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Cellulose-based materials represent a renewable, biodegradable, and environmentally friendly alternative to plastic from fossil resources. Nanopaper is a strong and lightweight material formed from cellulose nanofibrils (CNFs). Paper and nanopaper have been considered as excellent alternatives to plastics for use in agriculture and for packaging applications. However, common for both paper and nanopaper is their hydrophilic character, and consequently, poor water-resistance properties. ORMOCER®s are a class of inorganic–organic polymers with excellent barrier and protective properties used for a range of coating applications. Here we present ORMOCER®-coated paper and nanopaper. The coated papers and nanopapers are characterized, both in terms of their morphology, hydrophobicity, and mechanical properties. We demonstrate that the pressure used during the pressing and drying of paper and nanopaper influence their tear and tensile—properties, and that the morphology of the coated nanopaper differs significantly from that of the coated paper. While the ORMOCER® was impregnated within the porous network of the paper, a well-defined two-layered morphology was obtained with the coated nanopaper. Further, the biodegradability of the nanopaper with and without coating was assessed. The degradation study demonstrated that both the pressure used during the pressing and drying of the nanopaper, and the composition of the ORMOCER®, influenced the rate of degradation. Taken together, ORMOCER®-coated paper and nanopaper are promising for the preparation of materials that are both water-resistant, renewable, and biodegradable.

In this article, we explored solvents with lower harmfulness than established systems for UV spectrophotometry of lignin. By measuring the absorptivity in DMSO solvent at 280 nm, the purity of the lignin samples was addressed and compared with Klason and acid-soluble lignin. The general trend was an increasing absorptivity with increasing lignin purity; however, considerable scattering was observed around the sample mean. The Hansen solubility parameter (HSP) of four technical lignins was furthermore determined. The model was in line with the UV measurements, as solvents closer in HSP correlated with a higher absorptivity. Ethylene glycol was identified as a good solvent for lignin with low UV-cutoff. In addition, mixtures of propylene carbonate, water, and ethanol showed good suitability and a low cutoff of 215 nm. While DMSO itself was poorly suited for recording alkali spectra, blending DMSO with water showed great potential. Comparing three methods for determining phenolic hydroxyl units by UV spectrophotometry showed some discrepancies between different procedures and solvents. It appeared that the calibrations established with lignin model compounds may not be fully representative of the lignin macromolecule. More importantly, the ionization difference spectra were highly affected by the solvent of choice, even when using what are considered "good" solvents. At last, a statistical comparison was made to identify the most suitable solvent and method, and the solvent systems were critically discussed. We thus conclude that several solvents were identified, which are less harmful than established systems, and that the solubility of lignin in these is a crucial point to address when conducting UV spectrophotometry.

In this work, we aimed to tune cellulose nanocrystals (CNCs) properties by introducing different functional groups (aldehyde, carboxyl, silane, and ammonium groups) on the surface through different chemical modifications. These functional groups were obtained by combining: the periodate oxidation with TEMPO-oxidation, aminosylation or cationization. CNCs produced and their films were characterized to elucidate their performances. The results showed that the properties of obtained CNCs varied depending on the grafted functionalities on the surface. The results reveal that after each modification a colloidal stability is preserved. Interestingly, Periodate oxidation of cellulose nanocrystals results in film components that interact through intra- and intermolecular hemiacetals and lead to films with a tensile strength of 116 MPa compared to the pristine CNCs, in contrast the subsequent modifications led to lower tensile strength. Of note, remarkable thermal stability has been achieved after modifications reaching a maximum of 280 °C. The oxygen barrier properties of the films after modifications varied between 0.48 and 0.54 cm

This review is the first part of a comprehensive review of hydrophobisation of lignocellulosic materials. The purpose of this review has been to compare physical hydrophobisation methods of lignocellulosic materials. We have compared molecular physical adsorption with plasma etching and grafting. Adsorption methods are facile and rely upon the simple mixing or coating of the substrate with the hydrophobing agent. However, none of the surfactant-based methods reviewed here reach contact angles above 90°, making them unsuitable for applications where a high degree of hydrophobisation is required. Nevertheless, surfactant based methods are well suited for compatibilising the lignocellulosic material with a hydrophobic matrix/polymer in cases where only a slight decrease in the hydrophilicity of the lignocellulosic substrate is required. On the other hand, wax- and lignin-based coatings can provide high hydrophobicity to the substrates. Plasma etching requires a more complex set-up but is relatively cheap. By physically etching the surface with or without the deposition of a hydrophobic coating, the material is rendered hydrophobic, reaching contact angles well above 120°. A major drawback of this method is the need for a plasma etching set-up, and some researchers co-deposit fluorine-based layers, which have a negative environmental impact. An alternative is plasma grafting, where single molecules are grafted on, initiated by radicals formed in the plasma. This method also requires a plasma set-up, but the vast majority of hydrophobic species can be grafted on. Examples include fatty acids, silanes and alkanes. Contact angles well above 110° are achieved by this method, and both fluorine and non-toxic species may be used for grafting. Graphical abstract

