TEMPO-oxidized Cellulose Nanofibrils Research Articles

Fabrication of Loose Nanofiltration Membrane by Crosslinking TEMPO-Oxidized Cellulose Nanofibers for Effective Dye/Salt Separation

Dye/salt separation has gained increasing attention in recent years, prompting the quest to find cost-effective and environmentally friendly raw materials for synthesizing high performance nanofiltration (NF) membrane for effective dye/salt separation. Herein, a high-performance loose-structured NF membrane was fabricated via a simple vacuum filtration method using a green nanomaterial, 2,2,6,6-tetramethylpiperidine-1-oxide radical (TEMPO)-oxidized cellulose nanofiber (TOCNF), by sequentially filtrating larger-sized and finer-sized TOCNFs on a microporous substrate, followed by crosslinking with trimesoyl chloride. The resulting TCM membrane possessed a separating layer composed entirely of pure TOCNF, eliminating the need for other polymer or nanomaterial additives. TCM membranes exhibit high performance and effective dye/salt selectivity. Scanning Electron Microscope (SEM) analysis shows that the TCM membrane with the Fine-TOCNF layer has a tight layered structure. Further characterizations via Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) confirmed the presence of functional groups and chemical bonds of the crosslinked membrane. Notably, the optimized TCM-5 membrane exhibits a rejection rate of over 99% for various dyes (Congo red and orange yellow) and 14.2% for NaCl, showcasing a potential candidate for efficient dye wastewater treatment.

Two-dimensional rheo-optical measurement system to study dynamics and structure of complex fluids

Abstract We have developed a novel rheo-optical measurement system based on two-dimensional polarization analysis, which can evaluate the rheological properties and structure of a complex fluid simultaneously. To assess the utility of the system, we used it to investigate the relationship between yield behavior and structural evolution in a TEMPO-oxidized cellulose nanofiber (T-CNF) suspension, which is a yield-stress fluid that has been actively studied in recent years. To analyze the structural evolution of a T-CNF suspension, stress-ramp tests were conducted. A two-step yield behavior was observed, and distributions of retardation and orientation axis varied dramatically with increasing shear stress. In particular, different distributions were observed in the three regions: after the first yield point, before the second yield point, and after the second yield point. In experiments with a low-concentration T-CNF suspension that exhibits no yield behavior, the retardation increased monotonically with increasing shear stress, and its distribution was uniform. It was demonstrated that the yield behavior and related structures can be analyzed from these results. More detailed structural mechanisms require various rheological tests using the developed system. However, the present insights demonstrate the valuable information provided by the developed rheo-optical measurement system, contributing essential knowledge for applications in various fields.

Stabilizing the Bulk-Phase and Solid Electrolyte Interphase of Silicon Microparticle Anode by Constructing Gradient-Hierarchically Ordered Conductive Networks.

The poor bulk-phase and interphase stability, attributable to adverse internal stress, impede the cycling performance of silicon microparticles (µSi) anodes and the commercial application for high-energy-density lithium-ion batteries. In this work, a groundbreaking gradient-hierarchically ordered conductive (GHOC) network structure, ingeniously engineered to enhance the stability of both bulk-phase and the solid electrolyte interphase (SEI) configurations of µSi, is proposed. Within the GHOC network architecture, two-dimensional (2D) transition metal carbides (Ti3C2Tx) act as a conductive "brick", establishing a highly conductive inner layer on µSi, while the porous outer layer, composed of one-dimensional (1D) Tempo-oxidized cellulose nanofibers (TCNF) and polyacrylic acid (PAA) macromolecule, functions akin to structural "rebar" and "concrete", effectively preserves the tightly interconnected conductive framework through multiple bonding mechanisms, including covalent and hydrogen bonds. Additionally, Ti3C2Tx enhances the development of a LiF-enriched SEI. Consequently, the µSi-MTCNF-PAA anode presents a high discharge capacity of 1413.7 mAh g-1 even after 500 cycles at 1.0 C. Moreover, a full cell, integrating LiNi0.8Mn0.1Co0.1O2 with µSi-MTCNF-PAA, exhibits a capacity retention rate of 92.0% following 50 cycles. This GHOC network structure can offer an efficacious pathway for stabilizing both the bulk-phase and interphase structure of anode materials with high volumetric strain.

