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 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 abstractCellulose nanofibril (CNF) aerogels have attracted great interests in recent years due to the low cost, sustainability and biocompatibility of raw CNF. However, the poor thermal stability and flammable feature of CNF aerogels have limited their wider applications. In this paper, polydopamine/CNF composite aerogels with good comprehensive properties are fabricated by modification of CNF with polydopamine and metal coordination bonds crosslinking. The microstructure and properties of composite aerogels are thoroughly characterized by a variety of tests. It is found that the microstructure of aerogels are more regular and the compressive strength of aerogels are enhanced by the incorporation of polydopamine and Fe3+ crosslinking. Importantly, the thermal stability and flame resistance of aerogels are significantly improved, which permit the application of composite aerogels in high-temperature thermal insulation. In addition, the reversible characteristic of metal coordination bonds allows the water induced healing of fractured composite aerogels. This study is expected to provide information for future development of green and high-performance aerogels.
Graphic abstractUniformly-sized porous cellulose beads functionalized with amidoxime groups were prepared for the first time using a microfluidic method with N-methylmorpholine N-oxide (NMMO) monohydrate as a cellulose solvent. The molten state cellulose dope in NMMO monohydrate (cell/NMMO dope) as a disperse phase and hot mineral oil as a continuous phase were used in a T-junction microfluidic chip to produce uniformly-sized cell/NMMO droplets. Coagulation of the molten state cell/NMMO droplet at high temperature and amidoxime functionalization could prepare the highly-porous spherical amidoxime-functionalized cellulose beads with a uniform fibrous open internal structure. The prepared amidoxime-functionalized cellulose beads showed excellent metal adsorption properties with a maximum adsorption capacity of?~?80 mg g?1 in the case of Cu2+/phthalate ions. The newly developed highly-porous cellulose beads can open many new applications with other proper functionalization at the reactive hydroxyl groups of the cellulose.
Graphic abstractThe development of a simple surface barrier discharge plasma device is presented to enable more widespread access to and utilization of plasma technology. The application of the plasma device was demonstrated for pretreatment of wood prior to application of protective coatings for outdoor usage. The coatings' overall performance was increased, showing a reduction or absence of cracking due to weathering on plasma-pretreated specimens. Moreover, after ten months of outdoor weathering, the plasma-pretreated specimens showed fewer infections with biotic factors and improved adhesion performance in cross-cut tests, while the surface gloss performed independently from plasma pretreatment. In contrast to that, plasma-pretreated specimens were slightly more prone to discoloration due to outdoor weathering, whereas the plasma pretreatment did not impact the initial color after coating application.
Graphic abstractOceans and soils have been contaminated with traditional plastic due to its lack of degradability. Therefore, green biopolymer composites reinforced with cellulose nanocrystal-zinc oxide hybrids (ZnO hybrids) with good biodegradation ability provided a positive impact on reducing environmental challenges. In this work, the effect of various morphologies of ZnO hybrids on the biodegradation ability of poly(butylene adipate-co-terephthalate), PBAT) under seawater, soil burial, and UV aging conditions were investigated. Sheet-like ZnO hybrids (s-ZnO hybrid) efficiently enhanced the mechanical, UV-blocking properties and biodegradation ability of PBAT nanocomposite films. Compared to neat PBAT, the best tensile strength of PBAT nanocomposite with 2 wt% s-ZnO hybrid was increased by 15.1%, meanwhile this nanocomposite films showed the highest biodegradation rate after 80 days of soil degradation and 90 days of seawater degradation. Besides, three possible biodegradation mechanisms of green PBAT nanocomposite films were presented, hinting that such PBAT nanocomposite have great promising packaging applications.
Graphic abstractBacterial cellulose (BC) is a polymer with interesting conformation and properties. BC can be obtained in different shapes and is easily modified by chemical and physical means, so its applications in the production of new materials and nanocomposites for different purposes have been in the focus of many research projects. However, one of the major challenges to address in bacterium-derived polymer technology is to find suitable carbon sources as substrates that are cheap and do not compete with food production for achieving large scale industrial applications. Agricultural wastes are defined as the residues from the growing and processing of raw agricultural products such as crops, fruits, vegetables and dairy products. Their composition can vary depending on the type of agricultural activity and harvesting conditions, but these residues are suitable for the production of BC. The aim of this review is to give insight into the production of BC using agro-wastes and an overview of the most interesting and novel applications of this biopolymer in different areas i.e. environmental applications, optoelectronic and conductive devices, food ingredients and packaging, biomedicine, and 3D printing technology.