The use of wood-derived cellulose nanofibrils (CNFs) or galactoglucomannans (GGM) for emulsion stabilization may be a way to obtain new environmentally friendly emulsifiers. Both have previously been shown to act as emulsifiers, offering physical, and in the case of GGM, oxidative stability to the emulsions. Oil-in-water emulsions were prepared using highly charged (1352 ± 5 µmol/g) CNFs prepared by TEMPO-mediated oxidation, or a coarser commercial CNF, less charged (≈ 70 µmol/g) quality (Exilva forte), and the physical emulsion stability was evaluated by use of droplet size distributions, micrographs and visual appearance. The highly charged, finely fibrillated CNFs stabilized the emulsions more effectively than the coarser, lower charged CNFs, probably due to higher electrostatic repulsions between the fibrils, and a higher surface coverage of the oil droplets due to thinner fibrils. At a constant CNF/oil ratio, the lowest CNF and oil concentration of 0.01 wt % CNFs and 5 wt % oil gave the most stable emulsion, with good stability toward coalescence, but not towards creaming. GGM (0.5 or 1.0 wt %) stabilized emulsions (5 wt % oil) showed no creaming behavior, but a clear bimodal distribution with some destabilization over the storage time of 1 month. Combinations of CNFs and GGM for stabilization of emulsions with 5 wt % oil, provided good stability towards creaming and a slower emulsion destabilization than for GGM alone. GGM could also improve the stability towards oxidation by delaying the initiation of lipid oxidation. Use of CNFs and combinations of GGM and CNFs can thus be away to obtain stable emulsions, such as mayonnaise and beverage emulsions.

In this study, cellulose nanofibrils (CNF) of high charge (H-P-CNF) and screened size (H-P-CNF-S) were fabricated by increasing the charge of phosphorylated cellulose nanofibrils (P-CNFs) during the pre-treatment step of CNF production. Results show that the H-P-CNF have a significantly higher charge (3.41 mmol g-1) compared with P-CNF (1.86 mmol g-1). Centrifugation of H-P-CNF gave a supernatant with higher charge (5.4 mmol g-1) and a reduced size (H-P-CNF-S). These tailored nanocelluloses were added to polyvinyl alcohol (PVA) solutions and the suspensions were successfully coated on porous polysulfone (PSf) supports to produce thin-film nanocomposite membranes. The humid mixed gas permeation tests show that CO2 permeability increases for membranes with the addition of H-P-CNF-S by 52% and 160%, compared with the P-CNF/PVA membrane and neat PVA membrane, respectively.

Abstract Atomic force microscopy (AFM) can be used to quantitatively study nanomaterials in different media, e.g. vacuum, air, or submerged in a liquid. A technique was developed to study swelling of individual cellulose nanofibrils (CNFs) using AFM. As a case study, CNFs with different degrees of crystallinity (DoC) were examined for swellability going from dry to wet (submerged in de-ionized water). Swelling was found to depend on DoC, but no significant correlation between fibril diameter and swellability was seen. Upon introduction of de-ionized water high DoC samples ($$65\pm 2\%$$ 65 ± 2 % ) were found to have a diameter increase of 34% on average, whereas low DoC ($$44\pm 2\%$$ 44 ± 2 % ) were found to have a diameter increase of 44% on average. A tested control, consisting of platinum nanowires on silisium, did not swell. Graphic abstract

Lignocellulosic materials with hydrophobic properties are of great interest for developing sustainable products that can be used in various applications such as packaging, water-repellent and self-cleaning materials, oil and water separation or as reinforcements in biocomposite materials. The hydroxyl functional groups present in cellulose provide the possibility to perform various chemical modifications to the cellulosic substrates that can increase their hydrophobicity. This review is the second part of a comprehensive review on hydrophobization of lignocellulosic materials and summarizes the recent advances in the chemical modification of such substrates. The methods described in this review can provide changes in the hydrophilicity of the materials that range from a small decrease in the initial hydrophilicity of the substrate (contact angles below 90°) to superhydrophobic properties (contact angles above 150°). Additional attention has been paid to whether the modification is limited to the surface of the substrate or if it occurs in the bulk of the material. We also discuss hydrophobized cellulose material applications in packing and oil/water purification. Graphical abstract

This review is the third part of a series of reviews on hydrophobization of lignocellulosic materials, a relevant topic nowadays, due to the need to replace fossil fuel-based materials. The review provides an overview of the hydrophobization of lignocellulosic materials by polymer adsorption, and both chemical and radiation-induced grafting of polymers. While adsorbed polymers are only attached to the surfaces by physical interactions, grafted polymers are chemically bonded to the materials. Radiation-induced grafting is typically the most environmentally friendly grafting technique, even though it provides little control on the polymer synthesis. On the other hand, controlled radical polymerization reactions are more complex but allow for the synthesis of polymers with elaborated architectures and well-defined properties. Overall, a wide range of contact angles can be obtained by polymer adsorption and grafting, from a slight increase in hydrophobicity to superhydrophobic properties. The choice of modification technique depends on the end-use of the modified material, but there is a clear trend towards the use of more environmentally friendly chemicals and processes and the grafting of polymers with complex structures. Graphical abstract