In-situ synthesis and binding of silver nanoparticles to dialdehyde and carboxylated cellulose nanofibrils, and active packaging therewith

AbstractThe present work reveals the potential application of dialdehyde and carboxylated nanocellulose for the in-situ reduction of Ag+ and immobilization as silver nanoparticles (AgNPs) on cellulose surfaces. Tollens’ reagent (Ag(NH3)2OH) at concentrations ranging from 5·10–3 to 10–1 M was incorporated in both dialdehyde cellulose (DAC) and dialdehyde-modified TEMPO-oxidized cellulose nanofibers (DA-TOCNFs). The results showed that DA-TOCNFs facilitated faster reduction of Ag+ and effective immobilization of AgNPs on the nanocellulose surface. The resulting suspensions exhibited stability and demonstrated strong antimicrobial activity against Bacillus subtilis when coated on paper surfaces. Importantly, the coated papers did not show significant silver migration to food simulants B (3 vol% acetic acid) and D1 (ethanol/water mixture, 50 vol%), indicating the potential of these suspensions for active food packaging. The advantages of using DA-TOCNFs over DAC were attributed to their higher cationic demand and ζ-potential, resulting in a higher density of binding sites. Moreover, the charged and entangled network of DA-TOCNFs allowed for the individualization of AgNPs, unlike DAC, where some agglomerations were observed. Overall, this study presents an improved single-step process for the synthesis of AgNPs on nanocellulose surfaces, highlighting their potential for safe and high-performance applications in food packaging. Paper sheets coated with nanocellulose/AgNPs suspensions fully inhibited the growth of B. subtilis, at least for one month after coating, and caused damage to their cell membranes. This research provides a one-pot facile route to fabricating hybrid nanocellulose/AgNPs systems, stable in water, and may be used directly as a coating layer for board and paper active packaging with little or even undetectable release of Ag.

Structure-properties relationships of defined CNF single-networks crosslinked by telechelic PEGs

The high structural anisotropy and colloidal stability of cellulose nanofibrils' enable the creation of self-standing fibrillar hydrogel networks at very low solid contents. Adding methacrylate moieties on the surface of TEMPO oxidized CNFs allows the formation of more robust covalently crosslinked networks by free radical polymerization of acrylic monomers, exploiting the mechanical properties of these networks more efficiently. This technique yields strong and elastic networks but with an undefined network structure. In this work, we use acrylate-capped telechelic polymers derived from the step-growth polymerization of PEG diacrylate and dithiothreitol to crosslink methacrylated TEMPO-oxidized cellulose nanofibrils (MATO CNF). This combination resulted in flexible and strong hydrogels, as observed through rheological studies, compression and tensile loading. The structure and mechanical properties of these hydrogel networks were found to depend on the dimensions of the CNFs and polymer crosslinkers. The structure of the networks and the role of individual components were evaluated with SAXS (Small-Angle X-ray Scattering) and photo-rheology. A thorough understanding of hybrid CNF/polymer networks and how to best exploit the capacity of these networks enable further advancement of cellulose-based materials for applications in packaging, soft robotics, and biomedical engineering.

TEMPO-Oxidized Nanocellulose Films Modified by Tea Saponin Derived from Camellia oleifera: Physicochemical, Mechanical, and Antibacterial Properties.

Nanocellulose materials have been widely used in biomedicine, food packaging, aerospace, composite material, and other fields. In this work, cellulose obtained from Camellia shells through alkali boiling and subbleaching was micro-dissolved and regenerated using the DMAc (N,N-Dimethylacetamide)/LiCl system, and TOCNs (TEMPO-oxidized cellulose nanofibers) with different degrees of oxidation. The membrane was prepared by filtration of polytetrafluoroethylene (pore size 0.1 μm), and the oxidized nanocellulose film was obtained after drying, Then, the crystallinity, mechanical properties and oxygen barrier properties of the TOCN film were investigated. Furthermore, based on TS (tea saponin) from Camellia oleifera seed cake and TOCNs, TS-TOCN film was prepared by the heterogeneous reaction. The TS-TOCN film not only shows excellent oxygen barrier properties (the oxygen permeability is 2.88 cc·m-2·d-1) but also has good antibacterial effects on both Gram-negative and Gram-positive bacteria. The antibacterial property is comparable to ZnO-TOCN with the same antibacterial content prepared by the in-situ deposition method. Antioxidant activity tests in vitro showed that TS-TOCN had a significant scavenging effect on DPPH (2,2-Diphenyl-1-picrylhydrazyl) radicals. This design strategy makes it possible for inexpensive and abundant Camellia oleifera remainders to be widely used in the field of biobased materials.

