Lignin Nanoparticle Nucleation and Growth on Cellulose and Chitin Nanofibers.

Cellulose (CNF) and chitin (ChNF) nanofibers are known to form materials that are both tough and strong. In this study, we hypothesize that the inertness of networks produced from CNF and ChNF makes them ideal templates for heterogeneous reactions and in situ formation of nanoarchitectures. We expand nanoparticle templating on polysaccharide colloids by introducing a new and facile process that leads to the growth of organic nanoparticles on CNF and ChNF in aqueous media. The process, based on solvent shifting supported on solid interfaces, is demonstrated by direct observation of lignin nanoparticles that are further used for their photocatalytic activity. Importantly, the dynamics of nanoparticle nucleation and growth is correlated with the surface chemistry of the templating nanopolysaccharides. Electrostatic repulsion between the deprotonated lignin molecules and the slightly negative CNF support led to limited adsorption and was effective in producing free (nonbound) lignin nanoparticles (28 ± 7 nm) via precipitation. In contrast, the stronger interfacial interactions between the positively charged ChNF and lignin molecules facilitated instantaneous and extensive lignin adsorption, followed by nucleation and growth into relatively larger nanoparticles (46 ± 17 nm). The latter were homogeneously distributed and strongly coupled to the ChNF support. Overall, we introduce lignin nanoparticle nucleation and growth on renewable nanopolysaccharides, offering an effective route toward in situ synthesis of highly functional fibrils and related cohesive films that offer a great potential in packaging and other applications.

Valorization of Byproducts of Hemp Multipurpose Crop: Short Non-Aligned Bast Fibers as a Source of Nanocellulose.

Nanocellulose was extracted from short bast fibers, from hemp (Cannabis sativa L.) plants harvested at seed maturity, non-retted, and mechanically decorticated in a defibering apparatus, giving non-aligned fibers. A chemical pretreatment with NaOH and HCl allowed the removal of most of the non-cellulosic components of the fibers. No bleaching was performed. The chemically pretreated fibers were then refined in a beater and treated with a cellulase enzyme, followed by mechanical defibrillation in an ultrafine friction grinder. The fibers were characterized by microscopy, infrared spectroscopy, thermogravimetric analysis and X-ray diffraction after each step of the process to understand the evolution of their morphology and composition. The obtained nanocellulose suspension was composed of short nanofibrils with widths of 5-12 nm, stacks of nanofibrils with widths of 20-200 nm, and some larger fibers. The crystallinity index was found to increase from 74% for the raw fibers to 80% for the nanocellulose. The nanocellulose retained a yellowish color, indicating the presence of some residual lignin. The properties of the nanopaper prepared with the hemp nanocellulose were similar to those of nanopapers prepared with wood pulp-derived rod-like nanofibrils.

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.

Tailoring Rheological Properties of Thermoresponsive Hydrogels through Block Copolymer Adsorption to Cellulose Nanocrystals.

This study investigates the adsorption of a block copolymer composed of a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) cationic polyelectrolyte and a poly(di(ethylene glycol) methyl ethermethacrylate) (PDEGMA) on oxidized cellulose nanocrystals (TO-CNCs) to produce hydrogels. PDMEAMA- b-PDEGMA was synthesized by atom-transfer radical polymerization. The extent and dynamics of the adsorption of PDMAEMA- b-PDEGMA on TO-CNCs were determined by electromechanical microbalance and optical techniques. Electrostatic adsorption was identified on TO-CNCs with the quaternized block copolymer. Small-angle neutron scattering experiments were performed to investigate the polymer behavior on the TO-CNC surfaces. Depending on the temperature, block copolymer induces the aggregation of nanocrystals after adsorption by connecting CNCs bundles with block copolymer chains. A reversible liquid-to-gel transition, triggered by temperature, was clearly detected by rheological measurements for the copolymer-CNC mixtures. At the optimal copolymer to CNC ratio the viscosity increased by 4 orders of magnitude at low shear rates. These stimuli-responsive CNC-based materials could be used as injectable biomedical systems.

Current characterization methods for cellulose nanomaterials.