Cellulose nanofibrils (CNFs) have been proposed for use in low-fat food products due to their availability and excellent viscosifying and gel forming abilities. As the CNFs are negatively charged, the presence of other components in foods, such as electrolytes and food additives such as xanthan gum is likely to affect their rheological properties. Hence, the study of these interactions can contribute valuable information of the suitability of CNFs as rheology modifiers and fat replacers. Rheological measurements on aqueous dispersions of TEMPO-oxidized CNFs were performed with variations in concentration of CNFs, concentration of electrolytes and with varying CNF/xanthan ratios. UV–Vis Spectroscopy was used to evaluate the onset of CNF flocculation/aggregation in the presence of electrolytes. The CNF dispersions followed a power-law dependency for viscosity and moduli on CNF concentration. Low electrolyte additions strengthened the CNF network by allowing for stronger interactions, while higher additions led to fibril aggregation, and loss of viscosity, especially under shear. The CNF/xanthan ratio, as well as the presence of electrolytes were shown to be key factors in determining whether the viscosity and storage modulus of CNF dispersions increased or decreased when xanthan was added.

In this work fully biomass-based hydrogels were developed using a naturally occurring vegetable hydrocolloid co-mingled with wood-derived nanocellulose fibrils. Two distinct types of hydrocolloids have been considered: a seaweed-derived biopolymer (alginate) and a plant-derived biopolymer (pectin). To attain nano-structured binary hydrogels, surface-functionalized cellulose nanofibrils (CNFs) bearing carboxyl groups were employed. This study addresses a non-conventional approach of physical gelation that takes place in acidic conditions (pH

International audience; TEMPO-Oxidized cellulose nanofibrils (toCNF), in the form of highly entangled network such as membrane or cryogels, have proven to be of interest for various applications, including drug release or purification by pollutant adsorption. β-Cyclodextrins (β-CDs) have the ability to form inclusion complexes with large amount of hydrophobic molecules, and are considered as a promising way to bring new functionalities to these materials, by reducing drug burst release effect or improving the pollutant adsorption properties. The study of the adsorption β-CDs onto toCNF is then crucial to design toCNF/β-CDs materials, but is very complex due to the chemical proximity between these compounds. In this study, we develop toCNF cryogels containing various types of β-CDs derivatives by physical adsorption. Different protocols for analyzing the interactions between these compounds, such as Isothermal Titration Calorimetry (ITC), Quartz-Crystal Microbalance with dissipation monitoring (QCM-d) and a Phenolphthalein-based protocol (PhP protocol) have been performed. Adsorption between β-CD and toCNF was proven at two different temperatures with ITC. QCM-d measurements allowed measuring adsorption of different β-CDs derivatives onto toCNF, with higher adsorption measured for the modified β-CDs, and with estimated binding capacity ranging from 13.4 to 47.6 μmol/g toCNF. PhP protocol allowed us to monitor the amount of β-CDs released in aqueous environment, highlighting a lower release for modified β-CDs onto toCNF, and the results were consistent with the estimated binding capacity. This quantification of the binding adsorption capacity of various β-CDs is key results for optimizing the design of toCNF/β-CDs materials.

In this paper, we explore the use of nanocelluloses as an additive to poly (vinyl alcohol) (PVA) nanocomposite membranes for CO2/N2 mixed-gas separation. Our findings are that several types of nanocellulose can be used to improve membrane performance. PVA/cellulose nanocrystals (CNC) nanocomposite membranes have the most promising performance, with increased CO2 permeance (127.8 ± 5.5 GPU) and increased CO2/N2 separation factor (39 ± 0.4) compared to PVA composite membranes, with permeance 105.5 ± 1.9 GPU and separation factor 36 ± 0.5. The performance of PVA/CNC membranes is similar compared to PVA/carbon nanotubes (CNTs) membranes shown earlier. Thus, CNTs can be replaced by CNC that is biodegradable and non-toxic. Investigating several different nanocellulose types reveal that a high nanocellulose charge and small nanocellulose particles are important nanocellulose traits that improve membrane performance. © 2019. This is the authors’ accepted and refereed manuscript to the article. Locked until 26 December 2020 due to copyright restrictions. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

3D printed polycaprolactone (PCL) has potential as a scaffold for bone tissue engineering, but the hydrophobic surface may hinder optimal cell responses. The surface properties can be improved by coating the scaffold with cellulose nanofibrils material (CNF), a multiscale hydrophilic biocompatible biomaterial derived from wood. In this study, human bone marrow-derived mesenchymal stem cells were cultured on tissue culture plates (TCP) and 3D printed PCL scaffolds coated with CNF. Cellular responses to the surfaces (viability, attachment, proliferation, and osteogenic differentiation) were documented. CNF significantly enhanced the hydrophilic properties of PCL scaffolds and promoted protein adsorption. Live/dead staining and lactate dehydrogenase release assays confirmed that CNF did not inhibit cellular viability. The CNF between the 3D printed PCL strands and pores acted as a hydrophilic barrier, enhancing cell seeding efficiency, and proliferation. CNF supported the formation of a well-organized actin cytoskeleton and cellular production of vinculin protein on the surfaces of TCP and PCL scaffolds. Moreover, CNF-coated surfaces enhanced not only alkaline phosphatase activity, but also collagen Type-I and mineral formation. It is concluded that CNF coating enhances cell attachment, proliferation, and osteogenic differentiation and has the potential to improve the performance of 3D printed PCL scaffolds for bone tissue engineering.