Synthesis of Reusable CNF/Ag2Se Films as Visible-Light-Driven Photocatalysts for Photocatalytic Degradation of MB

AbstractIn our study’s scenario, flexible films were fabricated from TEMPO-oxidized cellulose nanofibers and silver selenide (CNF/Ag2Se) as efficient membranes for the degradation of methylene blue (MB). Different concentrations of Ag2Se particles were in situ prepared in the presence of CNF. The in-situ synthesis of Ag2Se nanoparticles in the presence of CNF was reported as efficient technique for the formation of submicrosize Ag2Se particles with a narrow size distribution and homogeneous dispersion onto CNF. TEM analysis revealed that the nanofibers had uniform width and diameter, while XRD demonstrated single-phase orthorhombic β-Ag2Se formation. 3D-FESEM showed tiny root measurer values of 28, 30, and 32.56 nm in polymeric films with 2.5, 5, and 10% Ag2Se-filled CNF. Polymeric films had visible-driven-light photocatalytic activity because the band gap fell from 4.61 eV (UV area) to 2.71 eV (visible region). The composite’s photocatalytic performance was assessed by MB degradation. 10% of CNF/Ag2Se demonstrated maximal photocatalytic activity under simulated sunlight for 60 min, pH 9, and 3 g/L composite weight. The factorial design statistical analysis showed that MB dye photodegradation is mostly affected by irradiation time and dye concentration. Environmental, social, and economic factors are all considered, making this study suitable for implementing photocatalysis to large-scale water treatment systems, which is a key component of sustainability.

Algal growth inhibition test with TEMPO-oxidized cellulose nanofibers

Ecotoxicity data on cellulose nanofibers (CNFs) are limited despite their wide potential applications prospects, such as structural and packaging materials, filters, coatings, foods, and cosmetics. In this study, toxicity tests of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized CNFs (TEMPO-CNFs), which are one of the major CNF products commercially available in Japan, on the green alga Raphidocelis subcapitata were conducted. As nanomaterials are considered difficult-to-test substances, the Organisation for Economic Co-operation and Development has released a guidance document that provides considerations regarding ecotoxicity tests of nanomaterials. In the algal growth inhibition tests of TEMPO-CNFs, there were specific issues to be examined, including the effects of medium components on the characteristics of TEMPO-CNFs, CNF interference with algal density measurements, algal interference with CNF measurements, and the effects of ion concentration changes in the test medium by the addition of CNFs on algal growth. To examine these issues, we conducted preliminary studies and established a suitable test method for algal growth inhibition tests of TEMPO-CNFs. We confirmed that the components in the medium for algal growth inhibition tests had negligible effects on the characteristics (zeta-potential, viscosity, and morphology) and concentration stability of TEMPO-CNFs and that in vitro and in vivo fluorescence measurements were applicable for estimating the algal densities, without interference by TEMPO-CNFs. In contrast, we observed that the grown algae interfered with the CNF concentration measurements. Therefore, we established a method to correct the measured CNF concentrations by estimating the algal contribution. Furthermore, we found that the nutrient salt concentrations in the medium changed due to interactions with CNFs; however, this change did not affect algal growth. Based on the results of the preliminary studies, algal growth inhibition tests of TEMPO-CNFs were conducted using in vitro and in vivo fluorescence measurements, along with measurements of CNFs and ion concentrations in the test dispersions. The test results showed that no growth inhibition was observed on growth rate or yield even at the maximum CNF concentration of 100 mg/L, suggesting that the ecological effect of TEMPO-CNFs on algae was relatively low. The results of this study will be valuable for conducting ecotoxicity assessments on additional CNFs and comparable nanomaterials in future studies.

