Understanding Nanocellulose-Water Interactions: Turning a Detriment into an Asset.

Modern technology has enabled the isolation of nanocellulose from plant-based fibers, and the current trend focuses on utilizing nanocellulose in a broad range of sustainable materials applications. Water is generally seen as a detrimental component when in contact with nanocellulose-based materials, just like it is harmful for traditional cellulosic materials such as paper or cardboard. However, water is an integral component in plants, and many applications of nanocellulose already accept the presence of water or make use of it. This review gives a comprehensive account of nanocellulose-water interactions and their repercussions in all key areas of contemporary research: fundamental physical chemistry, chemical modification of nanocellulose, materials applications, and analytical methods to map the water interactions and the effect of water on a nanocellulose matrix.

Aqueous Processable One-Dimensional Polypyrrole Nanostructured by Lignocellulose Nanofibril: A Conductive Interfacing Biomaterial.

One-dimensional (1D) nanomaterials of conductive polypyrrole (PPy) are competitive biomaterials for constructing bioelectronics to interface with biological systems. Synergistic synthesis using lignocellulose nanofibrils (LCNF) as a structural template in chemical oxidation of pyrrole with Fe(III) ions facilitates surface-confined polymerization of pyrrole on the nanofibril surface within a submicrometer- and micrometer-scale fibril length. It yields a core-shell nanocomposite of PPy@LCNF, wherein the surface of each individual fibril is coated with a thin nanoscale layer of PPy. A highly positive surface charge originating from protonated PPy gives this 1D nanomaterial a durable aqueous dispersity. The fibril-fibril entanglement in the PPy@LCNFs facilely supported versatile downstream processing, e.g., spray thin-coating on glass, flexible membranes with robust mechanics, or three-dimensional cryogels. A high electrical conductivity in the magnitude of several to 12 S·cm-1 was confirmed for the solid-form PPy@LCNFs. The PPy@LCNFs are electroactive and show potential cycling capacity, encompassing a large capacitance. Dynamic control of the doping/undoping process by applying an electric field combines electronic and ionic conductivity through the PPy@LCNFs. The low cytotoxicity of the material is confirmed in noncontact cell culture of human dermal fibroblasts. This study underpins the promises for this nanocomposite PPy@LCNF as a smart platform nanomaterial in constructing interfacing bioelectronics.

Human Dermal Fibroblast Viability and Adhesion on Cellulose Nanomaterial Coatings: Influence of Surface Characteristics.

Biodegradable and renewable materials, such as cellulose nanomaterials, have been studied as a replacement material for traditional plastics in the biomedical field. Furthermore, in chronic wound care, modern wound dressings, hydrogels, and active synthetic extracellular matrices promoting tissue regeneration are developed to guide cell growth and differentiation. Cells are guided not only by chemical cues but also through their interaction with the surrounding substrate and its physicochemical properties. Hence, the current work investigated plant-based cellulose nanomaterials and their surface characteristic effects on human dermal fibroblast (HDF) behavior. Four thin cellulose nanomaterial-based coatings produced from microfibrillar cellulose (MFC), cellulose nanocrystals (CNC), and two TEMPO-oxidized cellulose nanofibers (CNF) with different total surface charge were characterized, and HDF viability and adhesion were evaluated. The highest viability and most stable adhesion were on the anionic CNF coating with a surface charge of 1.14 mmol/g. On MFC and CNC coated surfaces, HDFs sedimented but were unable to anchor to the substrate, leading to low viability.

Solubility of Softwood Hemicelluloses.

It is demonstrated that the molecular solubility of softwood hemicelluloses is significantly influenced by pretreatment of the fibers, extraction, and downstream processing. To quantify these effects, four hemicellulose samples were extracted from different thermomechanical pulps of Norway spruce. The molecular solubility of the samples was characterized by size and molar mass distributions, and the morphology of the molecules was studied using high resolution microscopy techniques. All extracted samples were well dispersed in aqueous media creating transparent dispersions, but dynamic light scattering measurements showed that molecular solubility can only be achieved using specific pretreatments and extractions. The procedure yields acetylated galactoglucomannan (AcGGM)-rich hemicelluloses with an average molar mass of 21-35 kDa and a diameter up to 10 nm but also shows that water is a poor solvent for this sample since an association is detected as soon as the concentration is about 20 g/L. These associated hemicellulose dispersions are still absolutely clear on visual inspection, underlining the need for careful measurement when assessing the solubility of wood hemicelluloses.

Interfacial Engineering of Soft Matter Substrates by Solid-State Polymer Adsorption.