A new family of materials comprised of cellulose, cellulose nanomaterials (CNMs), having properties and functionalities distinct from molecular cellulose and wood pulp, is being developed for applications that were once thought impossible for cellulosic materials. Commercialization, paralleled by research in this field, is fueled by the unique combination of characteristics, such as high on-axis stiffness, sustainability, scalability, and mechanical reinforcement of a wide variety of materials, leading to their utility across a broad spectrum of high-performance material applications. However, with this exponential growth in interest/activity, the development of measurement protocols necessary for consistent, reliable and accurate materials characterization has been outpaced. These protocols, developed in the broader research community, are critical for the advancement in understanding, process optimization, and utilization of CNMs in materials development. This review establishes detailed best practices, methods and techniques for characterizing CNM particle morphology, surface chemistry, surface charge, purity, crystallinity, rheological properties, mechanical properties, and toxicity for two distinct forms of CNMs: cellulose nanocrystals and cellulose nanofibrils.

Cellulose nanofiber (CNF)-sakacin-A active material: production, characterization and application in storage trials of smoked salmon.

BACKGROUND: Sakacin-A due to its specific antimicrobial activity may represent a good candidate to develop active packaging solutions for food items supporting Listeria growth. In the present study a protein extract containing the bacteriocin sakacin-A, produced by Lactobacillus sakei Lb 706 in a low-cost culture medium containing deproteinized cheese whey, was adsorbed onto cellulose nanofibers (CNFs) to obtain an active material to be used as a mat (or a separator) in direct contact with foods. RESULTS: The applied fermentation conditions allowed 4.51 g L-1 of freeze-dried protein extract to be obtained, characterized by an antimicrobial activity of near 16 700 AU g-1 , that was used for the preparation of the active material by casting. The active material was then characterized by infrared spectra and thermogravimetric analyses. Antimicrobial trials were carried out in vitro using Listeria innocua as indicator strain; results were also confirmed in vivo, employing smoked salmon fillets intentionally inoculated with Listeria innocua: its final population was reduced to about 2.5-3 Log cycles after 28 days of storage at 6 °C in presence of sakacin-A, compared with negative control mats produced without the bacteriocin extract. CONCLUSION: This study demonstrates the possibility of producing an antimicrobial active material containing sakacin-A absorbed onto CNFs to decrease Listeria population in smoked salmon, a ready-to eat-food product. © 2019 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Impregnation of paper with cellulose nanocrystal reinforced polyvinyl alcohol: synergistic effect of infrared drying and CNC content on crystallinity.

Paper was impregnated with neat polyvinyl alcohol (PVOH) or cellulose nanocrystal (CNC) reinforced PVOH, and dried by infrared radiation. Complex phenomena involved during paper impregnation and drying have been rarely investigated in the scientific literature, although these steps are crucial for the properties of the ensuing paper. The drying kinetics was studied and it showed that CNC tends to reduce the skin effect classically observed during fast PVOH drying. Furthermore, the nanoparticles induced faster water removal at the end of the drying step, which can be explained by an increase of the absorbed heat flux density. In addition, PVOH crystallization mechanisms have been studied through classical equations (Avrami, and Arrhenius) and a model (the Hoffman-Weeks method) and it was proved that both the drying conditions and the presence of CNC act on the crystallization of the polymer.

Tunable Structural and Mechanical Properties of Cellulose Nanofiber Substrates in Aqueous Conditions for Stem Cell Culture.

Thin cellulose nanofiber (CNF) nanostructured substrates with varying roughness, stiffness (Young's modulus), porosity, and swelling properties were produced by varying the conditions used during fabrication. It was shown that with increased heat exposure, CNF substrate porosity in an aqueous state decreased while Young's modulus in a water submerged state increased. In this study, the adhesion and viability of mesenchymal stem cells (MSCs) cultured on this CNF substrate will be presented. Viability of D1/BALBc MSCs were assessed for 24 and 48 h, and it was shown that depending on the CNF substrate the viability varied significantly. The adhesion of MSCs after 6 and 24 h was conditional on material mechanical properties and porosity of the CNF in cell culture conditions. These results suggest that material properties of CNF nanostructured substrate within the aqueous state can be easily tuned with curing step without any chemical modification to the CNF and that these changes can affect MSC viability in cell culture.

Improvement of the Thermal Stability of TEMPO-Oxidized Cellulose Nanofibrils by Heat-Induced Conversion of Ionic Bonds to Amide Bonds.