Distribution of carboxy groups in TEMPO-oxidized cellulose nanofibrils prepared from never-dried Japanese cedar holocellulose, Japanese cedar-callus, and bacterial cellulose

We prepared 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized samples from never-dried Japanese cedar (JC) holocellulose, JC-callus, and bacterial cellulose (BC). The original never-dried samples and their TEMPO-oxidized products were characterized by neutral sugar composition analysis. TEMPO-oxidized cellulose nanofibrils (TEMPO-CNFs) were prepared from the TEMPO-oxidized samples by ultrasonication in water. The carboxy groups in TEMPO-CNFs were position-selectively esterified with 9-anthryl diazomethane (ADAM) to prepare TEMPO-CNF-COOCH2-C14H9 samples, which had UV absorption peak at 365 nm. The mass-average degree of polymerization (DPw) values of 1% lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) solutions of the original samples were determined by size-exclusion chromatography in combination with multi-angle laser-light scattering, ultraviolet absorption, and refractive index detection (SEC/MALLS/UV/RI), and were 5490, 2660, and 2380 for the JC holocellulose, JC-callus, and BC samples, respectively. The TEMPO-CNF-COOCH2-C14H9 sample solutions in 1% LiCl/DMAc were analyzed by SEC/MALLS/UV/RI to obtain SEC elution patterns. The patterns corresponded to the molar mass and carboxy group distributions of the samples, which were detected by RI and UV absorption of anthryl groups, respectively. The carboxy groups existed in the entire molar mass distribution regions of all the TEMPO-CNF samples, although their lower molar mass regions contained higher carboxy group densities. The obtained results indicate that random depolymerization occurred on the cellulose microfibril surfaces at the initial stage of TEMPO-catalyzed oxidation and/or ultrasonication in water. This depolymerization mechanism can explain all the obtained SEC-elution patterns of the TEMPO-CNFs, without considering the presence of periodically disordered regions in the cellulose microfibrils of the never-dried cellulose samples.Graphical abstract

Preparation of Silver Nanoparticles Deposited on TEMPO-Oxidized Cellulose Nanofibers

Silver nanoparticles (AgNPs) were synthesized by a chemical method in which cellulose nanofibers (CNFs) extracted from pineapple leaves served as a stabilizing and reducing agent. In this study, pineapple leaves were oxidized by the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation with sodium hypochlorite (NaClO) to obtain CNFs. After the oxidation, the transformation from hydroxyl groups to carboxylate groups of cellulose was confirmed by Fourier-transform infrared spectroscopy (FTIR), and TEMPO-oxidized CNFs with a higher carboxylate content were obtained. Then, TEMPO-oxidized CNFs with a carboxylate content of 2.49 mmol/g and non-oxidized CNFs with a carboxylate content of 0.68 mmol/g were used as a reducing agent to synthesize AgNPs. The formation of AgNPs was confirmed by color changes of the Ag solutions from white to yellow. Furthermore, AgNPs with an average diameter of 76.5 ± 22.15 nm were obtained when TEMPO-oxidized CNFs were used as a reducing agent, while non-oxidized CNFs generated AgNPs with a larger particle size of 181.2 ± 66.16 nm. This suggested that the TEMPO-oxidized CNFs could be used as a stabilizing and reducing agent for the synthesis of AgNPs with smaller diameters.

Surface charge manipulation for improved humidity sensing of TEMPO-oxidized cellulose nanofibrils

Cellulose-based humidity sensors have attracted great research interest due to their hydrophilicity, biodegradability, and low cost. However, they still suffer from relatively low humidity sensitivity. Due to the presence of negatively charged carboxylate groups, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibril (CNF) exhibits enhanced hydrophilicity and ion conductivity, which is considered a promising candidate for humidity sensing. In this work, we developed a facile strategy to improve the humidity sensitivity of CNF films by regulating their surface charge density. With the increase in surface charge density, both water uptake and charge carrier densities of the CNF films can be improved, enabling a humidity sensitivity of up to 44.5 % (%RH)−1, higher than that of most polymer-based humidity sensors reported in the literature. Meanwhile, the sensor also showed good linearity (R2 = 0.998) over the 15–75 % RH at 1 kHz. With these features, the CNF film was further demonstrated for applications in noncontact sensing, such as human respiration, moisture on fingertips, and water leakage, indicating the great potential of CNF film in humidity monitoring.

