Interfacial Adsorption of Oil-Soluble Kraft Lignin and Stabilization of Water-in-Oil Emulsions.

In this paper, the potential of esterified Kraft lignin as a novel oil-soluble surfactant was examined. The lignin was chemically modified by esterification with lauric or stearic acid, making it soluble in solvents such as toluene or n-decane. Adsorption at the oil-water interface was then studied by the Du Noüy ring-method. The oil-soluble lignin behaved similar to water-soluble lignin surfactants, both the qualitative and quantitative progression of interfacial tension. Modeling revealed a surface excess of 7.5-9.0 × 10-7 mol/m2, area per molecule of 185-222 Å2, and a diffusion coefficient within the range 10-10 to 10-14 m2/s; all of which are in line with existing literature on water-soluble lignosulfonates. The data further suggested that the pendant alkyl chains were extended well into the paraffinic solvent. At last, bottle tests showed that the oil-soluble lignin was able to stabilize oil-in-water emulsions. The emulsion stability was affected by the concentration of lignin or NaCl as well as the oil phase composition. Aromatic oils exhibited lower emulsion stability in comparison to the aliphatic oil. In conclusion, a new type of surfactant was synthesized and studied, which may contribute to developing green surfactants and novel approaches to valorize technical lignin.

UV-spectrophotometry dataset of technical lignin in solution after aging and looped measurements.

This article provides UV-spectrophotometry data of technical lignin samples in solutions, which were acquired after ambient aging for up to 110 days or looped measurements on fresh solutions. UV-spectrophotometry of lignin is a useful technique, as it can a) quantify the concentration and purity of lignin in a given sample, b) determine the abundance of phenolic hydroxyl groups, and c) yield qualitative information about chemical modification of the lignin macromolecule. In addition, the technique is rapid and easy to use. Still, solutions of lignin are known to be unstable; in particular at high pH or in presence of UV-light. The data in this article may hence serve as guide in the experimental conduct and design, as it shows the reproducibility of UV-spectrophotometry measurements of lignin. Stock solutions of technical lignin were made according to previously published procedure [1]. The solutions in dimethyl sulfoxide (DMSO) were aged in 100 mL volumetric flasks with glass stopper, taking periodic samples for measurements in a Shimadzu UV-1900 UV-vis spectrophotometer. The instrument recorded the spectrum from 500 to 200 nm at 1.0 nm intervals and medium speed, using quartz cuvettes with a pathlength of 1 cm. In addition, looped measurements were conducted on fresh solutions, where the instrument repeated the spectral range of 500 to 200 nm for in total sixteen times. The latter examined solutions of technical lignin in DMSO solvent as well as in 0.2 N NaOH in water.

Responses of Rat Mesenchymal Stromal Cells to Nanocellulose with Different Functional Groups.

Cellulose nanofibrils (CNFs) are multiscale hydrophilic biocompatible polysaccharide materials derived from wood and plants. TEMPO-mediated oxidation of CNFs (TO-CNF) turns some of the primary hydroxyl groups to carboxylate and aldehyde groups. Unlike carboxylic functional groups, there is little or no information about the biological role of the aldehyde groups on the surface of wood-based CNFs. In this work, we replaced the aldehyde groups in the TO-CNF samples with carboxyl groups by another oxidation treatment (TO-O-CNF) or with primary alcohols with terminal hydroxyl groups by a reduction reaction (TO-R-CNF). Rat mesenchymal stem/stromal cells (MSCs) derived from bone marrow were seeded on polystyrene tissue culture plates (TCP) coated with CNFs with and without aldehyde groups. TCP and TCP coated with bacterial nanocellulose (BNC) were used as control groups. Protein adsorption measurements demonstrated that more proteins were adsorbed from cell culture media on all CNF surfaces compared to BNC. Live/dead and lactate dehydrogenase assays confirmed that all nanocellulose biomaterials supported excellent cell viability. Interestingly, TO-R-CNF samples, which have no aldehyde groups, showed better cell spreading than BNC and comparable results to TCP. Unlike TO-O-CNF surfaces, which have no aldehyde groups either, TO-R-CNF stimulated cells, in osteogenic medium, to have higher alkaline phosphatase activity and to form more biomineralization than TCP and TO-CNF groups. These findings indicate that the presence of aldehyde groups (280 ± 14 µmol/g) on the surface of TEMPO-oxidized CNFs might have little or no effect on attachment, proliferation, and osteogenic differentiation of MSCs.

The influence of temperature on cellulose swelling at constant water density.