Polymer coating to substrates alters surface chemistry and imparts bulk material functionalities with a minute thickness, even in nanoscale. Specific surface modification of a substate usually requires an active substrate that, e.g., undergoes a chemical reaction with the modifying species. Here, we present a generic method for surface modification, namely, solid-state adsorption, occurring purely by entropic strive. Formed by heating above the melting point or glass transition and subsequent rinsing of the excess polymer, the emerging ultrathin (<10 nm) layers are known in fundamental polymer physics but have never been utilized as building blocks for materials and they have never been explored on soft matter substrates. We show with model surfaces as well as bulk substrates, how solid-state adsorption of common polymers, such as polystyrene and poly(lactic acid), can be applied on soft, cellulose-based substrates. Our study showcases the versatility of solid-state adsorption across various polymer/substrate systems. Specifically, we achieve proof-of-concept hydrophobization on flexible cellulosic substrates, maintaining irreversible and miniscule adsorption yet with nearly 100% coverage without compromising the bulk material properties. The method can be considered generic for all polymers whose Tg and Tm are below those of the to-be-coated adsorbed layer, and whose integrity can withstand the solvent leaching conditions. Its full potential has broad implications for diverse materials systems where surface coatings play an important role, such as packaging, foldable electronics, or membrane technology.

Stimuli-responsive thin film composites of conducting polymers and cellulose nanocrystals for tissue engineering.

Thin composite films comprising two primary representatives of conducting polymers, poly(3, 4-ethylenedioxythiophene) (PEDOT) and polypyrrole (PPy), with eco-friendly cellulose nanocrystals (CNC) were prepared through electrochemical polymerization. The combination of CNC and PEDOT (or PPy) results in the formation of films with highly different surface topography and thickness. Intriguingly, different surface conductivity of PEDOT and PPy was revealed by atomic force microscopy albeit that the electrochemical properties were rather similar. The biological properties of the composites in contact with prospective human induced pluripotent stem cells (hiPSC) and cardiomyocytes derived from hiPSC demonstrated good cytocompatibility of both composites and their potential in engineering of electro-sensitive tissues. The as-prepared conducting, eco-friendly and cytocompatible composites are thus promising candidates for biomedical applications where stimuli-responsivity is a crucial cell-instructive property.

Heteroaggregation effects on Pickering stabilization using oppositely charged cellulose nanocrystal and nanochitin.

Pickering emulsions are stabilized using complexes of cellulose nanocrystals (CNC) and nanochitin (NCh). The colloidal behavior and heteroaggregation in aqueous media are studied in relation to complex formation and net charge. The complexes are remarkably effective in stabilizing oil-in-water Pickering emulsions under conditions of slightly net positive or negative charges, as determined by the CNC/NCh mass ratio. Close to charge neutrality (CNC/NCh ~5), large heteroaggregates form, resulting in unstable emulsions. By contrast, under net cationic conditions, interfacial arrest of the complexes leads to non-deformable emulsion droplets with high stability (no creaming for 9 months). At given CNC/NCh concentrations, emulsions with up to 50% oil fraction are produced. This study shows how to control emulsion properties beyond consideration of the typical formulation variables, for instance, through adjusting CNC/NCh ratio or charge stoichiometry. We highlight the possibilities that are available for emulsion stabilization by using a combination of polysaccharide nanoparticles.

Injectable thiol-ene hydrogel of galactoglucomannan and cellulose nanocrystals in delivery of therapeutic inorganic ions with embedded bioactive glass nanoparticles.

We propose an injectable nanocomposite hydrogel that is photo-curable via light-induced thiol-ene addition between methacrylate modified O-acetyl-galactoglucomannan (GGMMA) and thiolated cellulose nanocrystal (CNC-SH). Compared to free-radical chain polymerization, the orthogonal step-growth of thiol-ene addition allows a less heterogeneous hydrogel network and more rapid crosslinking kinetics. CNC-SH reinforced the GGMMA hydrogel as both a nanofiller and a crosslinker to GGMMA resulting in an interpenetrating network via thiol-ene addition. Importantly, the mechanical stiffness of the GGMMA/CNC-SH hydrogel is mainly determined by the stoichiometric ratio between the thiol groups on CNC-SH and the methacrylate groups in GGMMA. Meanwhile, the bioactive glass nanoparticle (BaGNP)-laden hydrogels of GGMMA/CNC-SH showed a sustained release of therapeutic ions in simulated body fluid in vitro, which extended the bioactive function of hydrogel matrix. Furthermore, the suitability of the GGMMA/CNC-SH formulation as biomaterial resin to fabricate digitally designed hydrogel constructs via digital light processing (DLP) lithography printing was evaluated.

