In this paper, we developed a microbial route to fabricate wood-inspired biomimetic composites comparable to natural wood. Focusing on the chemical composition of woody biomass, we performed in situ bioprocessing of bacterial cellulose (BC) imbibed in modified cationic lignin (Catlig), which exhibited significant bioactivity in improving the microbial growth dynamics. The structural and morphological characteristics were enhanced by the formation of hydrophobic and electrostatic interactions between BC and Catlig during biosynthesis. Microbially derived BC/Catlig composites exhibited enhanced thermal stability and crystallinity, with oriented cellulose fibers. The tensile properties, toughness, and specific strength of BC/Catlig composites were comparable to those of a heavy wood species (Zelkova serrata) under hydrated conditions and synthetic soft materials.
Graphic abstractIncreasing electromagnetic pollution calls for electromagnetic interference (EMI) shielding materials, especially sustainable, lightweight, and environmentally stable, biomass-based materials. MXene-coated wood (M/wood) is prepared by simply spraying MXene sheets on the wood surface. Varying this spray coating manipulates the shielding performance and its application to different wood species. The M/wood exhibits high electrical conductivity (sheet resistance is only 0.65 Ω/sq) with an excellent EMI shielding effectiveness of 31.1 dB at 8.2?~?12.4 GHz and is also fire retardant. Furthermore, waterborne acrylic resin (WA) is coated on M/wood to enhance environmental stability. The WA coating improves EMI shielding performance stability after water-soaking and drying testing and prevents the peeling of MXene from wood. These satisfactory properties of WA-M/wood and the facile manufacturing approach promote the feasibility of wood-based EMI shielding materials.
Graphical abstractCellulose-based triboelectric nanogenerators (TENGs) can provide power for various monitoring devices and are environmentally friendly and sustainable. Chemical functional modification is a common method to improve the electrical output performance of cellulose-based TENGs. In this work, an environmentally friendly high-performance triboelectric nanogenerator based on a polydopamine/cellulose nanofibril (PDA/CNF) composite membrane and fluorinated ethylene propylene was developed. Dopamine generates polydopamine nanoparticles through oxidative self-polymerization and adheres to the surface of nanofibers. The synergistic effect of amino group introduction and membrane surface microstructure effectively enhanced the output performance of TENGs to a certain extent. The effects of PDA content, CNF composite film thickness and different working conditions on the electrical output were systematically investigated. The optimized PDA/CNF-TENGs exhibited an enhanced electrical output performance with voltage, current, and power density values of ≈205 V, ≈20 µA, and ≈48.75 μW·cm?2, respectively. The PDA/CNF-TENGs exhibited stable and identifiable signals when used as a self-powered sensor for human motion monitoring, showing the potential prospects of cellulose materials for TENGS and other electronic applications.
Graphical abstractIn this, an efficient flame retardant composite has been prepared using biowaste derived phosphorous groups decorated graphene supported nanomaterial. The eggshell was utilized as a source of calcium carbonate, which was converted to monocalcium phosphate (CP) by phosphoric acid treatment. As-prepared monocalcium phosphate was functionalized with graphene to prepare graphene functionalized monocalcium phosphate (GCP). The GCP-coated fabric didn't ignite during the flame test and sustained more than 600 s on continuous exposure to flame without changing its initial length and shape. Whereas, graphene oxide (GO), and CP coated cotton fabric burnt out very easily within a short time. The efficient flame retardant property of as synthesized GCP coated cotton fabric was confirmed with a high limiting oxygen index (34.1) and char length of 2.5 cm was generated from the VFT test. The synthesized GCP coated cotton fabric also confirmed efficient flame retardant properties. This facile method enables an easy process for mass production of cost-effective, bio-waste derived nanomaterial for a significantly highly efficient candidate for different applications in sustainable chemistry, including flame-retardant applications.
Graphical abstractThe surgical masks have been essential consumables for public in the COVID-19 pandemic. However, long-time wearing masks will make wearers feel uncomfortable and massive discarded non-biodegradable masks lead to a heavy burden on our environment. In this paper, we adopt degradable chitosan@silver (CS@Ag) core–shell fibers and plant fibers to prepare an eco-friendly mask with excellent thermal comfort, self-sterilization, and antiviral effects. The thermal network of CS@Ag core–shell fibers highly improves the in-plane thermal conductivity of masks, which is 4.45 times higher than that of commercial masks. Because of the electrical conductivity of Ag, the fabricated mask can be electrically heated to warm the wearer in a cold environment and disinfect COVID-19 facilely at room temperature. Meanwhile, the in-situ reduced silver nanoparticles (AgNPs) endow the mask with superior antibacterial properties. Therefore, this mask shows a great potential to address the urgent need for a thermally comfortable, antibacterial, antiviral, and eco-friendly mask.