We have in this paper investigated how water sorbs to cellulose. We found that both cellulose nanofibril (CNF) and cellulose nanocrystal (CNC) films swell similarly, as they are both mainly composed of cellulose. CNF/CNC films subjected to water at 0.018 kg/m3 at 25 °C and 39 °C, showed a decrease in swelling from ~ 8 to 2%. This deswelling increased the tensile index of CNF-films by ~ 13%. By molecular modeling of fibril swelling, we found that water sorbed to cellulose exhibits a decreased diffusion constant compared to bulk water. We quantified this change and showed that diffusion of sorbed water displays less dependency on swelling temperature compared to bulk water diffusion. To our knowledge, this has not previously been demonstrated by molecular modeling. The difference between bulk water diffusion (DWW) and diffusion of water sorbed to cellulose (DCC) increased from DWW - DCC ~ 3 × 10-5 cm/s2 at 25 °C to DWW - DCC ~ 8.3 × 10-5 cm/s2 at 100 °C. Moreover, water molecules spent less successive time sorbed to a fibril at higher temperatures.

Ultraviolet Spectrophotometry of Lignin Revisited: Exploring Solvents with Low Harmfulness, Lignin Purity, Hansen Solubility Parameter, and Determination of Phenolic Hydroxyl Groups.

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.

A comprehensive investigation on modified cellulose nanocrystals and their films properties.

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 cm3µm/(m2d*kPa) at 50 % RH.

A Core Flood and Microfluidics Investigation of Nanocellulose as a Chemical Additive to Water Flooding for EOR.

Cellulose nanocrystals (CNCs) and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (T-CNFs) were tested as enhanced oil recovery (EOR) agents through core floods and microfluidic experiments. Both particles were mixed with low salinity water (LSW). The core floods were grouped into three parts based on the research objectives. In Part 1, secondary core flood using CNCs was compared to regular water flooding at fixed conditions, by reusing the same core plug to maintain the same pore structure. CNCs produced 5.8% of original oil in place (OOIP) more oil than LSW. For Part 2, the effect of injection scheme, temperature, and rock wettability was investigated using CNCs. The same trend was observed for the secondary floods, with CNCs performing better than their parallel experiment using LSW. Furthermore, the particles seemed to perform better under mixed-wet conditions. Additional oil (2.9-15.7% of OOIP) was produced when CNCs were injected as a tertiary EOR agent, with more incremental oil produced at high temperature. In the final part, the effect of particle type was studied. T-CNFs produced significantly more oil compared to CNCs. However, the injection of T-CNF particles resulted in a steep increase in pressure, which never stabilized. Furthermore, a filter cake was observed at the core face after the experiment was completed. Microfluidic experiments showed that both T-CNF and CNC nanofluids led to a better sweep efficiency compared to low salinity water flooding. T-CNF particles showed the ability to enhance the oil recovery by breaking up events and reducing the trapping efficiency of the porous medium. A higher flow rate resulted in lower oil recovery factors and higher remaining oil connectivity. Contact angle and interfacial tension measurements were conducted to understand the oil recovery mechanisms. CNCs altered the interfacial tension the most, while T-CNFs had the largest effect on the contact angle. However, the changes were not significant enough for them to be considered primary EOR mechanisms.

Blending Gelatin and Cellulose Nanofibrils: Biocomposites with Tunable Degradability and Mechanical Behavior.

Many studies show how biomaterial properties like stiffness, mechanical stimulation and surface topography can influence cellular functions and direct stem cell differentiation. In this work, two different natural materials, gelatin (Gel) and cellulose nanofibrils (CNFs), were combined to design suitable 3D porous biocomposites for soft-tissue engineering. Gel was selected for its well-assessed high biomimicry that it shares with collagen, from which it derives, while the CNFs were chosen as structural reinforcement because of their exceptional mechanical properties and biocompatibility. Three different compositions of Gel and CNFs, i.e., with weight ratios of 75:25, 50:50 and 25:75, were studied. The biocomposites were morphologically characterized and their total- and macro- porosity assessed, proving their suitability for cell colonization. In general, the pores were larger and more isotropic in the biocomposites compared to the pure materials. The influence of freeze-casting and dehydrothermal treatment (DHT) on mechanical properties, the absorption ability and the shape retention were evaluated. Higher content of CNFs gave higher swelling, and this was attributed to the pore structure. Cross-linking between CNFs and Gel using DHT was confirmed. The Young's modulus increased significantly by adding the CNFs to Gel with a linear relationship with respect to the CNF amounts. Finally, the biocomposites were characterized in vitro by testing cell colonization and growth through a quantitative cell viability analysis performed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Additionally, the cell viability analysis was performed by the means of a Live/Dead test with Human mesenchymal stem cells (hMSCs). All the biocomposites had higher cytocompatibility compared to the pure materials, Gel and CNFs.

