Interfacial modulation of Ti3C2Tx MXene using functionalized cellulose nanofibrils for enhanced electrochemical actuation.

Electrochemical actuators (ECAs) with low voltage actuation and large deformation ranges generally require electrode materials with high ion kinetic energy transport, high charge storage, and excellent electrochemical-mechanical properties. However, the fabrication of such actuators remains a major challenge. In the present work, hybrid electroactive films were fabricated by self-assembling one-dimensional functionalized cellulose nanofibrils (CNFs) with two-dimensional MXene (Ti3C2Tx). The obtained ECA actuators fabricated by carboxymethylated cellulose nanofibrils (consisting of -CH2COO-surface groups) with Ti3C2Tx integrate excellent curvature (0.1041 mm-1), mechanical strength (21.68 MPa), a bending strain of 0.50 %, and a good actuation displacement of 9.3 mm at a low voltage range of -0.6 to 0.3 V. This may be attributed to the enlarged layer spacing (15.34 Å), which makes the embedding and transport of H+ easier, and excellent adaptivity of mechanical properties achieved by molecular-scaled strong hydrogen bonding, leading to better actuation performance. This study provides a potential research direction for the preparation of ECAs with large actuation deformation.

Reversibly Compressible Silanated Cellulose Nanofibril Aerogel for Triboelectric Taekwondo Scoring Sensors.

The integration of bio-based materials into triboelectric nanogenerators (TENGs) for energy harvesting from human body motions has sparked considerable research attention. Here, a silanated cellulose nanofibril (SCNF) aerogel is reported for structurally reliable TENGs and reversely compressible Taekwondo scoring sensors under repeated impacts. The preparation of the aerogel involves silanizing cellulose nanofibers (CNFs) with vinyltrimethoxysilane (VTMS), following by freeze-drying and post-heating treatment. The SCNF aerogel with crosslinked physico-chemical bonding and highly porous network is found to exhibit superior mechanical strength and reversible compressibility as well as enhanced water repellency and electron-donating ability. The TENG having a tribo-positive SCNF layer exhibits exceptional triboelectric performances, generating a voltage of 270 V, current of 11 µA, and power density of 401.1 mW m-2 under an applied force of 8 N at a frequency of 5 Hz. With its inherent merits in material composition, structural configuration, and device sensitivity, the SCNF TENG demonstrates the capability to seamlessly integrate into a Taekwondo protection gear, serving as an efficient self-powered sensor for monitoring hitting scores. This study highlights the significant potential of a facilely fabricated SCNF aerogel for the development of high-performance, bio-friendly, and cost-effective Bio-TENGs, enabling their application as self-powered wearable devices and sports engineering sensors.

Controlled Sol-Gel Transitions of Metal-Organic Membrane-Enveloped Cellulose Nanofibrils via Metal Coordination in Aqueous Media.

We report a metal coordination-driven sol-gel transition system where cellulose nanofibrils are enveloped by a rationally designed metal-organic membrane (MOM) in an aqueous medium. Specifically, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized bacterial cellulose (TOBC) is encapsulated within an MOM comprising Zn2+ and the chelator phytic acid (PA), denoted TOBCMOM. Using the DLVO theory, we elucidate how tuning the metal ion valence in TOBCMOM modulates the sol-gel transition by controlling interfibrillar attractive forces. Notably, TOBCMOM fluids exhibit relaxation times consistent with the Kohlrausch-Williams-Watts (KWW) function. Significantly, we demonstrate reversible, sustainable sol-gel transitions in TOBCMOM under stepwise mechanical strain. This facile approach enables rheological tailoring of aqueous media, promising for the development of advanced stimuli-responsive smart fluids for applications in cosmetics, food science, and pharmaceutical formulations.

Dialdehyde cellulose nanofibrils/polyquaternium stabilized ultra-fine silver nanoparticles for synergistic antibacterial therapy.