Graphical abstractIn this study, the effect of pectin extraction method on the properties of cellulose nanofibers (CNFs) isolated from sugar beet pulp (SBP) was studied. Pectin was extracted by the industrially practiced method by sulfuric acid hydrolysis or by enzymatic hydrolysis using a cellulase/xylanase enzymes mixture. The CNFs were then isolated by high-pressure homogenization and investigated in terms of their chemical composition, crystallinity, size, degree of polymerization, and re-dispersion in water after freeze-drying. The mechanical properties and surface characteristics of CNF films were also studied. The results showed that fibrillation of the de-pectinated SBP was more efficient for the acid hydrolyzed SBP. CNFs from the acid-hydrolyzed SBP had a slightly wider diameter, higher crystallinity, viscosity, and α-cellulose content but a lower degree of polymerization than CNFs from the enzyme-hydrolyzed SBP. Owing to the presence of more residual hemicelluloses in the CNFs from the enzyme-hydrolyzed SBP, the CNFs had higher re-dispersion ability in water. CNF films from enzyme-hydrolyzed SBP displayed slightly better mechanical properties and higher water contact angle than acid-hydrolyzed CNF films.
Graphic abstractLife-threatening diseases, especially those caused by pathogens and harmful ultraviolet radiation (UV-R), have triggered increasing demands for comfortable, antimicrobial, and UV-R protective clothing with a long service life. However, developing such textiles with exceptional wash durability is still challenging. Herein, we demonstrate how to fabricate wash durable multifunctional cotton textiles by growing in situ ZnO-TiO2 hybrid nanocrystals (NCs) on the surface of cellulosic fabrics. The ZnO-TiO2 hybrid NCs presented high functional efficiency, owing to their high charge transfer/separation. Ultrafine fiber surface pores, utilized as nucleating sites, endowed the uniform growth of NCs and their physical locking. The resulting fabrics presented excellent UV protection factors up to 54, displayed bactericidal efficiency of 100% against Staphylococcus aureus and Escherichia coli, and optimum self-cleaning efficacy. Moreover, the functionalized textiles exhibited robust washing durability, maintaining antibacterial and anti-UV-R efficiency even after 30 extensive washing cycles.
Graphical abstractA cellulosic material has been synthesized that could efficiently and selectively adsorb organic and inorganic contaminants from aqueous solutions without interference from competing adsorption sites. Cellulose-graft-tetraethylenepentamine molecular imprinted polymer (C-TEPA-MIP) was synthesized by using 4-nitrophenol (4-NP) as the template. The C-TEPA-MIP adsorbent could adsorb 4-NP and Cr(VI) simultaneously and selectively, without being affected by the competitive adsorption sites of each of these pollutants. The adsorption of 4-NP was predominantly due to the imprinted sites of 4-NP in C-TEPA-MIP that were located inside of the adsorbent, whereas that of Cr(VI) was primarily due to the amine groups of TEPA found on the surface of the adsorbent. Compared with the non-imprint polymer synthesized without the template, C-TEPA-MIP showed higher selectivity for both 4-NP and Cr(VI) in unitary and binary systems. In addition, C-TEPA-MIP exhibited good stability and recyclability for 4-NP, which makes it a promising candidate material for applications concerning wastewater treatment.
Graphical abstractThis study introduces an effective route to fabricate chitosan (CS)-based film. The films were prepared through cross-linking reaction between CS and hydroxyethyl cellulose (HEC) using epichlorohydrin (ECH) as the cross-linker and simultaneously in-situ loading with CuO nanoparticles. FT-IR and loading efficiency results indicated the occurrence of inter- and intra-molecular cross-linking reaction between CS and HEC. XRD and EDS analyses showed that the CuO nanoparticles were evenly deposited onto CS film matrixes. SEM characterization showed that the films were of compact, dense and uniform cross morphologies, as well as obvious voids. The films also exhibited desired swelling ratio and water vapor permeability. The enhanced tensile strength was obtained with a maximum value of 77.02?±?3.26 MPa, while the stretch-ability slightly decreased. The thermal stability of the films decreased after cross-linking with HEC. The antibacterial ability of the films was generally improved with the increase of HEC and ECH contents.