Graphic 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 abstractThere are growing research interests in flax fibers due to their renewable ‘green’ origin and high strength. However, these natural fibers easily absorb moisture and have poor adhesion with polymer matrix leading to low interfacial strength for the composites. A hybrid chemical treatment technique combining alkali (sodium hydroxide) and silane treatments is adopted in the current study to modify flax fibers for improved performances of flax/polypropylene composites. Changes in chemical composition, microstructure, wettability, surface morphology, crystallinity and tensile properties of single flax fiber before and after chemical treatments were comprehensively characterized using techniques including SEM, FTIR, AFM, XRD, micro-fiber tester, etc. It was found that hemicellulose and lignin at the fiber surface were removed due to alkali treatment, which helped to reduce moisture absorption of the composites. Alkali-treated flax fibers were later subjected to silane treatment, which helped to improve the compatibility between flax fiber and polypropylene matrix. After alkali-silane hybrid chemical treatment, moisture absorption of the composites was further decreased. At the same time, the interfacial bonding strength between flax and polypropylene is significantly enhanced. All these results validate the great advantage of the hybrid chemical treatment approach for flax/polypropylene composites, which has the potential to promote the application of chemical treatment techniques in the plant fiber composite industry.
Graphic abstractDifferent topical hemostatic materials are used to achieve effective hemostasis. High hemostatic activity, biocompatibility, bioresorbability, and easy manipulation are to be expected in such a developed product. In the surgical world with these specific requirements, finding a proper hemostatic agent is very difficult. The study compared several materials of various construction properties, which were assessed for structural and related properties by morphological analyses and assessed in vivo for their efficiency and behaviour using a model of rat partial nephrectomy. New sodium salt of carboxymethyl cellulose (CMC) sponge with the lowest porosity and free swell absorptive capacity contained the highest amount of hydroxyl and carboxyl groups. Results revealed that this CMC material in the form of a bioresorbable sponge may ensure the necessary hemostatic effects, while also providing a positive influence on the reaction of the local tissue. The CMC material also needed significantly less time to achieve hemostasis (p?<?0.001). Moreover, the sponge reached satisfactory results in the histopathological evaluation with the lowest destruction score and favorable healing reaction. This modified product proved itself to be a promising bioresorbable hemostat, which, according to its design, matches with its surgical applications. In general, the obtained data elucidated the dependency of the total effect on its structure and composition.
Graphic 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 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 abstractMultifunctional fibers have attracted widespread attention due to applications in flexible smart wearable devices. However, simultaneously obtaining a strong and functional woven fiber is still a great challenge owing to the conflict between the properties mentioned above. Herein, mechanically strong and highly conductive cellulose/carbon nanotube (CNT) composite fibers were spun using an aqueous alkaline/urea solution. The microstructure as well as physical properties of the resulting fibers were characterized via scanning electron microscopy, infrared spectroscopy, mechanical and electrical measurement. We demonstrated that carboxylic CNTs can be well dispersed in alkali/urea aqueous systems which also dissolved cellulose well. The subsequent wet spinning process aligned the CNTs and cellulose molecules inside the regenerated composite fiber well, enhancing the interaction between these two components and endowing the composite fiber having a 20% CNT loading with an excellent mechanical strength of 185 MPa. Benefiting from the formation of conductive paths, the composite fiber with the diameter of about 50 μm possessed an electrical conductivity value in the range of 64–1274 S/m for 5–20 wt% CNT loading. This excellent mechanical strength and high electrical conductivity enable the composite fiber to exhibit a great potential in joule heating; the heating temperature of cellulose/CNT-20 fiber reached more than 55 °C within 15 s at 9 V. In addition, the multifunctional filaments are further manufactured as a water sensor to measure humidity. This work provides a potential material that can be applied in the fields of wearable electronics and smart flexible fabrics.