Dialdehyde cellulose nanofibrils (DACNF) and Polyquaternium-10 (PQ: chloro-2-hydroxy-3-(trimethylamino) propyl polyethylene glycol cellulose) have become increasingly favored as antibacterial substances due to their advantageous characteristics. DACNF exhibits exceptional mechanical properties and biocompatibility, whereas PQ demonstrates a positive charge that enhances its antibacterial activity. Combined in a DACNF/PQ mixture, they provide an excellent template material for preparing and stabilizing ultra-fine (~ 10.3 nm) silver nanoparticles (AgNPs) at room temperature. Here, the dialdehyde group of DACNF functions as a reducing agent, while the quaternary ammonium of PQ and carboxylate groups of DACNF synergistically helped in-situ generation of AgNPs uniformly. The synthesized nanocomposites, namely PQ@AgNPs, AgNPs@DACNF, and AgNPs@DACNF/PQ, were subjected to comprehensive characterization using various advanced analytical techniques. The films containing AgNPs@DACNF and AgNPs@DACNF/PQ, fabricated via vacuum filtration, exhibited excellent mechanical properties of 9.78 ± 0.21 MPa, and demonstrated superior antibacterial activity against both Escherichia coli and Staphylococcus aureus. Additionally, the silver ion leaching from the prepared composite films was well controlled. The fabricated nanocomposites also effectively inhibited bacterial biofilm formation. It was also found to be highly biocompatible and non-toxic to human skin fibroblast cells. Furthermore, the nanocomposites exhibited enhanced migration of human dermal fibroblasts, suggesting their potential in facilitating wound healing processes.

Exploiting the Properties of Non-Wood Feedstocks to Produce Tailorable Lignin-Containing Cellulose Nanofibers.

Lignin-containing cellulose nanofibrils (LCNFs) are mainly produced commercially from treated wood pulp, which can decrease some of the carbon-negative benefits of utilizing biomass feedstock. In this work, LCNFs are prepared from non-wood feedstocks, including agricultural residues such as hemp, wheat straw, and flax. These feedstocks allowed for the preparation of LCNFs with a variety of properties, including tailored hydrophobicity. The feedstocks and their subsequent LCNFs are extensively characterized to determine the roles that feedstocks play on the morphology and properties of their resultant LCNFs. The LCNFs were then incorporated into paper handsheets to study their usefulness in papermaking applications, which indicated good potential for the use of wheat straw LCNFs as a surface additive to improve the oil resistance coating.

In Vitro Gastrointestinal Digestion of Corn-Oil-in-Water Pickering Emulsions: Influence of Lignin-Containing Cellulose Nanofibrils Loading.

There is a growing trend in incorporating biomass-based engineered nanomaterials into food products to enhance their quality and functionality. The zeta potential, droplet size, microstructure, and content of free fatty acid (FFA) release were determined to investigate the influence of a plant-derived particle stabilizer, i.e., lignin-containing cellulose nanofibrils (LCNFs). Remarkable differences were observed during digestion stages, which were found to be correlated with the concentrations of LCNFs. The gradual FFA release in the small intestine stage from LCNF-coated lipid droplets was monitored over time, with a final lowest release of FFAs amounting to 26.3% in the emulsion containing 20.0% (v/v) of the dispersed phase stabilized by 3 mg/mL of LCNFs. This release can be attributed to the physical barrier at lipid droplet surfaces and the network effect created by the free LCNFs in the continuous phase. This work provides a foundation for the potential application of nature-derived LCNF materials in reducing fat absorbance.

Can pure cellulose nanofibril films replace polyolefins as water vapor barriers in packaging?

Despite significant research into cellulose nanofibril (CNF) films as substitutes to synthetic plastic materials, commercial applications remain very limited. One major hindrance is the poor water vapor barrier properties of CNF films compared to polyolefins, a critical property for product protection, such as food safety and preservation. To date, it is unknown whether full moisture barrier properties can be achieved with materials made by the assembly of nanofibers and fibrils. A comprehensive understanding of the effect of film structure on water vapor transport properties is required. Here, over 200 films were produced with a wide range of grammages from 30 g/m2 to 580 g/m2 by casting and spray deposition. Their structures were quantified by µCT and SEM and related to their water vapor transmission rates (WVTRs). Porosity and pore connectivity decreased with increasing film grammage, which correlates with the exponential decrease in WVTR. However, the WVTR plateaued at 30 g/m2day, indicating that the known open space and adsorption diffusion mechanisms cannot be fully eliminated by producing high grammage films. Pure cellulose nanofibril films therefore cannot replace polyolefins in packaging applications, requiring modifications such as coating and nanofillers.