Graphical abstractPreparation and properties of epichlorohydrin-cross-linked chitosan/hydroxyethyl cellulose based CuO nanocomposite films
Several eucalyptus pulps (85% of cellulose) with different lignin and HexA content (unbleached, TCF and ECF) as well as cotton linters (97% of cellulose) were treated with ozone (at different pH and ozone doses) in order to modify its fibre-components. Special interest was given in the introduction of functional groups in carbohydrates. The presence of these groups was mainly identified by the chain scissions due to carbonyl groups (CSC=O) produced in cellulose during viscosity measurement. At a dose of 0.5% odp of ozone, the greatest amount of CSC=O (0.5) was created at acidic pH and with the ECF pulp, followed by the TCF (0.3) and by the unbleached (0.2). The same CSC=O (0.2) was obtained in cotton pulp. In this pulp, the ozone concentration had to be increased for the treatment to be effective. A further increase in the accessibility in both pulps was achieved by applying a washing stage between two ozone stages at 0.5% (0.5?+?0.5). With this treatment, the CSC=O was increased to 5.3 in the ECF, to 0.8 in the TCF and only to 0.3 in cotton. Brightness reversion and the amount of DNPH consumed were also used to verify the presence of functional groups. At 0.5?+?0.5, brightness reversion was increased from 16 to 55% in ECF, from 27 to 46% in TCF and from 7 to 31% in cotton. Therefore, it is shown that functional groups can be introduced by ozone in carbohydrates, but this effect strongly depends on the lignin, HexA and hemicellulose content.
Graphical abstractWearable flexible sensors with quick response time and high stability are required in the fields of human motion detection, personal health monitoring, and artificial electronic skin. However, their design remains a challenge. To address this need, we fabricate a piezoresistive sensor with a wide detection limit, fast response time, and excellent stability in this work. Nickel (Ni) and copper (Cu) films are deposited on cotton fabric (CF) by in-situ polymerization of polyaniline (PANI) using magnetic filtration cathode vacuum arc deposition technology to obtain copper/polyaniline cotton (Cu/PANI/CF) and nickel/polyaniline cotton (Ni/PANI/CF). The pressure sensor is then fabricated by self-assembly. The proposed pressure sensor has a wide detection limit (0–180 kPa), rapid response time (30 ms), high cycle stability (>5000), and can detect the movement of each joint of the human body (such as the knee, finger, elbow, etc.). The sensor can also monitor different facial micro-expressions, including smiles and blinking. Based on the practical application of human motion signals and the detection of subtle stress, the proposed sensor demonstrates significant potential as a wearable electronic product for health monitoring.
Graphical abstractA variety of liquid energy exists in papermaking engineering and has not yet been developed and utilized. In addition, for the papermaking industry, the presence of slime can seriously affect the quality of the finished paper and can lead to paper breaking. The current slime control strategies cannot completely solve the problem and also have some low toxicity. In this study, a method of self-powered sterilization of cellulose fibers by using triboelectric pulsed direct current is reported. A liquid–solid triboelectric nanogenerator (L–S TENG) was used to convert the liquid energy of nanocellulose suspension into electrical energy and convert this electrical energy into pulsed direct current for self-powered sterilization of cellulose fiber. A hydrophobic coating material is used as solid triboelectric material and electrode for sterilization. Driven by L–S TENG, the electrodes exhibited an excellent sterilization rate against four microorganisms including Escherichia coli, Aspergillus niger, Candida albicans, and Klebsiella pneumoniae, which from slime in the papermaking industry. This study could provide a basic research theory for liquid energy harvesting in the papermaking industry, and also provide a new strategy for pulp sterilization.