The current study aims to demonstrate the influence of the surface chemistry of wood-derived cellulose nanofibril (CNF) hydrogels on fibroblasts for tissue engineering applications. TEMPO-mediated oxidation or carboxymethylation pretreatments were employed to produce hydrogels with different surface chemistry. This study demonstrates the following: first, the gelation of CNF with cell culture medium and formation of stable hydrogels with improved rheological properties; second, the response of mouse fibroblasts cultured on the surface of the hydrogels or sandwiched within the materials with respect to cytotoxicity, cell attachment, proliferation, morphology, and migration. Indirect cytotoxicity tests showed no toxic effect of either hydrogel. The direct contact with the carboxymethylated hydrogel adversely influenced the morphology of the cells and limited their spreading, while typical morphology and spreading of cells were observed with the TEMPO-oxidized hydrogel. The porous fibrous structure may be a key to cell proliferation and migration in the hydrogels.

Recent studies have discovered a substantial viscosity increase of aqueous cellulose nanocrystal (CNC) dispersions upon heat aging at temperatures above 90 &deg, C. This distinct change in material properties at very low concentrations in water has been proposed as an active mechanism for enhanced oil recovery (EOR), as highly viscous fluid may improve macroscopic sweep efficiencies and mitigate viscous fingering. A high-temperature (120 &deg, C) core flood experiment was carried out with 1 wt. % CNC in low salinity brine on a 60 cm-long sandstone core outcrop initially saturated with crude oil. A flow rate corresponding to 24 h per pore volume was applied to ensure sufficient viscosification time within the porous media. The total oil recovery was 62.2%, including 1.2% oil being produced during CNC flooding. Creation of local log-jams inside the porous media appears to be the dominant mechanism for additional oil recovery during nano flooding. The permeability was reduced by 89.5% during the core flood, and a thin layer of nanocellulose film was observed at the inlet of the core plug. CNC fluid and core flood effluent was analyzed using atomic force microscopy (AFM), particle size analysis, and shear rheology. The effluent was largely unchanged after passing through the core over a time period of 24 h. After the core outcrop was rinsed, a micro computed tomography (micro-CT) was used to examine heterogeneity of the core. The core was found to be homogeneous.

Reservoir production is frequently supported by using flooding fluids, often seawater. The efficiency is affected by various factors, such as the wettability of the reservoir rock and the mobility ratio between reservoir oil and injected fluid phase. These factors again influence sweep efficiency, which is the fraction of the total reservoir oil volume in contact with injected fluid during oil recovery. Addition of nanoparticles can affect the sweep efficiency on a macroscopic level by increasing the volume of petroleum in contact with the flooding fluid. Presented here are core-flooding studies performed using cellulose nanocrystals (CNC) of different concentrations in low-saline water. The studies were performed to investigate the injectivity of CNC into a high-permeable sandstone core, and to observe the effects addition of electrolytes had on the rheological properties of a low concentration dispersion of CNC. Zeta- potential and shear viscosity of dilute dispersions containing CNC was investigated under increasing electrolyte concentration. The flooding experiments show that the CNC has good injectivity in sandstone for all concentrations used, and the viscosity measurements performed on the effluent prove that the particles are able to travel through the core. Being sufficiently small for injection into sandstone and showing good colloidal stability at low salinities, CNC particles have the premises necessary to function properly as a flooding additive for enhanced oil recovery (EOR) in sandstone reservoirs.

Pretreatment, fractionation and hydrolysis remains costly and challenging process steps in biochemical conversion of softwoods. Here, ionic liquid pretreatment using 1-ethyl-3-methylimidazolium acetate (EMIM-OAc) at high temperature (100 °C, 6 h) and alkali based (NaOH/urea) pretreatment at sub-zero temperature (−18 °C, 24 h) were compared and combined in studies of Norway Spruce biomass deconstruction. Both treatments significantly improved the enzymatic digestibility of the biomass. EMIM-OAc gave higher glucan than mannan digestibility, indicating a more pronounced effect on the cellulose polymer than on the hemicellulose polymer. In contrast, low temperature alkali pretreatment using NaOH or NaOH + urea gave a more pronounced effect on mannan than on glucan digestibility. By combining the two methods the total monosugar yield after enzymatic hydrolysis was improved by 20–50% as compared to using ionic liquid or alkali based pretreatment alone. Lignin dissolution was low for both methods under the conditions studied.