Graphic 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
The present work aims to investigate the feasibility of oxalic acid-choline chloride deep eutectic solvent (OA-ChCl DES), which serves as a promising green solvent that utilized in the acidic deep eutectic solvent (DES) hydrolysis. Oxalic acid-choline chloride DES cellulose nanocrystal (OA-ChCl DES CNC) was isolated from the bleached DES treated pulp (BP) through the acidic DES hydrolysis using 1:1 molar ratio of OA-ChCl DES. The functional groups, crystallinity index, morphological structure, particle size, zeta potential, thermal stability and surface chemistry of the OA-ChCl DES CNC were compared with the sulphuric acid cellulose nanocrystal (SA-CNC) that prepared via sulphuric acid hydrolysis. The findings revealed the presence of negatively charged carboxyl groups on OA-ChCl DES CNC surface after the acidic DES hydrolysis. The physicochemical analyses verified that the OA-ChCl DES CNC was in nano-sized range with polydispersity index (PdI) of 0.56, indicating slightly monodispersed nanoparticles. A stable OA-ChCl DES CNC colloidal suspension with zeta potential value of ?52.1?±?5.2 mV was obtained. The OA-ChCl DES CNC outweighed the SA-CNC in term of thermal stability (288 °C) despite having a slightly lower crystallinity index (76.7%). In fact, the OA-ChCl DES CNC with a yield of 55.1% was achieved through the acidic DES hydrolysis, suggesting that the OA-ChCl DES was capable of promoting efficient cleavage of strong hydrogen bonds in BP.
Graphic abstractHerein, cellulose nanofibrils (CNF), alkali lignin (AL), and montmorillonite (MMT) were used to produce reinforced polyvinyl alcohol (PVA) hydrogels. The effects of MMT and AL contents on the rheological properties of reinforced hydrogel were studied. Compared with PVA/CNF hydrogel, the storage modulus of 40 wt% MMT-reinforced PVA hydrogel was increased by 41.4%. The rheological properties of MMT-enhanced PVA hydrogel could be adjusted by the variation of MMT loading. Also, as the PVA matrix had a synergistic effect with the embedded MMT and AL, the composite hydrogel demonstrated high efficiency in the removal of methylene blue dye (MB) from wastewater. Adsorption tests conducted at various time intervals (60–360 min) show that the hydrogels containing same content of MMT had higher removal efficiency. The MB adsorption of PVA/2CNF-0Li-40MMT was over 98.0%, whereas its adsorption equilibrium time and maximum adsorption capacity (qm) were 360 min and 67.2 mg/g, respectively. However, an extremely high content of MMT reduced the MB adsorption rate.
Graphic abstractInspired by mussels, a new cellulose-based (CTP) adhesive was fabricated by simply blending via cellulose nanofibrils (CNFs), tannic acid (TA), and polyethyleneimine (PEI), where the preparation method was green, facile, and simple. The structure and properties were examined by FT-IR, TGA, XRD, SEM, lap shear tensile, and water absorption tests. The results showed that chemical bonds, hydrogen bonds, and chain entanglement were formed among CNFs, TA, and PEI. Compared with the CNF adhesive, the dry shear strength of the CTP adhesive increased 103% to 392.2?±?32.2 kPa. And the wet shear strength of CTP adhesive increased from 0 kPa to 144.7?±?20.1 kPa, indicating that the CTP adhesive can be used in humid or even water environments. Meanwhile, the water absorption of CTP adhesive decreased from 37.9?±?14.1% to 12.8?±?5.9%. It was the introduction of catechol groups and physical–chemical interactions of three components that endow the CTP adhesive with improved dry and wet adhesion strength and water resistance. Moreover, the proposed CTP adhesive could be used on the surface of various materials, including rubber, plastic, paper, wood, metal, and glass. Overall, this work shows that the CTP adhesive has a wide range of application prospects.
Graphical abstractArrowroot starch (AA)-based films incorporated with a carnauba wax nanoemulsion (CWN), cellulose nanocrystals (CNCs), and essential oils (EOs) from Mentha spicata (MEO) and Cymbopogon martinii (CEO) were produced using the casting technique and then characterized in terms of their water barrier, tensile, thermal, optical, and microstructural properties and in vitro antifungal activity against Rhizopus stolonifer and Botrytis cinerea. Whereas the incorporation of CNCs decreased the moisture content and water vapor permeability of the AA/CWN/CNC film, the additional incorporation of either EO decreased the transparency and affected the microstructure of the AA/CWN/CNC/EO nanocomposites. MEO and CEO incorporation improved the thermal stability of the films and provided excellent protection against fruit-spoiling fungi. Because of their excellent barrier properties against fungal growth, water vapor permeability, and ultraviolet and visible light, these AA/CWN/CNC/EO films have promising potential for application as active food packaging or coating materials.
Graphic 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 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 abstract