Water-soluble polysaccharides promoting production of redispersible nanocellulose.

To date, the energy-intensive production and high-water content severely limits nanocellulose applications on a large scale off-site. In this study, adding water-soluble polysaccharides (PS) to achieve an integrated process of water-redispersible nanocellulose production was well established. The addition of PS, in particular carboxymethylated-galactoglucomannan (cm-GGM), facilitates fibre fibrillation enabling homogenization at a higher solid content at 1.5 wt% compared with around 0.4 wt% for neat fibre. More importantly, the addition of cm-GGM saved 73 % energy in comparison without PS addition. Good water redispersibility of thus-prepared nanocellulose was validated in viewpoints of size distribution, morphology, viscosity and film properties as compared with neat nanocellulose. The tensile strength and optical transmittance of nanocellulose films increased to 116 MPa and 77 % compared to those without PS addition of 62 MPa and 74 %, respectively. Collectively, this study provides a new avenue for large-volume production of redispersible nanocellulose at a high solid content with less energy-consumption.

Solid-state polymer adsorption for surface modification: The role of molecular weight.

HYPOTHESIS: Solid-state polymer adsorption offers a distinct approach for surface modification. These ultrathin, so-called Guiselin layers can easily be obtained by placing a polymer melt in contact with an interface, followed by a removal of the non-adsorbed layer with a good solvent. While the mechanism of formation has been well established for Guiselin layers, their stability, crucial from the perspective of materials applications, is not. The stability is a trade-off in the entropic penalty between cooperative detachment of the number of segments directly adsorbed on the substrate and consecutively pinned monomers. EXPERIMENTS: Experimental model systems of Guiselin layers of polystyrene (PS) on silicon wafers with native oxide layer on top were employed. The stability of the adsorbed layers was studied as a function of PS molecular weight and polydispersibility by various microscopic and spectroscopic tools as well as quasi-static contact angle measurements. FINDINGS: Adsorbed layers from low molecular weight PS were disrupted with typical spinodal decomposition patterns whereas high molecular weight (>500 kDa) PS resulted in stable, continuous layers. Moreover, we show that Guiselin layers offer an enticing way to modify a surface, as demonstrated by adsorbed PS that imparts a hydrophobic character to initially hydrophilic silicon wafers.

Pickering Emulsions via Interfacial Nanoparticle Complexation of Oppositely Charged Nanopolysaccharides.

We consider the variables relevant to adsorption of renewable nanoparticles and stabilization of multiphase systems, including the particle's hydrophilicity, electrostatic charge, axial aspect, and entanglement. Exploiting the complexation of two oppositely charged nanopolysaccharides, cellulose nanofibrils (CNFs) and nanochitin (NCh), we prepared CNF/NCh aqueous suspensions and identified the conditions for charge balance (turbidity and electrophoretic mobility titration). By adjusting the composition of CNF/NCh complexes, below and above net neutrality conditions, we produced sunflower oil-in-water Pickering emulsions with adjustable droplet diameters and stability against creaming and oiling-off. The adsorption of CNF/NCh complexes at the oil/water interface occurred with simultaneous partitioning (accumulation) of the CNF on the surface of the droplets in net negative or positive systems (below and above stochiometric charge balance relative to NCh). We further show that the morphology of the droplets and size distribution were preserved during storage for at least 6 months under ambient conditions. This long-term stability was held with a remarkable tolerance to changes in pH (e.g., 3-11) and ionic strength (e.g., 100-500 mM). The mechanism explaining these observations relates to the adsorption of the CNF in the complexes, counteracting the charge losses resulting from the deprotonation of NCh or charge screening. Overall, CNF/NCh complexes and the respective interfacial nanoparticle exchange greatly extend the conditions, favoring highly stable, green Pickering emulsions that offer potential in applications relevant to foodstuff, pharmaceutical, and cosmetic formulations.

Current advances and future perspectives of 3D printing natural-derived biopolymers.

3D printing enables the complex or customized structures production in high speed and resolution. However, the lack of bio-based materials with user-defined biochemical and mechanical property is a significant barrier that limits the widespread adoption of 3D printing for products fabrication. Development of eco-friendly natural-derived biopolymers for 3D printing technologies and their promising application in different areas are of huge academic, and environmental interests. This paper reviews the state-of-the-art in terms of 3D printing technology using natural-derived feedstocks, including lignocellulose, starch, algae, and chitosan-based biopolymers. Special consideration is given to the development of lignocellulosic materials, i.e. cellulose, hemicellulose, lignin, and their derivatives as 3D printing feedstocks. A strategical development roadmap with identified material property requirements, key challenges, as well as possible solutions was proposed. It serves as guideline aiming to explore natural-derived biopolymers as novel feedstocks for different 3D printing technologies that will be potentially applied in various areas.