Graphical abstractIonic cellulose nanocrystals (CNCs) are interesting surface-active particles for encapsulating a lipophilic liquid in water. A CNC is modified chemically to a negative charge (an S-CNC) by surface treatment with sulfuric acid. Despite the amphiphilic nature of S-CNCs, it is difficult to determine the degree of substitution for emulsification of lipophilic liquids, especially when the surface energy is low and polarity is high. Here, we control the substitution of S-CNCs by desulfation of S-CNCs (dS-CNCs) using a low-concentration hydrochloric acid solution. Decreased surface charge of S-CNCs was expected, and the lipophilic affinity of dS-CNCs increased compared with those of S-CNCs. Six oils with differing surface tensions were selected for determination of the effect of charged CNCs on emulsification. The stability of the emulsion was evaluated by emulsion fraction, emulsion particle size, and surface tension of emulsified solutions from dS-CNCs and oils.
Graphical abstractThe horse chestnut seed shell (HC) and chestnut seed shell (CT) were evaluated as renewable, sustainable, and cheap raw materials transformed into valuable products, “cellulose nanocrystals (CNCs).” Alkali and bleaching treatments were performed to obtain horse chestnut cellulose (HCS) and chestnut cellulose (CTS) and subsequently isolated to the horse chestnut cellulose nanocrystal (HC-CNC) and chestnut cellulose nanocrystal (CT-CNC) by sulphuric acid hydrolysis. Raw materials and their products were comparatively investigated at each stage of the isolation process. The cellulose, hemicellulose, and lignin content of HC and CT were determined via chemical composition analysis. The structural analysis was performed using Fourier transform infrared spectroscopy and X-ray diffraction technics for CNCs. Morphological analysis and size range determination of the samples were carried out via atomic force microscopy (AFM) and particle size analysis. Zeta potential and particle size distribution were determined by analyzing the surface and particle size. The thermal behaviors were investigated at different phases of treatments using thermal gravimetric analysis (TGA/DTG). HC-CNC demonstrates a higher crystallinity index value of 85.49% and a lower yield of 20.46%, whereas CT-CNC shows a lower crystallinity of 65.06% and a higher yield of 36.59%. A differentiation in structural, thermal, and morphological properties of extracted celluloses and isolated CNCs was observed depending on the source of the raw materials. However, a morphological alteration in CNC structures has emerged relative to precursor cellulose after the acid hydrolysis process as an essential finding via AFM studies. The solid wastes horse chestnut and chestnut seed shells offer great potential as suitable, sustainable, and environmentally friendly starting raw materials to produce CNC and in applications, including wastewater treatments, biosensing, wound dressing, and reinforcement for polymer composites due to their excellent thermal and structural properties.
Graphical abstractFabricating mechanically strong hydrogels that can withstand the conditions in internal tissues is a challenging task. We have designed hydrogels based on multicomponent systems by combining chitosan, starch/cellulose, PVA, and PEDOT:PSS via one-pot synthesis. The starch-based hydrogels were homogeneous, while the cellulose-based hydrogels showed the presence of cellulose micro- and nanofibers. The cellulose-based hydrogels demonstrated a swelling ratio between 121 and 156%, while the starch-based hydrogels showed higher values, from 234 to 280%. Tensile tests indicated that the presence of starch in the hydrogels provided high flexibility (strain at break?>?300%), while combination with cellulose led to the formation of stiffer hydrogels (elastic moduli 3.9–6.6 MPa). The ultimate tensile strength for both types of hydrogels was similar (2.8–3.9 MPa). The adhesion and growth of human osteoblast-like SAOS-2 cells was higher on hydrogels with cellulose than on hydrogels with starch, and was higher on hydrogels with PEDOT:PSS than on hydrogels without this polymer. The metabolic activity of cells cultivated for 3 days in the hydrogel infusions indicated that no acutely toxic compounds were released. This is promising for further possible applications of these hydrogels in tissue engineering or in wound dressings.
Graphical abstractThis study prepared a waterproof cellulose nanofibril (CNF) sheet via the deposition of an alkyl ketene dimer (AKD) on the sheet’s controlled porous structure. The porosity of the CNF sheet was controlled by drying under different conditions, which included hot-press drying (HD) and solvent-exchange drying (SD), and the effect on the hydrophobization and water-related barrier performance of the sheet were investigated. When the SD sheet was immersed in an AKD wax solution, the sheet exhibited super-hydrophobicity and a lower water vapor transmission rate, compared with the HD sheet. This indicated that the porous structure of the SD sheet enabled AKD to be adsorbed on both the surface and the inner surface and it filled in the pores of the sheet, thereby giving rise to excellent waterproofing properties. The performance of a hydrophobized SD sheet as a water barrier material was comparable to a linear low-density polyethylene film. This study confirms the possibility for AKD wax to be immersed in a porous CNF sheet and used as a potential barrier material in hydrogel packaging.