Improving thermal stability of TEMPO-oxidized cellulose nanofibrils (TOCNs) is a major challenge for the development and preparation of new nanocomposites. However, thermal degradation of TOCNs occurs at 220 °C. The present study reports a simple way to improve thermal stability of TOCNs by the heat-induced conversion of ionic bonds to amide bonds. Coupling amine-terminated polyethylene glycol to the TOCNs is performed through ionic bond formation. Films are produced from the dispersions by the casting method. Infrared spectroscopy and thermogravimetric analysis confirm conversion of ionic bonds to amide bonds for the modified TOCN samples after heating. As a result, improvement of TOCNs' thermal stability by up to 90 °C is successfully achieved.

Antibacterial paperboard packaging using microfibrillated cellulose.

The industry and consumers are focusing more and more on the development of biodegradable and lightweight food-packaging materials, which could better preserve the quality of the food and improve its shelf-life. In an attempt to meet these requirements, this study presents a novel bio-substrate able to contain active bio-molecules for future food-packaging applications. Based on a paperboard substrate, the development of an antibacterial bio-packaging material is, therein, achieved using a chlorhexidine digluconate (CHX) solution as a model of an antibacterial molecule, mixed with microfibrillated cellulose (MFC) and used as coating onto paperboard samples. AFM and FE-SEM analyses were performed to underline the nanoporous MFC network able to trap and to progressively release the CHX molecules. The release study of CHX was conducted in an aqueous medium and showed a lower proportion (20 %) of CHX released when using MFC. This led to the constant release of low amounts of CHX over 40 h. Antibacterial tests were carried out to assess the preservation of the antibacterial activity of the samples after the release studies. Samples remained active against Bacillus subtilis, with better results being obtained when MFC was used. The preservation of the quality of a model food was finally evaluated paving the way for future promising applications in the food packaging industry.

Green process for chemical functionalization of nanocellulose with carboxylic acids.

An environmentally friendly and simple method, named SolReact, has been developed for a solvent-free esterification of cellulose nanocrystals (CNC) surface by using two nontoxic carboxylic acids (CA), phenylacetic acid and hydrocinnamic acid. In this process, the carboxylic acids do not only act as grafting agent, but also as solvent media above their melting point. Key is the in situ solvent exchange by water evaporation driving the esterification reaction without drying the CNC. Atomic force microscopy and X-ray diffraction analyses showed no significant change in the CNC dimensions and crystallinity index after this green process. The presence of the grafted carboxylic was characterized by analysis of the "bulk" CNC with elemental analysis, infrared spectroscopy, and (13)C NMR. The ability to tune the surface properties of grafted nanocrystals (CNC-g-CA) was evaluated by X-ray photoelectron spectroscopy analysis. The hydrophobicity behavior of the functionalized CNC was studied through the water contact-angle measurements and vapor adsorption. The functionalization of these bionanoparticles may offer applications in composite manufacturing, where these nanoparticles have limited dispersibility in hydrophobic polymer matrices and as nanoadsorbers due to the presence of phenolic groups attached on the surface.

Enzymatic pretreatment for preparing starch nanocrystals.

Starch nanocrystals (SNCs) are crystalline platelets resulting from the acid hydrolysis of starch. A limiting factor for their more widespread use is their preparation duration. Therefore, this study investigates the possibility of developing an enzymatic pretreatment of starch to reduce the acid hydrolysis duration. A screening of three types of enzymes, namely, α-amylase, ß-amylase, and glucoamylase, is proposed, and the latter was selected for a pretreatment. Compared with the regular kinetics of hydrolysis for preparing SNC, that of pretreated starch was much faster. The extent of hydrolysis normally reached in 24 h was obtained after only 6 h, and the regular final yield (15% after 5 days) was reached in 45 h. AFM and X-ray diffraction measurements confirmed that the obtained nanoparticles were indeed SNC.

Water redispersible dried nanofibrillated cellulose by adding sodium chloride.

The present study reports for the first time a method to obtain water redispersible dried NFC using freeze-drying. No chemical surface modification was required to get this kind of product. Salt addition (sodium chloride: NaCl) strategy has been selected to block and then to regenerate hydrogen bonds during the drying and the redispersion steps, respectively. Several samples were produced at different pH (i.e., 4, 6, 8, and 10). All the redispersed NFC were characterized by different techniques (e.g., FE-SEM, XRD, EPMA-EDX) to check the effect of salt on NFC aggregation. The interactions between NFC and NaCl at different pH conditions have been discussed and the rheology of the redispersed NFC suspension has been performed. All the results prove a perfect water redispersion at pH 8 and exactly similar suspension is obtained after water dispersion of dried NFC following our procedure. These results are very promising for increasing application of NFC.