Polysaccharides are finding an increasing number of applications in medical and pharmaceutical fields thanks to their biodegradability, biocompatibility, and in some cases bioactivity. Two approaches were applied to use hemicelluloses as crosslinkers to tune the structural and mechanical properties of nanofibrillated cellulose (NFC) hydrogel scaffolds, and thus to investigate the effect of these properties on the cellular behavior during wound healing application. Different types of hemicellulose (galactoglucomannan (GGM), xyloglucan (XG), and xylan) were introduced into the NFC network via pre-sorption (Method I) and in situ adsorption (Method II) to reinforce the NFC hydrogels. The charge density of the NFC, the incorporated hemicellulose type and amount, and the swelling time of the hydrogels were found to affect the pore structure, the mechanical strength, and thus the cells’ growth on the composite hydrogel scaffolds. The XG showed the highest adsorption capacity on the NFC, the highest reinforcement effect, and facilitated/promoted cell growth. The pre-sorbed XG in the low-charged NFC network with a lower weight ratio (NFC/XG-90:10) showed the highest efficacy in supporting the growth and proliferation of fibroblast cells (NIH 3T3). These all-polysaccharide composite hydrogels may work as promising scaffolds in wound healing applications to provide supporting networks and to promote cells adhesion, growth, and proliferation.

The applicability of cellulose nanofibrils (CNFs) as viscosifying agent in a starch-reduced low-fat mayonnaise and in an oil-reduced full-fat mayonnaise has been considered. For low-fat mayonnaise a 50 wt% reduction in the ordinary starch content was performed, while for full-fat mayonnaise, the oil content was reduced from 79 to 70 wt%. To study if the stability was affected when CNFs were added, analyses as visual and accelerated stability tests, droplet size measurements and rheology studies, determining the shear viscosity, and the loss and storage moduli, were conducted after 1 day, 1 week and 1 month of storage in room temperature. Even though changes in droplet size distributions and rheological properties indicated some coalescence, the visual stability was not changed after 1 month of storage for any of the samples. The decrease in viscosity and moduli inflicted by reduction of starch or fat, could be regained by the addition of CNFs at 0.75 wt % and 0.42 wt %, respectively. Based on the results in this work, mayonnaise with reduced starch or fat content can be produced when CNFs are used as a viscosifying agent.

The assessment of several ink formulations for 3D printing based on two natural macromolecular compounds is presented. In the current research we have exploited the fast crosslinking potential of pectin and the remarkable shear-thinning properties of carboxylated cellulose nanofibrils, which is known to induce a desired viscoelastic behavior. Prior to 3D printing, the viscoelastic properties of the polysaccharide inks were evaluated by rheological measurements and injectability tests. The reliance of the printing parameters on the ink composition was established through one-dimensional lines printing, the base units of 3D-structures. The performance of the 3D-printed structures after ionic cross-linking was evaluated in terms of mechanical properties and rehydration behavior. MicroCT was also used to evaluate the morphology of the 3D-printed objects regarding the effect of pectin/nanocellulose ratio on the geometrical features of scaffolds. The proportionality between the two polymers proved to be the determining factor for the firmness and strength of the printed objects.

Inks for 3D printing based on cellulose nanofibrils (CNFs) or mixtures of CNFs and either cellulose nanocrystals (CNCs) or alginate were assessed by determining their viscoelastic properties i.e. complex viscosity and storage and loss moduli (G′ and G″). Two types of alginates were used, i.e. from Laminaria hyperborea stipe and Macrocystis pyrifera. Shape fidelity of 3D printed grids were qualitatively evaluated and compared to the viscoelastic properties of the inks. The biocomposite gels containing alginate were post stabilized by crosslinking with Ca2+. Mechanical properties of the crosslinked biocomposite gels were assessed. The complex viscosity, G′ and G″ of CNF suspensions increased when the solid content was increased from 3.5 to 4.0 wt%, but levelled off by further increase in CNF solid content. The complex viscosity at low angular frequency at 4 wt% was as high as 104 Pa·s. This seemed to be the necessary viscosity level for obtaining good shape fidelity of the printed structures for the studied systems. By replacing part of the CNFs with CNCs, the complex viscosity, G′ and G″ were reduced and so was also the shape fidelity of the printed grids. The changes in complex viscosity and moduli when CNFs was replaced with alginate depended on the relative amounts of CNFs/alginate. The type of alginate (from either L. hyp. stipe or M. pyr.) did not play a role for the viscoelastic properties of the inks, nor for the printed grids before post stabilization. Replacing CNFs with up to 1.5 wt% alginate gave satisfactory shape fidelity. The effect of adding alginate and subsequent crosslinking with Ca2+, strongly affected the strength properties of the gels. By appropriate choice of relative amounts of CNFs and alginate and type of alginate, the Young’s modulus and rupture strength could be controlled within the range of 30–150 kPa and 1.5–6 kg, respectively. The deformation at rupture was around 55%. The alginate from L. hyp. stipe yields higher Young’s modulus and lower syneresis compared to M. pyr. This shows that the choice of alginate plays a significant role for the mechanical properties of the final product, although it does not influence on the viscoelastic properties of the ink. The choice of alginate should be L. hyp. stipe if high strength is desired.