Revalorization of Yerba Mate Residues: Biopolymers-Based Films of Dual Wettability as Potential Mulching Materials.

Biodegradable mulching films are a very attractive solution to agronomical practices intended to achieve more successful crop results. And, in this context, the employment of agricultural and industrial food residues as starting material for their production is an alternative with economic and environmental advantages. This work reports the preparation of bilayer films having two different wettability characteristics from three bio-derived biopolymers: TEMPO-oxidized cellulose nanofibers isolated from infused Yerba Mate residues, Chitosan and Polylactic acid. The infused Yerba Mate residues, the isolated and oxidized cellulose nanofibers, and the films were characterized. Nanofibrillation yield, optical transmittance, cationic demand, carboxyl content, intrinsic viscosity, degree of polymerization, specific surface area and length were studied for the (ligno)cellulose nanofibers. Textural and chemical analysis, thermal and mechanical properties studies, as well as water and light interactions were included in the characterization of the films. The bilayer films are promising materials to be used as mulching films.

Preparation of tannic acid-reinforced cellulose nanofiber composites for all-water-based high-performance wood adhesives

Traditional adhesives easily release toxic gases during the preparation process or apply to wood composite products, which have adverse effects on the human body and the environment. Herein, an all-water-based high-performance wood adhesive is prepared using TEMPO-oxidized cellulose nanofiber (TOCNF), acrylamide (AM), and tannic acid (TA) through free radical polymerization. Different characteristics of the prepared composites, including morphology, injectability, and adhesion properties, have been investigated. Results showed that the TA/TOCNF/PAM composite has excellent injectability. The addition of TA can enhance the lap shear strength of the TA/TOCNF/PAM composites and with the increment of TA content, the lap shear strength gradually decreases. The formation of effective hydrogen bonds and Van der Waals interaction among the rich functional groups in the composite, lead to strong lap shear strength on different substrates. The composite with 5.0 g of AM, 5.0 g of the TOCNF suspension and 0.1 g TA possesses a high lap shear strength of 10.5 MPa on wood and 1.5 MPa on aluminium. Based on strong adhesion properties and excellent injectability, the TA/TOCNF/PAM composites have great potential in the furniture construction and building industries.

Green, recyclable and high latent heat form-stable phase change composites supported by cellulose nanofibers for thermal energy management

Efficiently addressing the challenge of leakage is crucial in the advancement of solid-liquid phase change thermal storage composite materials; however, numerous existing preparation methods often entail complexity and high energy consumption. Herein, a straightforward blending approach was adopted to fabricate stable phase change nanocomposites capitalizing on the interaction between TEMPO-oxidized cellulose nanofibers (TOCNF) and polyethylene glycol (PEG) molecules. By adjusting the ratio of TOCNF to PEG and the molecular weights of PEG, TOCNF/PEG phase change composites (TPCC) with customizable phase transition temperature (40.3–59.1 °C) and high phase transition latent heat (126.3–172.1 J/g) were obtained. The TPCC of high-loaded PEG (80–95 wt%) ensured a leakage rate of less than 1.7 wt% after 100 heating-cooling cycles. Moreover, TPCC exhibits excellent optical properties with a transmittance of over 90 % at room temperature and up to 96 % after heating. The thermal response analysis of TPCC demonstrates exceptional thermal-induced flexibility and good thermal stability, as well as recyclability and reshaping ability. This study may inspire others to design bio-based phase change composites with potential applications in thermal energy storage and management of smart-energy buildings, photothermal response devices, and waste heat-generating electronics.

