the level of their nanoscale building blocks and their interactions, which in turn are decisive for their macroscopic properties.

Membranes and separators are crucial components in many processes and devices. The state-of-the-art fossil-based membranes have a high carbon footprint, and polyfluorinated membranes are increasingly phased out. These limitations lead to an inevitable transition that calls for carbon-neutral membranes with the same or even better performance that can be produced at scale and low cost. Cellulose membranes have the potential to fulfill these criteria if they can be tuned for different purposes. A way to tailor cellulose membranes by preparing them from cellulose fibrils of different refining degrees is presented. The membranes’ effective pore size and permeability to PEG, Fluorescein, and different ions were characterized. The membranes were efficiently used as separators in aqueous-based Zn-ion batteries and PEDOT supercapacitors. This work demonstrates a route toward high-performing and versatile cellulose membranes that can be produced at scale in a more sustainable membrane industry.

Research interest in quaternization of cellulose fibres has increased considerably over the past decades. However, there is little or no consensus regarding how to characterize the material in terms of degree of substitution (DS), and the literature suggests a range of different methods focusing on charge determination as well as nitrogen content quantification. This work aims to fill the knowledge gap regarding how the different methods perform in relation to each other, and for what cellulosic systems each method has advantages, disadvantages and even potential pitfalls. FT-IR and NMR measurements are used to establish successful modification and determine the relative number of substituent groups. Another six methods are compared for the determination of the DS of cellulosic fibres and nanofibrils. The methods include Kjeldahl measurements, nitrogen determination by chemiluminescence, determination of molecular nitrogen by the Dumas method, colloidal titration, conductometric titration and polyelectrolyte adsorption. It can be concluded that most techniques investigated are reliable within certain ranges of DS and/or when using appropriate post-treatment of the quaternized material and suitable sample preparation techniques. The results from the present work hence provide recommendations to make an educated choice of method, and experimental protocol, based on the technique at hand.

Plant cells represent smart cargo carriers with great socioeconomic potential in oral drug delivery applications. The two exterior barriers, featuring a rigid cell wall and a dense plasma membrane, are unique with complementary structural, mechanical, and chemical properties. Current strategies for producing therapeutic drugs within plant cells for oral delivery are efficient, but largely limited to recombinant pharmaceutical proteins, and involve complex genetic modification of plants. To address this, we engineer plant cell–inspired delivery systems with cellulose nanofiber–based shells and lipid layers through a bottom-up assembly strategy, which offers greater flexibility to encapsulate nonprotein compounds and nanoparticles. Notably, the layered shell structure resists degradation in acidic environments, and two barriers respond differently to external stimuli in simulated gastrointestinal medium, resulting in size-dependent dual-triggered release mechanisms. The cytocompatibility was shown by incubation with Caco-2 cells. Our results open avenues for developing next generation of bioinspired oral delivery systems for multisite-specific gastrointestinal release in a low-cost and sustainable manner.

Cellulosic nanomaterials are ideal reinforcers in hydrogel composites, but the current techniques that ensure defined nano-dimensions reduce sustainability. A different strategy for the synthesis of hydrogels from pulp fibers using green chemistry could offer a more sustainable solution. This work explores a mild, straightforward chemical modification with maleic anhydride that simultaneously decorates the fibers with carboxylate and alkene groups. Tuning the temperature of the reaction enables control over the surface charge ranging from 150 to 1,000 μmol/g. The fibers are used to construct a rubber-like, water-stable hydrogel composite prepared by in situ telechelic PEG polymerization followed by thermal or UV-induced free radical crosslinking. The initiation strategy, molecular weight of telechelic PEG, and degree of modification of the fibers enable control over the network formation within and around the fibers. The hydrogel composite is designed to be hydrolytically degradable under alkaline conditions, allowing separate recovery of both fibers and polymer precursors.

Developing ionotronic interface layers for zinc anodes with superior mechanical integrity is one of the efficient strategies to suppress the growth of zinc dendrites in favor of the cycling stability of aqueous zinc-ion batteries (AZIBs). Herein, we assembled robust 2D MXene-based hydrogel films cross-linked by 1D cellulose nanofibril (CNF) dual networks, acting as interface layers to stabilize Zn anodes. The MXene-CNF hydrogel films integrated multifunctionalities, including a high in-plane toughness of 18.39 MJ m-3, high in-plane/out-of-plane elastic modulus of 0.85 and 3.65 GPa, mixed electronic/ionic (ionotronic) conductivity of 1.53 S cm-1 and 0.52 mS cm-1, and high zincophilicity with a high binding energy (1.33 eV) and low migration energy barrier (0.24 eV) for Zn2+. These integrated multifunctionalities, endowed with coupled multifield effects, including strong stress confinement and uniform ionic/electronic field distributions on Zn anodes, effectively suppressed dendrite growth, as proven by experiments and simulations. An example of the MXene-CNF|Zn showed a reduced nucleation overpotential of 19 mV, an extended cycling life of over 2700 h in Zn||Zn cells, and a high capacity of 323 mAh g-1 in Zn||MnO2 cells, compared with bare Zn. This work offers an approach for exploring mechanically robust 1D/2D ionotronic hydrogel interface layers to stabilize the Zn anodes of AZIBs.