Graphical abstractEucalyptus cellulose is usually pre-treated by oxidation with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), NaBr and NaClO at pH 10.5 and 25 °C before the mechanical process required to obtain cellulose nanofibers (CNFs). In this study, different aspects to improve the effectiveness and sustainability of the TEMPO-mediated oxidation are analyzed. The optimization was carried out at different reaction times by modifying both the concentration of the NaClO and the amount of the catalysts (TEMPO and NaBr). Results show that the carboxyl groups increased up to 1.1 mmol/g with 5 mmol NaClO/g after 50 min, and that the catalyst concentration can be reduced to 0.025 mmol TEMPO/g and 0.5 mmol NaBr/g to minimize costs while maintaining the high fibrillation degree of the CNFs. The kinetic of the reaction can be considered as zero-order with respect to NaClO, and as first order with respect to cellulose. As a result of this work, the catalyst doses are reduced up to 75% compared to the most widely used catalyst doses (0.1 mmol/g TEMPO and 1 mmol/g NaBr), obtaining highly fibrillated CNFs with a lower environmental impact. This reduction of catalyst doses will reduce the costs and facilitate the implementation of CNF production at industrial scale.
Graphical abstractMembrane applications for the separation of surfactant-stabilized emulsions are often constrained by a deficiency in permeability and anti-fouling properties. Herein, special wetted cotton fabric with a protective layer (P-MH@CF) for durable anti-fouling performance was synthesized by a two-step method, which was related to interfacial ion migration technology and unilateral spraying treatment. Permeability of water and separation performance of P-MH@CF membrane were investigated systematically. Emulsions stabilized by anionic, cationic, or non-ionic surfactant were successfully separated with high efficiency. In the process of separation, the oil droplets surrounded by surfactants were difficult to demulsify and gathered physically on the membrane surface to form a “cream layer”. The stearic acid acted as a protective layer, like a quilt, protecting the membrane from contamination. The membrane retained robust reusability for separation even after the “cream layer” had been washed off, which was promising for the remediation of oily wastewater containing surfactants.
Graphical abstractThe complex anatomy of teeth limits the accessibility and efficacy of regenerative treatments. Therefore, the application of well-known inducers as injectable hydrogels for the regeneration of the dentin-pulp complex is considered a promising approach. In this regard, this study aimed to develop an injectable hydrogel containing mineral trioxide aggregate (MTA). The injectable chitosan/oxidized-nanocrystalline cellulose/MTA (CS/OCNC/MTA) hydrogels were prepared, and the physicochemical properties of these hydrogels were evaluated by TGA, FTIR, Rheological analysis, and SEM. Moreover, the effect of MTA on the swelling and degradability of scaffolds was assessed. The proliferative effects of synthesized hydrogels were also determined on human dental pulp stem cells (hDPSCs) by MTT assay. For induction of differentiation and biomineralization in these cells, the alkaline phosphatase activity and Alizarin Red S staining tests were performed in the presence of fabricated scaffolds. The proliferation of hDPSCs was significantly increased in the presence of these hydrogels. Moreover, the addition of MTA to hydrogel structure dramatically improved the differentiation of hDPSCs. These results suggested that this novel injectable hydrogel provides appropriate physiochemical properties and can be considered a promising scaffold for regenerative endodontic procedures.
Graphical abstractVulcanized fibers are all-cellulose materials made from cotton and/or wood cellulose after aqueous zinc chloride treatment. These materials were invented in the UK in the mid-nineteenth century and is widely used because of their excellent characteristics, such as impact resistance and electrical insulation. Recently the matured vulcanized fibers have been recognized as renewable and biodegradable materials and reevaluated with advanced cellulose technologies derived from cellulose nanofibers (CNFs) and all-cellulose composites. The microscopic analysis based on the improved freeze-drying method revealed that the strength of vulcanized fiber sheets can be attributed to the chemically defibrillated CNFs. The architecture is similar to all-cellulose composites made from the same raw materials in which the residual cellulose fibers serve as reinforcement, and the CNFs serve as adhesives or matrix components. In this report, we describe the history and structural characteristics of vulcanized fibers and introduce a new aspect in aqueous zinc chloride treatment of cellulose.
Graphical abstract