The influence of cellulose crystallinity on mechanical properties of cellulose nano-fibrils (CNF) was investigated. Degree of crystallinity (DoC) was modified using liquid anhydrous ammonia. Such treatment changes crystal allomorph from cellulose I to cellulose III, a change which was reversed by subsequent boiling in water. DoC was measured using solid state nuclear magnetic resonance (NMR). Crystalline index (CI) was also measured using wide angle X-ray scattering (WAXS). Cotton linters were used as the raw material. The cotton linter was ammonia treated prior to fibrillation. Reduced DoC is seen to associate with an increased yield point and decreased Young modulus. Young modulus is here defined as the maximal slope of the stress–strain curves. The association between DoC and Young modulus or DoC and yield point are both statistically significant. We cannot conclude there has been an effect on strainability. While mechanical properties were affected, we found no indication that ammonia treatment affected degree of fibrillation. CNF was also studied in air and liquid using atomic force microscopy (AFM). Swelling of the nanofibers was observed, with a mean diameter increase of 48.9%.

Two wood-derived cellulose nanofibril (CNF) porous scaffolds were prepared by TEMPO-oxidation and carboxymethylation. The effects of these scaffolds on the production of inflammatory cytokines by human macrophage-like cells (U937) was profiled in vitro after 1 and 3 days and in subcutaneous tissues of rats after 4 and 30 days, using PCR and Multiplex arrays. Tissue culture plates (TCP) and gelatin scaffolds served as controls in vitro and in vivo respectively. After 3 days in vitro, there was no significant difference between the effects of CNF scaffolds and TCP on the production of chemokines/growth factors and pro-inflammatory cytokines. At day 4 in vivo there was significantly higher gene expression of the anti-inflammatory IL-1Ra in the CNF scaffolds than the gelatin scaffold. Production of IL-1β, IL-6, MCP-1, MIP-1α CXCL-1 and M-CSF was significantly less than in the gelatin, demonstrating an early mild inflammatory response. At day 30, both CNF scaffolds significantly stimulated the production of the anti-inflammatory cytokine IL-10. Unlike gelatin, neither CNF scaffold had degraded 180 days post-implantation. The slow degradation of CNF scaffolds resulted in a foreign body reaction, with high production of IL-1β, IL-2, TNF-α, IFN-ϒ, MCP-1, MIP-1α, M-CSF, VEGF cytokines and expression of MMP-9 gene. The surface chemistry of the CNF scaffolds elicited a modest effect on cytokine production and did not shift the inflammatory profile in vitro or in vivo. The decisive role in development of the foreign body reaction was the slow degradation of the CNF scaffolds.

Biopolymers such as gelatin (Gel) and cellulose nanofibrils (CNF) have many of the essential requirements for being used as scaffolding materials in tissue regeneration; biocompatibility, surface chemistry, ability to generate homogeneous hydrogels and 3D structures with suitable pore size and interconnection, which allows cell colonization and proliferation. The purpose of this study was to investigate whether the mechanical behaviour of the Gel matrix can be improved by means of functionalization with cellulose nanofibrils and proper cross-linking treatments. Blending processes were developed to achieve a polymer nanocomposite incorporating the best features of both biopolymers: biomimicry of the Gel and structural reinforcement by the CNF. The designed 3D structures underline interconnected porosity achieved by freeze-drying process, improved mechanical properties and chemical stability that are tailored by CNF addition and different cross-linking approaches. In vitro evaluations reveal the preservation of the biocompatibility of Gel and its good interaction with cells by promoting cell colonization and proliferation. The results support the addition of cellulose nanofibrils to improve the mechanical behaviour of 3D porous structures suitable as scaffolding for tissue regeneration.

Pickering o/w emulsions prepared with 40 wt % rapeseed oil were stabilized with the use of low charged enzymatically treated cellulose nanofibrils (CNFs) and highly charged 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized CNFs. The emulsion-forming abilities and storage stability of the two qualities were tested in the presence of NaCl and acetic acid, at concentrations relevant to food applications. Food emulsions may be an important future application area for CNFs due to their availability and excellent viscosifying abilities. The emulsion characterization was carried out by visual inspection, light microscopy, viscosity measurements, dynamic light scattering and mild centrifugation, which showed that stable emulsions could be obtained for both CNF qualities in the absence of salt and acid. In addition, the enzymatically stabilized CNFs were able to stabilize emulsions in the presence of acid and NaCl, with little change in the appearance or droplet size distribution over one month of storage at room temperature. The work showed that enzymatically treated CNFs could be suitable for use in food systems where NaCl and acid are present, while the more highly charged TEMPO-CNFs might be more suited for other applications, where they can contribute to a high emulsion viscosity even at low concentrations. © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Wood-based cellulose nanofibrils (CNFs) have, in addition to high specific surface area and high surface reactivity, ability to mimic nanostructured collagen in bone extracellular matrix. These properties make CNFs promising materials for bone tissue engineering (BTE). The CNFs degrade slowly in vivo. By blending and cross-linking gelatin (Gel) with CNFs, scaffolds were produced with tuned degradation rate and enhanced mechanical properties, more suitable for BTE applications. This in vitro study aimed to examine initial biological responses of human bone marrow mesenchymal stem cells to cross-linked Gel-CNF scaffolds. The scaffolds were fabricated from 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized CNF blended with Gel and cross-linked either by dehydrothermal treatment (DHT) or by a combination of hexamethylenediamine, genipin, and DHT. CNF scaffolds without cross-linking served as control. The produced scaffolds supported cell attachment, spreading, and osteogenic differentiation. However, the early cell attachment after 1 day and the expression of RUNX2 and SPP1 genes after 7 days were highest in the CNF scaffolds. The results suggest that cross-linked Gel-CNF are cytocompatible and holds potential for BTE applications.