Production and Mechanical Characterisation of TEMPO-Oxidised Cellulose Nanofibrils/ß-Cyclodextrin Films and Cryogels.

Wood-based TEMPO-oxidised cellulose nanofibrils (toCNF) are promising materials for biomedical applications. Cyclodextrins have ability to form inclusion complexes with hydrophobic molecules and are considered as a method to bring new functionalities to these materials. Water sorption and mechanical properties are also key properties for biomedical applications such as drug delivery and tissue engineering. In this work, we report the modification with ß-cyclodextrin (ßCD) of toCNF samples with different carboxyl contents viz. 756 ± 4 µmol/g and 1048 ± 32 µmol/g. The modification was carried out at neutral and acidic pH (2.5) to study the effect of dissociation of the carboxylic acid group. Films processed by casting/evaporation at 40 °C and cryogels processed by freeze-drying were prepared from ßCD modified toCNF suspensions and compared with reference samples of unmodified toCNF. The impact of modification on water sorption and mechanical properties was assessed. It was shown that the water sorption behaviour for films is driven by adsorption, with a clear impact of the chemical makeup of the fibres (charge content, pH, and adsorption of cyclodextrin). Modified toCNF cryogels (acidic pH and addition of cyclodextrins) displayed lower mechanical properties linked to the modification of the cell wall porosity structure. Esterification between ßCD and toCNF under acidic conditions was performed by freeze-drying, and such cryogels exhibited a lower decrease in mechanical properties in the swollen state. These results are promising for the development of scaffold and films with controlled mechanical properties and added value due to the ability of cyclodextrin to form an inclusion complex with active principle ingredient (API) or growth factor (GF) for biomedical applications.

Bioinspired 3D printable pectin-nanocellulose ink formulations.

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.

High-Temperature Core Flood Investigation of Nanocellulose as a Green Additive for Enhanced Oil Recovery.

Recent studies have discovered a substantial viscosity increase of aqueous cellulose nanocrystal (CNC) dispersions upon heat aging at temperatures above 90 °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 °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.

Wood-based nanocellulose and bioactive glass modified gelatin-alginate bioinks for 3D bioprinting of bone cells.

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.

Oil-in-Water Emulsions Stabilized by Cellulose Nanofibrils-The Effects of Ionic Strength and pH.

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.

Inflammatory responses and tissue reactions to wood-Based nanocellulose scaffolds.

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-1ß, 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-1ß, 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.

Polymeric 3D scaffolds for tissue regeneration: Evaluation of biopolymer nanocomposite reinforced with cellulose nanofibrils.

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.

Coating 3D Printed Polycaprolactone Scaffolds with Nanocellulose Promotes Growth and Differentiation of Mesenchymal Stem Cells.

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.

Identification of Nanocellulose Retention Characteristics in Porous Media.

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.

Swelling and Free-Volume Characteristics of TEMPO-Oxidized Cellulose Nanofibril Films.

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.

Cytocompatibility of Wood-Derived Cellulose Nanofibril Hydrogels with Different Surface Chemistry.

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.

Mechanical Properties of Composite Hydrogels of Alginate and Cellulose Nanofibrils.

Alginate and cellulose nanofibrils (CNF) are attractive materials for tissue engineering and regenerative medicine. CNF gels are generally weaker and more brittle than alginate gels, while alginate gels are elastic and have high rupture strength. Alginate properties depend on their guluronan and mannuronan content and their sequence pattern and molecular weight. Likewise, CNF exists in various qualities with properties depending on, e.g., morphology and charge density. In this study combinations of three types of alginate with different composition and two types of CNF with different charge and degree of fibrillation have been studied. Assessments of the composite gels revealed that attractive properties like high rupture strength, high compressibility, high gel rigidity at small deformations (Young's modulus), and low syneresis was obtained compared to the pure gels. The effects varied with relative amounts of CNF and alginate, alginate type, and CNF quality. The largest effects were obtained by combining oxidized CNF with the alginates. Hence, by combining the two biopolymers in composite gels, it is possible to tune the rupture strength, Young's modulus, syneresis, as well as stability in physiological saline solution, which are all important properties for the use as scaffolds in tissue engineering.