Multilayers of Renewable Nanostructured Materials with High Oxygen and Water Vapor Barriers for Food Packaging.

Natural biopolymers have become key players in the preparation of biodegradable food packaging. However, biopolymers are typically highly hydrophilic, which imposes limitations in terms of barrier properties that are associated with water interactions. Here, we enhance the barrier properties of biobased packaging using multilayer designs, in which each layer displays a complementary barrier function. Oxygen, water vapor, and UV barriers were achieved using a stepwise assembly of cellulose nanofibers, biobased wax, and lignin particles supported by chitin nanofibers. We first engineered several designs containing CNFs and carnauba wax. Among them, we obtained low water vapor permeabilities in an assembly containing three layers, i.e., CNF/wax/CNF, in which wax was present as a continuous layer. We then incorporated a layer of lignin nanoparticles nucleated on chitin nanofibrils (LPChNF) to introduce a complete barrier against UV light, while maintaining film translucency. Our multilayer design which comprised CNF/wax/LPChNF enabled high oxygen (OTR of 3 ± 1 cm3/m2·day) and water vapor (WVTR of 6 ± 1 g/m2·day) barriers at 50% relative humidity. It was also effective against oil penetration. Oxygen permeability was controlled by the presence of tight networks of cellulose and chitin nanofibers, while water vapor diffusion through the assembly was regulated by the continuous wax layer. Lastly, we showcased our fully renewable packaging material for preservation of the texture of a commercial cracker (dry food). Our material showed functionality similar to that of the original packaging, which was composed of synthetic polymers.

Evidence of micro- and nanoscaled particles during starch nanocrystals preparation and their isolation.

Great work has been done to reduce the batch production time of starch nanocrystals (SNCs) and improve their compatibilization with different matrices. However, only one study was reported on SNC production kinetics and none on size distributions and isolation techniques. This study was designed to assess if nonsolubilized particles in the hydrolyzed starch suspension reflect the actual amount of SNC. It was observed that SNCs are produced from a very early stage. It suggests, for the first time, that (i) nanocrystals are mixed together with other microparticles and (ii) some nanocrystals might turn to sugar by the end of the batch production process explaining the low yields. An isolation process has been proposed, but limits of differential centrifugations as washing step and isolation technique were also evidenced. This study clearly shows the need for a continuous production and extraction process of SNC.

Alkaline treatment combined with enzymatic hydrolysis for efficient cellulose nanofibrils production.

Cellulose nanofibrils were efficiently produced from eucalyptus fibers using a combined NaOH and enzymatic treatment followed by a pilot scale grinding process. The structural changes of fibers were assessed after NaOH treatments at 5, 10 and 15 wt% concentrations. A progressive shift from a cellulose I to a cellulose II crystalline structure was observed with X-ray diffraction (XRD) and nuclear magnetic resonance (NMR). The further enzymatic hydrolysis was improved for the NaOH treated samples. The increase of crystallinity indices due to enzymatic hydrolysis was of + 4.7 %, + 3.5 %, and +10.3 % for samples treated with NaOH 5, 10 and 15 wt% respectively, and DP values were drastically reduced to 340, 190 and 166 respectively. A morphological analysis underlined an optimum with the combination of NaOH 10 wt% and enzymatic hydrolysis. This treatment followed by the grinding process resulted in CNF with a rigid structure, with diameters ranging from 10 to 20 nm and lengths between 150 and 350 nm. A multi-scale analysis enabled to study the impact of this combined treatment on CNF properties and energy consumption. A decrease in mechanical properties of nanopapers was observed for the combined treatment and NaOH treatment alone compared to enzymatic hydrolysis alone, with Young's modulus of 8.94, 4.84 and 11.21 GPa respectively. However, optical properties were improved, with transmittance values of 42.2, 15.4 and 7.1 % respectively. This new pretreatment can therefore lead to CNF with tunable properties depending on the application, with possible industrialization thanks to the reduction of energy needs.

Cellulose fibers deconstruction by twin-screw extrusion with in situ enzymatic hydrolysis via bioextrusion.