The application of nanotechnology to the petroleum industry has sparked recent interest in increasing oil recovery, while reducing environmental impact. Nanocellulose is an emerging nanoparticle that is derived from trees or waste stream from wood and fiber industries. Thus, it is taken from a renewable and sustainable source, and could therefore serve as a good alternative to current Enhanced Oil Recovery (EOR) technologies. However, before nanocellulose can be applied as an EOR technique, further understanding of its transport behavior and retention in porous media is required. The research documented in this paper examines retention mechanisms that occur during nanocellulose transport. In a series of experiments, nanocellulose particles dispersed in brine were injected into sandpacks and Berea sandstone cores. The resulting retention and permeability reduction were measured. The experimental parameters that were varied include sand grain size, nanocellulose type, salinity, and flow rate. Under low salinity conditions, the dominant retention mechanism was adsorption and when salinity was increased, the dominant retention mechanism shifted towards log-jamming. Retention and permeability reduction increased as grain size decreased, which results from increased straining of nanocellulose aggregates. In addition, each type of nanocellulose was found to have significantly different transport properties. Experiments with Berea sandstone cores indicate that some pore volume was inaccessible to the nanocellulose. As a general trend, the larger the size of aggregates in bulk solution, the greater the observed retention and permeability reduction. Salinity was found to be the most important parameter affecting transport. Increased salinity caused additional aggregation, which led to increased straining and filter cake formation. Higher flow rates were found to reduce retention and permeability reduction. Increased velocity was accompanied by an increase in shear, which is believed to promote breakdown of nanocellulose aggregates. © 2018 by the authors. Funding details: CERC35, CERC, Canada Excellence Research Chairs, Government of Canada; Funding details: 974 767 880; Funding details: 262644, I-CORE, Israeli Centers for Research Excellence; Funding details: RGPAS/477902-2015, NSERC, Natural Sciences and Engineering Research Council of Canada; Funding details: 244615/E30, Norges Forskningsråd; Funding details: 244615/E30; Funding details: 262644, CERC, Canada Excellence Research Chairs, Government of Canada; Funding details: NSERC, Natural Sciences and Engineering Research Council of Canada

Nanoparticles in air are of particular concern for public health and employee exposure in work-places. Therefore, it is very important to prepare effective filters for their removal. In this work filters were prepared from nanocellulose, i.e. cellulose nanofibrils (CNF). CNF was produced using two methods giving two different qualities of CNF. One quality had negative charges on the fibril surfaces while the other was neutral, and had in addition thinner fibrils compared to the other qualities. Filter samples were produced from water dispersions of CNF, by removal of the water by freeze drying. The performance of the CNF based filters was assessed and compared with filters based on synthetic polymer fibres. The ability to collect NaCl particles with a broad size distribution, ranging from nanometer to micrometer scale, was determined. CNF filters showed quality values comparable with the synthetic polymer based filters. Filters based on both the two CNF qualities had very good filtration efficiency for a given pressure drop across the filter.

Cellulose nanocrystals (CNC) were investigated for use in a potential new application, enhanced oil recovery. Core flooding experiments were performed on outcrop sandstone cores using CNC particles dispersed in low salinity brine (CNC–LS). Core flooding experiments performed on fully water-saturated cores confirm that a majority of viscosity-generating CNC particles successfully traverse the cores at temperature conditions ranging from 60 to 120 °C. Oil recovery tests performed on crude oil saturated sandstone cores at 60 and 90 °C show that when CNC–LS is applied in tertiary mode, ultimate oil recovery increases. During tertiary CNC–LS injection, CNC particles exacerbate differential pressure fluctuations, a phenomenon attributable to log jamming in pore throats, causing remobilisation of oil trapped within pore space regions. Results from the current work indicate that CNC particles dispersed in low saline brine remain promising for implementation in enhanced oil recovery operations. This is a post-peer-review, pre-copyedit version of an article published in Cellulose. The final authenticated version is available online at: https://doi.org/10.1007/s10570-018-1715-5