Effect of TEMPO-oxidized bacterial cellulose nanofibers stabilized Pickering emulsion of cinnamon essential oil on structure and properties of gelatin composite films

Pure gelatin film often exhibits high hydrophilicity and a lack of antibacterial activity, hindering its practical application in the field of food preservation. To address these issues, we incorporated 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized bacterial cellulose (TOBC) nanofibers stabilized cinnamon essential oil (CEO) Pickering emulsions into the gelatin matrix to develop active food packaging films. The study revealed that the good distribution of emulsion droplets in the film matrix. While with increasing Pickering emulsion proportion, the microstructures of composite films were more heterogeneous, showing some pores or cavities. In addition, the insertion of TOBC-stabilized CEO emulsions could improve the elongation at break (EAB), water-resistance, UV blocking ability, and antibacterial activity of film, but reduced its tensile strength (TS) and water vapor barrier properties (WVP). Notably, the film prepared with 4 % TOBC-stabilized CEO Pickering emulsion demonstrated enhanced preservation of strawberries. Overall, the as-prepared gelatin-based active composite films have considerable potential for food packaging.

Cellulose nanofibrils-stabilized food-grade Pickering emulsions: Clarifying surface charge's contribution and advancing stabilization mechanism understanding

Pickering emulsions stabilized by cellulose nanofibrils (CN) have sparked significant attention, however the fundamental mechanisms underpinning the stabilization process remain insufficiently elucidated. Focusing on an academic debate of surface charge's contribution to stabilization, this study first explored how the varying carboxyl group contents of TEMPO-oxidized CN (TCNs) impacted Pickering emulsions' formation and stability. TCNs with 662 μmol/g carboxyl groups exhibited distinctive attributes, including larger particle sizes (322 nm in length), improved thermal stability (maximum decomposition temperature of 317 °C), and increased viscosity (1.57 Paִִ⋅s) compared to their counterparts with 963–1011 μmol/g charge density. Notably, the former one, with a larger three-phase contact angle (51.5°), higher interfacial tension, and greater detachment energy (21.69 × 10−18 J), resulted in a homogeneous dispersion of spherical oil droplets and super-stable Pickering emulsions with a consistent emulsifying index of 100% over 30 days. These findings clearly clarified that TCNs with a lower charge density exhibit superior emulsifying properties. In addition, for the first time, a distinct oil droplet-decorated fibrillar structure was observed, probably suggesting that TCNs might be able to serve as anchoring matrixes to guide the distribution of oil droplets. These structures seemed to impeded the migration and accumulation of the oil droplets, consequently enhancing the stability of the resulting Pickering emulsions. To sum, this study clearly elucidated the role of surface charge in stabilizing cellulose-based Pickering emulsions and proposed a new model to expound the cellulose-oil interaction mechanisms, thus providing new theoretical and practical insights on utilization of CN as highly effective emulsifier for super-stable food-grade Pickering emulsions.

Effects of UV irradiation of TEMPO-oxidized cellulose nanofibril/water dispersions on chemical structure, molar mass, and morphology

A commercial TEMPO-oxidized cellulose (TOC) and three laboratory-made TOC samples prepared under different conditions were converted to aqueous 0.4% dispersions of TEMPO-oxidized cellulose nanofibrils (TEMPO-CNFs) by high-pressure homogenization in water under the same conditions. The obtained TEMPO-CNF/water dispersions were irradiated with ultraviolet (UV) light for 0–48 h using a high-pressure mercury lamp at a main wavelength of 365 nm. The changes in the light transmittance, viscosity, pH, zeta-potential, and average particle size of the dispersions, and mass recovery ratio, molar mass, and carboxylate content of the acid-insoluble and freeze-dried fractions separated and isolated from the UV-irradiated dispersions were investigated. The results were analyzed in terms of the UV-irradiation time. The dispersion pH, and the mass recovery ratio, carboxylate content, and mass-average degree of polymerization (DPw) of the acid-soluble fraction decreased with increasing UV-irradiation time. This shows that some acid-soluble acidic compounds were formed from the TEMPO-CNFs via UV-induced depolymerization, degradation, and removal of carboxylate groups from the TEMPO-CNFs in water, depending on the UV-irradiation time. The average CNF length, which was determined from atomic force microscopy images, decreased with increasing UV-irradiation time. After UV irradiation of dispersions of the laboratory-made TEMPO-CNFs for 12 h, the average CNF lengths were 130–150 nm and their length distributions were narrower. UV irradiation of TEMPO-CNF/water dispersions is therefore a promising method for efficiently decreasing the dispersion viscosity, DPw, and average CNF length, depending on the TEMPO-CNF properties and UV-irradiation conditions.Graphical abstract