Janus nanocellulose membrane by nitrogen plasma: Hydrophilicity to hydrophobicity selective switch.

Cellulose nanofibrils are one of the keystone materials for sustainable future, yet their poor water repellency hinders their push into industrial applications. Due to complexity and poor economical outcome and/or processing toxicity of the existing hydrophobization methods, nanocellulose loses against its antagonist plastic in medical and food industries. Herein, we demonstrate for the first time the "one-side selective water-repellency activation" in nanocellulose membranes by the means of mild N2-plasma treatment, exhibiting lowest wettability after 20 s of treatment. Hydrophobicity and accompanying Janus character were justified by the topological, chemical and structural reorganizations in cellulose nanofibrils. The findings suggest that the mechanism behind the hydrophilic/hydrophobic change primarily relies on the interplay between OH removal and appearance of SiCH3, originating from the polysiloxanes-based substrate, as well as complementary CNH2 groups formation. First-principles calculations show that NH2 groups moderately increase hydrophobicity, while various SiCH3 substitutions wholly change the character of the surface to repel water. Using nitrogen is shown to be crucial, as N(H)Si(CH3)3 groups induce greater hydrophobicity than simple OSi(CH3)3. Finally, the obtained materials absorb water on the hydrophilic side, while remaining hydrophobic on the other, exhibit high tensile strength, and protection against UV light, demonstrating applicability over wide range of applications.

Tough polyacrylic acid hydrogels with stable swelling and active functionalities enabled by quaternized cellulose nanofibrils and iron ions for absorbent pad interlayers.

Hydrogels are highly sought-after absorbent materials for absorbent pads; however, it is still challenging to achieve a satisfactory balance between mechanical performance, water absorption capacity, and active functionalities. In this work, we presented double-network hydrogels synthesized through acrylic acid (AA) polymerization in the presence of quaternized cellulose nanofibrils (QCNF) and Fe3+. Spectroscopic and microscopic analyses revealed that the combined QCNF and Fe3+ facilitated the formation of double-network hydrogels with combined chemical and physical crosslinking. The synergistic effect of QCNF and Fe3+ resulted in impressive mechanical properties, including tensile strength of 1.98 MPa, fracture elongation of 838.8 %, toughness of 7.47 MJ m-3, and elastic modulus of 0.35 MPa. In comparison to the single-network PAA hydrogel, the PAA/QCNF/Fe3+ (PQFe) hydrogels showed higher and relatively stable swelling ratios under varying pH levels and saline conditions. The PQFe hydrogels exhibited notable antioxidant activity, as evidenced by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, and demonstrated effective antibacterial activity against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). These hydrogels show promising potential as an absorbent interlayer in absorbent pads for active food packaging.

Ultrastrong Nanopapers with Aramid Nanofibers and Silver Nanowires Reinforced by Cellulose Nanofibril-Assisted Dispersed Graphene Nanoplates for Superior Electromagnetic Interference Shielding.

High-strength, lightweight, ultrathin, and flexible electromagnetic interference (EMI) shielding materials with a high shielding effectiveness (SE) are essential for modern integrated electronics. Herein, cellulose nanofibrils (CNFs) are employed to homogeneously disperse graphene nanoplates (GNPs) into an aramid nanofiber (ANF) network and silver nanowire (AgNW) network, respectively, producing high-performance nanopapers. These nanopapers, featuring nacre-mimetic microstructures and layered architectures, exhibited high tensile strength (601.11 MPa) and good toughness (103.56 MJ m-3) with a thickness of only 24.58 µm. Their specific tensile strength reaches 447.59 MPa·g-1·cm3, which is 1.74 times that of titanium alloys (257 MPa·g-1·cm3). The AgNW/GNP composite conductive layers exhibit an electrical conductivity of 12010.00 S cm-1, providing the nanopapers with great EMI shielding performance, achieving an EMI SE of 63.87 dB and an EMI SE/t of 25978.80 dB cm-1. The nanopapers also show reliable durability, retaining a tensile strength of 500.96 MPa and an EMI SE of 57.59 dB after 120,000 folding cycles. Additionally, they have a good electrical heating performance with a fast response time, low driving voltage, effective deicing capability, and reliable heating capacity in water. This work presents a strategy to develop a high-performance nanopaper, showing great potential for applications in electromagnetic compatibility, national defense, smart electronics, and human health.