Cellulose nanofibrils (CNFs) are becoming increasingly ubiquitous in diverse technologies requiring sustainable nanoscale species to form or modify films. The objective of the present study is to investigate the swelling behavior and accompanying free volume of self-standing TEMPO-oxidized (TO) CNF films in the presence of water vapor. For this purpose, we have performed time-resolved swelling experiments on films, prepared according to different experimental protocols, at 90% relative humidity (RH) and ambient temperature. Corresponding free-volume characteristics are elucidated by positron annihilation lifetime spectroscopy (PALS) conducted at ambient temperature and several RH levels. Increasing the drying temperature of the films (from ambient to 50 °C) is observed to promote an increase in film density, which serves to reduce bulk swelling. These elevated drying temperatures likewise cause the free-volume pore size measured by PALS to decrease, while the corresponding total free-volume fraction remains nearly constant. Similarly, dispersion of TO-CNF into aqueous suspensions by ultrasonication prior to film formation increases both the total free-volume fraction and pore size but reduces the size of individual nanofibrils with little net change in bulk swelling. The swelling and concurrent free-volume measurements reported here generally reveal an increase in the free volume of TO-CNF films with increasing RH.

Artifact-free imaging of cellulose nanofibrils (CNFs) from aqueous nanocellulose suspensions is nontrivial due to frequent irreversible agglomeration and structure damage during the course of sample preparation, especially as water is solidified prior to freeze-drying. In this study, we have examined the morphologies of CNF suspensions prepared by rapid vitrification in two different liquid cryogens—nitrogen and ethane—followed by freeze-drying. Results obtained by scanning electron microscopy confirm that vitrification in liquid ethane not only greatly improves the survivability of fine-scale CNF structural elements but also significantly reduces the propensity for CNF to agglomerate. This is a post-peer-review, pre-copyedit version of an article published in [Cellulose] Locked until 5.6.2019 due to copyright restrictions. The final authenticated version is available online at: https://doi.org/10.1007/s10570-018-1854-8

Xylan is the second most abundant polysaccharide and the most abundant hemicellulose component of soda bagasse pulp. In this study, bleached soda bagasse pulp (SB) and bleached bagasse dissolving pulp (DB) with varying amounts of xylan were fibrillated with a homogenization process. The produced fibrillated materials were used for making nanopaper structures. The surface, physical, mechanical and optical properties of the nanopaper were measured, and the effect of xylan was assessed. Laser profilometry (LP) and field emission scanning electron microscopy were applied to study the degree of the fibrillation. The pulp having the highest xylan content, SB, showed the highest yield of cellulose nanofibrils. Nanopaper produced from SB had a more consolidated structure than that produced from DB. Additionally, SB nanopaper yielded higher tensile strength, lower LP roughness, a higher barrier against oxygen and lower opacity. These results indicate a higher degree of fibrillation of the SB pulp compared to the DB pulp. Hence, the positive effect of xylan for facilitating the fibrillation of the starting pulp fibers was demonstrated.

Cellulose nanofibrils (CNF) form hydrogels at low concentrations. These hydrogels are held together by transient interactions such as entanglement of fibrils, non-specific ionic interactions and hydrogen bonds; and are thus vulnerable for changes in the chemical environment or the influence of mechanical forces. By a covalent crosslinking of the fibrils, stable permanent gels can be formed. In this study we have produced CNF by using TEMPO mediated oxidation followed by fibrillation. During this procedure, carboxyl and aldehyde groups are introduced on the CNF surfaces. The aldehyde groups are suitable sites for crosslinking, as aldehydes readily form covalent bonds to primary amines through formation of Schiff bases. For this purpose the diamines ethylenediamine and hexamethylenediamine, differing with four carbon atoms in the chain, were used as crosslinker molecules. The results show that by varying the concentration and length of the crosslinker molecules, the elastic modulus of the gels could be controlled. The reversible gels were in this way transformed to irreversible gels by a simple water based reaction. Controlling gel strength is one important premise for the use of CNF in applications such as tissue engineering.

A challenge in the extrusion-based bioprinting is to find a bioink with optimal biological and physicochemical properties. The aim of this study was to evaluate the influence of wood-based cellulose nanofibrils (CNF) and bioactive glass (BaG) on the rheological properties of gelatin-alginate bioinks and the initial responses of bone cells embedded in these inks. CNF modulated the flow behavior of the hydrogels, thus improving their printability. Chemical characterization by SEM-EDX and ion release analysis confirmed the reactivity of the BaG in the hydrogels. The cytocompatibility of the hydrogels was shown to be good, as evidenced by the viability of human osteoblast-like cells (Saos-2) in cast hydrogels. For bioprinting, 4-layer structures were printed from cell-containing gels and crosslinked with CaCl2. Viability, proliferation and alkaline phosphatase activity (ALP) were monitored over 14 d. In the BaG-free gels, Saos-2 cells remained viable, but in the presence of BaG the viability and proliferation decreased in correlation with the increased viscosity. Still, there was a constant increase in the ALP activity in all the hydrogels. Further bioprinting experiments were conducted using human bone marrow-derived mesenchymal stem cells (hBMSCs), a clinically relevant cell type. Interestingly, hBMSCs tolerated the printing process better than Saos-2 cells and the ALP indicated BaG-stimulated early osteogenic commitment. The addition of CNF and BaG to gelatin-alginate bioinks holds great potential for bone tissue engineering applications.