Biomimetic highly porous nanocellulose–nanohydroxyapatite scaffolds for bone tissue engineering

Wood-derived TEMPO-oxidized cellulose nanofibrils (CNFs) have potential as scaffolding for bone tissue engineering. Although biocompatible, the material lacks osteoconductive and appropriate mechanical properties. Incorporation of nano-hydroxyapatite (nHA) and modification of scaffold preparation methods could improve applicability. In this study, freeze-dried porous scaffolds were prepared using a range of nHA (0, 20, 33, 50%) and CNF compositions. Not only the microarchitecture but also the chemical composition of the scaffolds was studied. Osteoblast-like osteosarcoma derived cells (Saos-2) were cultured on the scaffolds and their responses (viability, attachment, proliferation, and osteogenic phenotype) to the different scaffolds were documented. The results show that incorporation of nHA influenced the microarchitecture, mechanical stiffness and surface properties of the scaffolds. Moreover, biological characterization demonstrated good cell viability in all the groups. However, the increase of nHA concentration beyond 20% does not offer further advantages. It is concluded that the incorporation of 20% nHA resulted in the widest and most biomimetic pore size distribution, increased surface roughness and improved protein adsorption. These changes in material properties enhanced cell spreading and the osteogenic gene expression of osteoblast-like cells seeded on the scaffolds. Moreover, 20% nHA warrants further investigation as a potential scaffolding material for bone tissue engineering.Graphical abstract

Transparent biodegradable composite plastic packaging film from TEMPO-oxidized cellulose nanofibers

In this research, we develop a method to create biodegradable food packaging films. Initially, TEMPO-oxidized cellulose nanofiber (TOCNF) undergoes sonication to produce well-dispersed single-strain nanofibers. These nanofibers are then blended with waterborne polyurethane (WPU) to enhance their extensibility. To further enhance compatibility between these two components, a non-ionic surfactant, Tween 80, is introduced into the TOCNF/WPU mixture to improve the dispersion of the WPU within the blend. The addition of Tween 80 significantly increases the transparency of the resulting film (Transmittance: 89.4 %, Haze: 2.2 %). Furthermore, the incorporation of the surfactant effectively reduces the formation of wrinkles and cracks during the film drying process, preventing adverse impacts on the film's barrier properties. The thin film further undergoes esterification crosslinking with citric acid to remove its hydrophilic groups for better water vapor barrier properties. The resulting bio-based packaging film exhibits remarkable transparency, strong biodegradability, and superior gas-barrier properties (water vapor and oxygen) compared to commonly used food packaging.

Silver Nanoparticles Supported onto TEMPO-Oxidized Cellulose Nanofibers for Promoting Cd2+ Cation Adsorption.

Nanocellulose constitutes a sustainable and biobased solution both as an efficient sorbent material for water treatment and as support for other inorganic nanomaterials with sorbent properties. Herein, we report the synthesis of a nanocomposite by deposition of in situ-generated silver nanoparticles (AgNPs) onto TEMPO-oxidized cellulose nanofibers (TOCNFs). Following an in-depth analytical investigation, we unveil for the first time the key role of AgNPs in enhancing the adsorption efficiency of TOCNF toward Cd2+ ions, chosen as model heavy metal contaminants. The obtained nanocomposite shows a value of Cd2+ sorption capacity at equilibrium from 150 mg L-1 ion aqueous solutions of ∼116 mg g-1 against the value of 78 mg g-1 measured for TOCNF alone. A combination of field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS) analyses suggests that Cd2+ ions are mainly adsorbed in the neighborhood of AgNPs. However, XPS characterization allows us to conclude that the role of AgNPs relies on increasing the exposure of carboxylic groups with respect to the original TOCNF, suggesting that these groups are still responsible for absorption. In fact, X-ray absorption spectroscopy (XAS) analysis of the Cd-K edge excludes a direct interaction between Ag0 and Cd2+, supporting the XPS results and confirming the coordination of the latter with carboxyl groups.