Surface Engineered Biomimetic Inks Based on UV Cross-Linkable Wood Biopolymers for 3D Printing.

Owing to their superior mechanical strength and structure similarity to the extracellular matrix, nanocelluloses as a class of emerging biomaterials have attracted great attention in three-dimensional (3D) bioprinting to fabricate various tissue mimics. Yet, when printing complex geometries, the desired ink performance in terms of shape fidelity and object resolution demands a wide catalogue of tunability on the material property. This paper describes surface engineered biomimetic inks based on cellulose nanofibrils (CNFs) and cross-linkable hemicellulose derivatives for UV-aided extrusion printing, being inspired by the biomimetic aspect of intrinsic affinity of heteropolysaccharides to cellulose in providing the ultrastrong but flexible plant cell wall structure. A facile aqueous-based approach was established for the synthesis of a series of UV cross-linkable galactoglucomannan methacrylates (GGMMAs) with tunable substitution degrees. The rapid gelation window of the formulated inks facilitates the utilization of these wood-based biopolymers as the feeding ink for extrusion-based 3D printing. Most importantly, a wide and tunable spectrum ranging from 2.5 to 22.5 kPa of different hydrogels with different mechanical properties could be achieved by varying the substitution degree in GGMMA and the compositional ratio between GGMMA and CNFs. Used as the seeding matrices in the cultures of human dermal fibroblasts and pancreatic tumor cells, the scaffolds printed with the CNF/GGMMA inks showed great cytocompatibility as well as supported the matrix adhesion and proliferative behaviors of the studied cell lines. As a new family of 3D printing feedstock materials, the CNF/GGMMA ink will broaden the map of bioinks, which potentially meets the requirements for a variety of in vitro cell-matrix and cell-cell interaction studies in the context of tissue engineering, cancer cell research, and high-throughput drug screening.

A honeycomb-like paper-based thermoelectric generator based on a Bi2Te3/bacterial cellulose nanofiber coating.

The intrinsic properties of paper, such as its light weight, flexibility, foldability, portability and degradability, have led to increasing interest in fabricating flexible energy storage devices and power supply devices on paper-based substrates. Hereby, a robust honeycomb-like thermoelectric generator (TEG) inspired by the origami and kirigami techniques was established in the present study. A thermoelectric ink with the properties of high electrical conductivity and low thermal conductivity was formulated by Bi2Te3 and bacterial cellulose (BC). The formulated ink was printed on a paper surface using a facile processing method. The manufactured paper was further folded and bonded to fabricate a honeycomb-like TEG. This honeycomb-like paper-based TEG exhibited 96 p-n junctions, achieving a maximum voltage and output power of ∼70.5 mV and ∼596 nW, respectively, at a 55 K temperature difference. Moreover, the honeycomb structure was able to withstand a large number of bending and stretching cycles while maintaining its pristine structure. This unique honeycomb structure thus provides a new strategy for future development of paper-based TEGs.

On Low-Concentration Inks Formulated by Nanocellulose Assisted with Gelatin Methacrylate (GelMA) for 3D Printing toward Wound Healing Application.

Cellulose nanofibrils (CNFs) in the form of hydrogels stand out as a platform biomaterial in bioink formulation for 3D printing because of their low cytotoxicity and structural similarity to extracellular matrices. In the present study, 3D scaffolds were successfully printed with low-concentration inks formulated by 1 w/v % 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized CNF with less than 1 w/v % gelatin methacrylate (GelMA). Quartz crystal microbalance with dissipation monitoring (QCM-D) measurements showed strong interaction between the two biopolymers. The UV cross-linking ability of GelMA (≤1 w/v %) was enhanced in the presence of TEMPO-oxidized CNFs. Multiple factors including strong physical interaction between CNF and GelMA, in situ cross-linking of CNF by Ca2+, and UV cross-linking of GelMA enabled successful 3D printing of low-concentration inks of CNF/GelMA into scaffolds possessing good structural stability. The mechanical strength of the scaffolds was tuned in the range of 2.5 to 5 kPa. The cell culture with 3T3 fibroblasts revealed noncytotoxic and biocompatible features for the formulated inks and printed scaffolds. More importantly, the incorporated GelMA in the CNF hydrogel promoted the proliferation of fibroblasts. The developed low-concentration CNF/GelMA formulations with a facile yet effective approach to fabricate scaffolds showed great potential in 3D printing for wound healing application.

Three-Dimensional Printing of Wood-Derived Biopolymers: A Review Focused on Biomedical Applications.