Eumelanin-Enhanced Photothermal Disinfection of Contact Lenses Using a Sustainable Marine Nanoplatform Engineered with Electrospun Nanofibers.

Bacterial keratitis (BK) is a severe eye infection commonly associated with Staphylococcus aureus (S. aureus), posing a significant risk to vision, especially among contact lens wearers. This research introduces a novel smart nanoplatform (deMS@cNF), developed from demineralized mussel shells (deMS) and reinforced with chitin (CT) nanofibrils, specifically designed for portable photothermal disinfection of contact lenses. The nanoplatform leverages the photothermal properties of eumelanin in mussel shells (MS), which, when activated by a simple bike flashlight, rapidly heats to temperatures up to 95 °C, effectively destroying bacterial contamination. In vitro tests demonstrate that the nanoplatform is biocompatible and non-toxic, making it suitable for medical applications. This study highlights an innovative approach to converting marine biowaste into a safe, effective, and low-cost portable method for disinfecting contact lenses, showcasing the potential of the deMS@cNF platform for broader antimicrobial applications.

Multifunctional composite film of curcumin Pickering emulsion stabilized by lignocellulose nanofibrils isolated from bamboo shoot shells for monitoring shrimp freshness.

Concerns about food safety and environmental impact from chemical surfactants have prompted interest in natural lignocellulosic materials as alternatives. In this study, we combined hydrated deep eutectic solvent (DES) pretreatment with ultrasound treatment to prepare lignocellulosic nanofibrils (LCNF) from bamboo shoot shells with appropriate surface properties for stabilizing Pickering emulsions. The pretreatment intensity effectively modulated the surface characteristics of LCNF, achieving desirable wettability through lignin retention and in-situ esterification. The resulting LCNF/curcumin Pickering emulsion (CPE) demonstrated curcumin protection and pH-responsive color changes, while the ensuing CPE/PVA composite film exhibited ultraviolet shielding, mechanical strength, oxygen barrier, and antioxidant properties. Furthermore, the CPE/PVA film showed promise as a real-time indicator for monitoring shrimp freshness, maintaining sensitivity to spoilage even after six months of storage. These findings advance the advancement of green LCNF technologies, providing eco-friendly solutions for valorizing bamboo shoot shells and enhancing the application of LCNF in Pickering emulsions.

Carbon dots-loaded cellulose nanofibrils hydrogel incorporating Bi2O3/BiOCOOH for effective adsorption and photocatalytic degradation of lignin.

A novel photocatalytic adsorbent, a cellulose nanofibrils based hydrogel incorporating carbon dots and Bi2O3/BiOCOOH (designated as CCHBi), was developed to address lignin pollution. CCHBi exhibited an adsorption capacity of 435.0 mg/g, 8.9 times greater than that of commercial activated carbon. This enhanced adsorption performance was attributed to the 3D porous structure constructed using cellulose nanofibrils (CNs), which increased the specific surface area and provided additional sorption sites. Adsorption and photocatalytic experiments showed that CCHBi had a photocatalytic degradation rate constant of 0.0140 min-1, 3.1 times higher than that of Bi2O3/BiOCOOH. The superior photocatalytic performance of CCHBi was due to the Z-scheme photocatalytic system constructed by carbon dots-loaded cellulose nanofibrils and Bi2O3/BiOCOOH, which facilitated the separation of photoinduced charge carriers. Additionally, the stability of CCHBi was confirmed through consecutive cycles of adsorption and photocatalysis, maintaining a removal efficiency of 85 % after ten cycles. The enhanced stability was due to the 3D porous structure constructed by CNs, which safeguarded the Bi2O3/BiOCOOH. This study validates the potential of CCHBi for high-performance lignin removal and promotes the application of CNs in developing new photocatalytic adsorbents.

Biointerfacial supramolecular self-assembly of whey protein isolate nanofibrils on probiotic surface to enhance survival and application to 3D printing dysphagia foods.