Aqueous organic redox flow battery (AORFB) is a technological route towards the large-scale sustainable energy storage. However, several factors need to be controlled to maintain the AORFB performance. Prevention of posolyte and negolyte cross-contamination in asymmetric AORFBs, one of the main causes of capacity decay, relies on their membranes' ability to prevent migration of the redox-active species between the two electrolytes. The barrier properties are often traded for a reduction in ionic conductivity which is crucial to enable the device operation. Another factor greatly affecting quinone-based AORFBs is the Michael addition reaction (MAR) on the charged posolyte, quinone, which has been identified as a major reason for all-quinone AORFBs performance deterioration. Herein, we investigate deterioration scenarios of an all-quinone AORFB using both experimental and computational methods. The study includes a series of membranes based on sulfonated cellulose nanofibrils and different membrane modifications. The layer-by-layer (LbL) surface modifications, i.e. the incorporation of inorganic materials and the reduction of the pore size of the sulfonated cellulose membranes, were all viable routes to reduce the passive diffusion permeability of membranes which correlated to an increased cycling stability of the battery. The kinetics of MAR on quinone was detected using NMR and its impact on the performance fading was modeled computationally. The localization of MAR close to the membrane, which can be assigned to the surface reactivity, affects the diffusion of MAR reagent and the deterioration dynamics of the present all-quinone AORFB.

With the increasing global demand for net-zero carbon emissions, actions to address climate change have gained momentum among policymakers and the public. The urgent need for a sustainable economy is underscored by the mounting waste crisis in landfills and oceans. However, the proliferation of distributed electronic devices poses a significant challenge due to the resulting electronic waste. To combat this issue, the development of sustainable and environmentally friendly materials for these devices is imperative. Cellulose, an abundant and CO2-neutral substance with a long history of diverse applications, holds great potential. By integrating electrically interactive components with cellulosic materials, innovative biobased composites have been created, enabling the fabrication of bulk electroactive paper and the establishment of new, potentially more sustainable manufacturing processes for electronic devices. This review explores recent advances in bulk electroactive paper, including the fundamental interactions between its constituents, manufacturing techniques, and large-scale applications in the field of electronics. Furthermore, it addresses the importance and challenges of scaling up production of electroactive paper, highlighting the need for further research and development.

Thermoplastic properties in cellulosic materials can be achieved by opening the glucose rings in cellulose and introducing new functional groups. Using molecular dynamics, we simulated amorphous cellulose and eight modified versions under dry and moist conditions. Modifications included ring openings and functionalization with hydroxy, aldehyde, hydroxylamine, and carboxyl groups. These modifications were analyzed for density, glass transition temperature, thermal expansivity, hydrogen bond features, changes in energy term contributions during deformation, diffusivity, free volume, and tensile properties. All ring-opened systems exhibited higher molecular mobility, which, consequently, improved thermoplasticity (processability) compared to that of the unmodified amorphous cellulose. Dialcohol cellulose and hydroxylamine-functionalized cellulose were identified as particularly interesting due to their combination of high molecular mobility at processing temperatures (425 K) and high stiffness and strength at room temperature (300 K). Water and smaller side groups improved processability, indicating that both steric effects and electrostatics have a key role in determining the processability of polymers.

In this work we have investigated the effect of surface modification of fibres on the overall mechanical properties of high-density papers. Paper sheets were prepared by a combination of heat-pressing and polyelectrolyte Layer-by-Layer (LbL) modification of different softwood fibres. LbLs of Polyallylamine Hydrochloride (PAH) and Hyaluronic Acid (HA) were adsorbed onto unbleached kraft fibres and bleached Chemo-ThermoMechanical Pulp (CTMP) to improve the strength of the fibre–fibre joints in papers made from these fibres. Additionally, different sheet-making procedures were used to prepare a range of network densities with different degrees of fibre–fibre interaction in the system. The results demonstrate that interfacial adhesion within fibre–fibre joints plays a pivotal role in the network's performance, even at higher paper densities. Hygroexpansion measurements and fracture zone imaging with Scanning Electron Microscopy (SEM) further support the claim that stronger interactions between the fibres allow for a better utilisation of the inherent fibre properties. Surface treatments and network densification significantly improved the paper sheets' mechanical properties. Specifically, LbL-treatments alone increased specific stiffness up to 60% and specific strength by over 100%. This improvement is linked to the build-up of residual stresses during drying. Due to a high interaction between the fibres during water removal the fibres become constrained, leading to increased stretching of fibre segments. Strengthened fibre joints intensify this constraint, further increasing the stretch and, consequently, the paper's strength.