Wood-derived biopolymers have attracted great attention over the past few decades due to their abundant and versatile properties. The well-separated three main components, i.e., cellulose, hemicelluloses, and lignin, are considered significant candidates for replacing and improving on oil-based chemicals and materials. The production of nanocellulose from wood pulp opens an opportunity for novel material development and applications in nanotechnology. Currently, increased research efforts are focused on developing 3D printing techniques for wood-derived biopolymers for use in emerging application areas, including as biomaterials for various biomedical applications and as novel composite materials for electronics and energy devices. This Review highlights recent work on emerging applications of wood-derived biopolymers and their advanced composites with a specific focus on customized pharmaceutical products and advanced functional biomedical devices prepared via three-dimensional printing. Specifically, various biofabrication strategies in which woody biopolymers are used to fabricate customized drug delivery devices, cartilage implants, tissue engineering scaffolds and items for other biomedical applications are discussed.

3D printing of nanocellulose hydrogel scaffolds with tunable mechanical strength towards wound healing application.

We present for the first time approaches to 3D-printing of nanocellulose hydrogel scaffolds based on double crosslinking, first by in situ Ca2+ crosslinking and post-printing by chemical crosslinking with 1,4-butanediol diglycidyl ether (BDDE). Scaffolds were successfully printed from 1% nanocellulose hydrogels, with their mechanical strength being tunable in the range of 3 to 8 kPa. Cell tests suggest that the 3D-printed and BDDE-crosslinked nanocellulose hydrogel scaffolds supported fibroblast cells' proliferation, which was improving with increasing rigidity. These 3D-printed scaffolds render nanocellulose a new member of the family of promising support structures for crucial cellular processes during wound healing, regeneration and tissue repair.

Novel biorenewable composite of wood polysaccharide and polylactic acid for three dimensional printing.

Hemicelluloses, the second most abundant polysaccharide right after cellulose, are in practice still treated as a side-stream in biomass processing industries. In the present study, we report an approach to use a wood-derived and side-stream biopolymer, spruce wood hemicellulose (galactoglucomannan, GGM) to partially replace the synthetic PLA as feedstock material in 3D printing. A solvent blending approach was developed to ensure the even distribution of the formed binary biocomposites. The blends of hemicellulose and PLA with varied ratio up to 25% of hemicellulose were extruded into filaments by hot melt extrusion. 3D scaffold prototypes were successfully printed from the composite filaments by fused deposition modeling 3D printing. Combining with 3D printing technique, the biocompatible and biodegradable feature of spruce wood hemicellulose into the composite scaffolds would potentially boost this new composite material in various biomedical applications such as tissue engineering and drug-eluting scaffolds.

Synthesis of tunable hydrogels based on O-acetyl-galactoglucomannans from spruce.

Hydrogels with tunable mechanical properties based on O-acetyl-galactoglucomannans (GGMs) from spruce functionalized with tyramine, a molecule containing crosslinkable phenolic groups, were prepared. Gel formation was induced by enzymatic crosslinking at the addition of horse radish peroxidase and hydrogen peroxide to the modified GGMs. The degree of substitution determined the hydrogels final properties, and was varied by TEMPO oxidation of GGM to a degree of oxidation from 10 to 60%. GGM and its derivatives were characterized by gas chromatography and high pressure size exclusion chromatography to analyze sugar composition and molar mass, respectively. Tyramine-conjugated GGM was evaluated by nuclear magnetic resonance, fourier transform infrared spectroscopy and elemental analysis. Measurements of moduli over time showed crosslinking within 20s and maximum stress of the prepared gels were compared by compression testing. Overall this system presents a cell friendly hydrogel from a renewable, low cost resource which could be applied in cell delivery, wound dressings, and biofabrication.

Cellulose nanocrystals prepared via formic acid hydrolysis followed by TEMPO-mediated oxidation.

Cellulose nanocrystals (CNCs) as a renewable and biodegradable nanomaterial have wide application value. In this work, CNCs were extracted from bleached chemical pulp using two stages of isolation (i.e. formic acid (FA) hydrolysis and 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) mediated oxidation) under mild conditions. In the first stage, FA was used to remove hemicellulose, swell cellulose fibers, and release CNCs. The FA could be readily recovered and reused. In the second stage, the CNCs isolated by FA were further modified by TEMPO-mediated oxidation to increase the surface charge of CNCs. It was found that the modified CNCs with more ordered crystal structure and higher surface charge had better redispersibility and higher viscosity in aqueous phase. Therefore, the modified CNCs could be more effective when used as rheology modifier in the fields of water based coating, paint, food etc.