Personalized three-dimensional (3D) printed foods rich in probiotics were investigated. Lactiplantibacillus plantarum (Lp), as a representative of probiotics, was used to investigate the 3D printing of probiotic-rich dysphagia foods. Here, whey protein isolate nanofibrils (WPNFs) were coated and anchored on bacterial surfaces via biointerfacial supramolecular self-assembly, providing protection against environmental stress and the 3D printing process. The optimized composite gels consisting of High acyl gellan gum (0.25 g), whey protein isolate (1.25 g), fructooligosaccharides (0.75 g), Lp-WPNFs-Glyceryl tributyrate emulsion (Φ = 40%, 3.75 mL) can realize 3D printing, and exhibit high resolution, and stable shape. The viable cell count is higher than 8.0 log CFU/g. They are particularly suitable for people with dysphagia and are classified as level 5-minced & moist in the international dysphagia diet standardization initiative framework. The results provide new insights into the development of WPNFs-coating on bacterial surfaces to deliver probiotics and 3D printed food rich in probiotics.

A solar-driven nanocellulose Janus aerogel with excellent floating stability and dual functions of oil-water separation and photocatalytic degradation of organic pollutants.

Effective and practical cleanup of viscous crude oil spills is extremely important in real harsh marine environments. Herein, we designed a solar-driven, nanocellulose-based Janus aerogel (Janus-A) with excellent floating stability and dual function of oil-water separation and degradation of aqueous organic pollutants. Janus-A, with its amphiprotic nature, was prepared through polypyrrole (PPy) deposition, freeze-drying, octyltrichlorosilane (OTS) impregnation, TiO2 spraying on the bottom surface, and UV irradiation treatment. The photothermal conversion effect of PPy coating raised the surface temperature of aerogel to 75.8 °C within 6 min under one simulated solar irradiation, which greatly reduced the viscosity of the crude oil and increased the absorption capacity of the aerogel to 36.7 g/g. Benefiting from the balance between the buoyancy generated by the hydrophobic part and water absorption of the hydrophilic part, Janus-A showed excellent floating stability under simulated winds and waves. In addition, Janus-A exhibited high degradation efficiency for organic pollutants in water owing to the synergistic photocatalytic properties of TiO2 and PPy. These excellent performances make Janus-A ideal for integrated water-oil separation and water remediation.

Structure-property relations in rheology of cellulose nanofibrils-based hydrogels.

Hydrogels prepared from self-assembled cellulose nanofibrils (CNFs) are widely used in biomedicine, electronics and environmental technology. Their ability to serve as inks for extrusion-based 3D printing is conventionally evaluated by means of rheological tests. A model is developed that describes the response of CNF gels in small- and large-amplitude oscillatory tests in a unified manner. The model involves a reasonably small number of material parameters, ensures good agreement between results of simulation and observations in oscillatory tests and correctly predicts the stress-strain Lissajous curves, experimental data in hysteresis loop tests, and measurements of the steady-state viscosity. The model is applied to analyze how composition and preparation conditions for CNF gels affect transition from shear thinning to weak strain overshoot in large-amplitude shear oscillatory tests. Based on the model, simple relations are derived for the fractal dimension of CNF clusters and the storage modulus of gels prepared in aqueous solutions of multivalent salts. The validity of these equations is confirmed by comparison of their predictions with observations in independent tests.

Cholic Acid/Glutathione-Assembled Nanofibrils for Stabilizing Pickering Emulsion Biogels.

Achieving the delicate balance required for both emulsion and gel characteristics, while also imparting biological functionality in gelled emulsions, poses a significant challenge. Herein, Pickering emulsion biogels stabilized is reported by novel biological nanofibrils assembled from natural glutathione (GSH) and a tripod cholic acid derivative (TCA) via electrostatic interactions. GSH, composed of tripeptides with carboxyl groups, facilitates the protonation and dissolution of TCA compounds in water and the electrostatic interactions between GSH and TCA trigger nanofibrillar assembly. Fibrous nuclei initially emerge, and the formed mature nanofibrils can generate a stable hydrogel at a low solid concentration. These nanofibrils exhibit efficient emulsifying capability, enabling the preparation of stable Pickering oil-in-water (O/W) emulsion gels with adjustable phase volume ratios. The entangled nanofibrils adsorbed at the oil-water interface restrict droplet movement, imparting viscoelasticity and injectability to the emulsions. Remarkably, the biocompatible nanofibrils and stabilized emulsion gels demonstrate promising scavenging properties against reactive oxygen species (ROS). This strategy may open new scenarios for the design of advanced emulsion gel materials using natural precursors and affordable building blocks for biomedical applications.