The aim of this work was to study the cellulose fibers deconstruction by twin-screw extrusion with in situ enzymatic hydrolysis via bioextrusion, for cellulose nanofibrils (CNF) production. Cellulose pulp was extruded with an optimized screw profile, with or without (reference) the addition of an enzymatic solution. An increase of crystallinity index from 67.0% to 73.7% and decrease of DP from 1003 to 419 were observed with bioextrusion. Direct activity measurements of the enzyme confirmed its activity during the process (sugar content increasing from 0.07 ± 0.004 to 2.38 ± 0.003 mg/mL) and after the process (specific activities around 0.20 CMCU/mL). Enzymes were not deactivated during bioextrusion and could be recycled. CNF properties were higher with bioextrusion compared to reference (respective quality indices of 55.5 ± 2.7 and 39.8 ± 2.8), with a lower energy consumption. This proof of concept could be optimized for the industrial production of highly concentrated CNF.

Short communication on the role of cellulosic fiber-based packaging in reduction of climate change impacts.

This short communication describes the climate change impacts of using cellulose, and more precisely cellulosic fiber-based materials, in food packaging, representing current and emerging industrial state of the art technology, without specific reference to current scientific advances. First, the different types of cellulosic fiber-based packaging materials, which can be used to replace fossil-based packaging materials, are presented for flexible and rigid applications. The focus is on technological solutions with packaging properties that enable the protection of commonly sold food products. The manufacturing processes associated with these cellulosic fiber-based materials is described and the environmental impact assessment of 4 selected case studies presented: stand-up pouches, flexible flow wraps, frozen or chilled food trays, and molded pulp lids. A simplified eco-design Life Cycle Assessment (LCA) was then performed to compare each solution with its fossil-based counterpart. Differences and similarities between the various cellulosic solutions have been identified. Furthermore, the assessment confirms that cellulosic fiber-based materials have reduced environmental impacts as compared to fossil-based counterparts, if a similar packaging weight is obtained. Indeed, all impacts of plastics are between 3 and 5 kg CO2eq/kg, while all impacts of cellulosic fiber-based materials are below 1.5 kg CO2eq/kg.

Film thickness limits of a buckling-based method to determine mechanical properties of polymer coatings.

Characterizing the mechanical properties of polymer coatings typically requires access to specialty equipment, the analysis through which can be tedious despite instrumental precision. An alternative method reported in the literature,strain-induced elastic buckling instability for mechanical measurements (SIEBIMM), is a high throughput, facile yet accurate method, used to characterize the Young's modulus of supported films and coatings. SIEBIMM can easily be implemented in both academic and industrial settings. HYPOTHESIS: We hypothesize that the SIEBIMM method has an upper coating thickness limit beyond which the assumptions and practicality of the method are no longer valid. EXPERIMENTS: The Young's moduli of model polyvinyl alcohol coatings (on polydimethylsiloxanesubstrates) with thicknesses ranging from 67 nm to 40 µm were determined using the SIEBIMM method and the data were subjected to a rigorous statistical analysis. FINDINGS: SIEBIMM could accurately characterize coatings up to 35 µm thick. The Young's modulus of all coatings ≤ 35 µm was 1.6 ± 0.1 GPa at 50% RH, which agreed with free-standing polyvinyl alcohol films measured by traditional tensile testing. For the method to be used on thicker coatings, it is essential to consistently measure coating thickness and buckling wavelength at the same location to minimize potential error.

Development of Bio-Inspired Hierarchical Fibres to Tailor the Fibre/Matrix Interphase in (Bio)composites.

Several naturally occurring biological systems, such as bones, nacre or wood, display hierarchical architectures with a central role of the nanostructuration that allows reaching amazing properties such as high strength and toughness. Developing such architectures in man-made materials is highly challenging, and recent research relies on this concept of hierarchical structures to design high-performance composite materials. This review deals more specifically with the development of hierarchical fibres by the deposition of nano-objects at their surface to tailor the fibre/matrix interphase in (bio)composites. Fully synthetic hierarchical fibre reinforced composites are described, and the potential of hierarchical fibres is discussed for the development of sustainable biocomposite materials with enhanced structural performance. Based on various surface, microstructural and mechanical characterizations, this review highlights that nano-objects coated on natural fibres (carbon nanotubes, ZnO nanowires, nanocelluloses) can improve the load transfer and interfacial adhesion between the matrix and the fibres, and the resulting mechanical performances of biocomposites. Indeed, the surface topography of the fibres is modified with higher roughness and specific surface area, implying increased mechanical interlocking with the matrix. As a result, the interfacial shear strength (IFSS) between fibres and polymer matrices is enhanced, and failure mechanisms can be modified with a crack propagation occurring through a zig-zag path along interphases.