The Preparation of a Polyamidoxime-Phosphorylated Cellulose Nanofibrils Composite Aerogel for the Selective Extraction of Uranium from Seawater.

Uranium is the most important fuel for nuclear power operations, and the safe supply of its resources is the key to the development of nuclear power in China. Because of the complex seawater environment and extremely low uranium concentration, extracting uranium from natural seawater poses a significant challenge. In this study, a polyamidoxime-phosphorylated cellulose nanofibril composite aerogel was prepared as an adsorbent for uranium extraction from seawater. An adsorption kinetics test, equilibrium adsorption isotherm model fitting, an adsorption-desorption cycle test, and a selectivity test were carried out to evaluate the adsorption performance of the composite aerogel for uranium extraction. The adsorption capacities for the initial concentrations of 4 and 8 ppm in uranium-spiked pure water were 96.9 and 204.3 mg-U/g-Ads, respectively. The equilibrium uranium adsorption capacities of uranium-spiked simulated seawater were 38.9 and 51.7 mg-U/g-Ads, respectively. The distribution coefficient KD of uranium was calculated to be 2.5 × 107 mL/g. The results show that the polyamidoxime-phosphorylated cellulose nanofiber composite aerogels prepared in this study have the advantages of low cost and high uranium selectivity for uranium extraction from seawater.

Engineering an Extracellular Matrix Mimic Using Hemoglobin Protein Nanofibrils.

Extracellular matrix (ECM) is essential for tissue development, providing structural support and a microenvironment that is necessary for cells. As tissue engineering advances, there is a growing demand for ECM mimics. Polycaprolactone (PCL) is a commonly used synthetic polymer for ECM mimic materials. However, its biologically inactive surface limits its direct application in tissue engineering. Our study aimed to improve the biocompatibility of PCL by incorporating hemoglobin nanofibrils (HbFs) into PCL using an electrospinning technique. HbFs were formed from bovine hemoglobin (Hb) extracted from industrial byproducts and designed to offer PCL an improved cell adhesion property. The fabricated HbFs@PCL electrospun scaffold exhibits improved fibroblast adherence, proliferation, and deeper fibroblast infiltration into the scaffold compared with the pure PCL scaffold, indicating its potential to be an ECM mimic. This study represents the pioneering utilization of Hb-sourced nanofibrils in the electrospun PCL scaffolds for tissue engineering applications.

Cellulose Membranes: Synthesis and Applications for Water and Gas Separation and Purification.

Membranes are a selective barrier that allows certain species (molecules and ions) to pass through while blocking others. Some rely on size exclusion, where larger molecules get stuck while smaller ones permeate through. Others use differences in charge or polarity to attract and repel specific species. Membranes can purify air and water by allowing only air and water molecules to pass through, while preventing contaminants such as microorganisms and particles, or to separate a target gas or vapor, such as H2 and CO2, from other gases. The higher the flux and selectivity, the better a material is for membranes. The desirable performance can be tuned through material type (polymers, ceramics, and biobased materials), microstructure (porosity and tortuosity), and surface chemistry. Most membranes are made from plastic from petroleum-based resources, contributing to global climate change and plastic pollution. Cellulose can be an alternative sustainable resource for making renewable membranes. Cellulose exists in plant cell walls as natural fibers, which can be broken down into smaller components such as cellulose fibrils, nanofibrils, nanocrystals, and cellulose macromolecules through mechanical and chemical processing. Membranes made from reassembling these particles and molecules have variable pore architecture, porosity, and separation properties and, therefore, have a wide range of applications in nano-, micro-, and ultrafiltration and forward osmosis. Despite their advantages, cellulose membranes face some challenges. Improving the selectivity of membranes for specific molecules often comes at the expense of permeability. The stability of cellulose membranes in harsh environments or under continuous operation needs further improvement. Research is ongoing to address these challenges and develop advanced cellulose membranes with enhanced performance. This article reviews the microstructures, fabrication methods, and potential applications of cellulose membranes, providing some critical insights into processing-structure-property relationships for current state-of-the-art cellulosic membranes that could be used to improve their performance.