Deep eutectic supramolecular polymer functionalized MXene for enhancing mechanical properties, photothermal conversion, and bacterial inactivation of cellulose textiles.

Two-dimensional (2D) transition metal carbides (Ti3C2Tx MXene) have gained significant attention for their potential in constructing diverse functional materials, However, MXene is easily oxidized and weakly bound to the cellulose matrix, which pose challenges in developing MXene-decorated non-woven fabric with strong bonding and stable thermal management properties. Herein, we successfully prepared deep eutectic supramolecular polymer (DESP) functionalized MXene to address these issues. MXene can be wrapped with DESP to be insulated from water and protected from being oxidized. Subsequently, we achieved an efficient in-situ deposition of DESP-functionalized MXene onto fibers through a combination of dip coating and photopolymerization technique. The resulting nonwoven fabric (CNs-DESP@M) exhibited excellent photothermal conversion properties along with rapid thermal response and functional stability. Interestingly, the interface bonding between MXene and the fiber surface was significantly enhanced due to the abundant pyrogallol groups in DESP, resulting in the composite textile exhibiting commendable mechanical properties (2.68 MPa). Moreover, the as-prepared textile demonstrates outstanding bactericidal efficacy against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The multifunctional textile, created through a facile and efficient approach, demonstrates remarkable potential for applications in smart textiles, catering to the diverse needs of individuals in the future.

Functionalized cellulose nanofibrils based supramolecular system-assisted molding enabled strong, antibacterial chitosan bioplastics.

Bioplastics are considered as potential alternatives to non-renewable and non-biodegradable petroleum-based plastics. Inspired by ionic and amphiphilic properties of mussel protein, we proposed a versatile and facile strategy for the fabrication of a high-performance chitosan (CS) composite film. This technique incorporates a cationic hyperbranched polyamide (QHB) and a supramolecular system based on the lignosulphonate (LS)-functionalized cellulose nanofibrils (CNF) (LS@CNF) hybrids. The cationic QHB was synthesized by a one-step process from hyperbranched polyamide and quaternary ammonium salt. Meanwhile, the functional LS@CNF hybrids act as a well-dispersed and rigid cross-linked domain in CS matrix. Owing to the interconnected hyperbranched and enhanced supramolecular network, the toughness and tensile strength of the CS/QHB/LS@CNF film simultaneously increased to 19.1 MJ/m3 and 50.4 MPa, 170.2 % and 72.6 % higher than the pristine CS film. Additionally, the functional QHB/LS@CNF hybrids endow the films with superior antibacterial activity, water resistance, UV shielding, and thermal stability. This bioinspired strategy provides a novel and sustainable method for the production of multifunctional CS films.

Bioinspired phenol-amine chemistry for developing bioadhesives based on biomineralized cellulose nanocrystals.

Inspired by the phenol-amine chemistry and biomineralization of insect cuticles, we developed a green and facile strategy for preparing a bio-adhesive with excellent adhesion properties, mildew resistance, and antibacterial activity. This biomimetic strategy incorporates functional catechol-modified ε-polylysine and vanillin via grafting and Schiff base reactions. The biomineralized cellulose nanocrystals were prepared using a cellulose nanocrystal bio-template by regulating the in-situ biomineralization of inorganic nanoparticles, thereby building an optimized organic-inorganic mineralization framework in the polymer. The bonding strength of composite adhesive was significantly improved by multiple cross-linking networks through sacrificial hydrogen bonds, electrostatic interactions, and dynamic covalent bonds. The adhesion strength of the composite adhesive reached 1.13 MPa, which was 151% higher than the pristine adhesive. As a result of the synergistic effect of the catechol component, cationic ε-polylysine, and aldehyde group, the bio-adhesive also exhibited favorable anti-mildew and anti-bacterial properties.

Phytic acid-assisted fabrication for soybean meal/nanofiber composite adhesive via bioinspired chelation reinforcement strategy.

Adhesives are commonly used in the wood industry, such as plywood, fiberboard, and particleboard, for making furniture, flooring, kitchen cabinets, and wall materials. However, almost all of these adhesives come from petroleum resources and release toxic substances that pollute the environment and endanger human health. Therefore, it is necessary to promote the production of eco-friendly adhesives. The development of plant-protein-based adhesives can increase the value of agricultural wastes and reduce the environmental hazards. However, their industrial application is limited by their poor mechanical strength and inferior water resistance. The main purpose of this study was to prepare a green effective reinforcer to improve the water resistance and mechanical strength of soybean meal (SM) adhesive. To achieve the above goals, a natural chelating agent phytic acid (PA)-mediated aminoclay-cellulose nanofiber (AC@CNF) nanohybrid was prepared. Then, the AC@CNF-PA nanohybrids were combined with SM to prepare a high-performance SM-based adhesive. The water resistance of the modified adhesive was remarkably improved, with 105.2 % higher than that of the unmodified SM adhesive in wet shear strength. Moreover, the modified adhesive showed good cytocompatibility, biodegradability, and flame retardancy. This work suggested a new approach in preparing green high-performance protein-based adhesives.

Development of conductive protein-based film reinforced by cellulose nanofibril template-directed hyperbranched copolymer.

Smart conductive soft materials prepared from natural polymers are arousing ever-increasing attention in numerous advanced applications. However, achieving the synergistic properties of high biocompatibility, mechanical performance, and conductivity remains a key challenge. Herein, a novel and green strategy is proposed to fabricate a soy protein (SP)-based composite by the incorporation of hyperbranched poly(amino ester)-pyrrole (HPPy) via in situ polymerization into a bio template of cellulose nanofibril (CNF). The formed HPPy@CNF nanohybrids not only serve as dynamic cross-linking sites to construct a strong and stable network, but also impart a remarkable conductive ability to biopolymer materials. The tensile stress and toughness of the modified SP-based film increased by 362.1 % and 718.8 %, respectively superior to those of previously reported reinforcing approaches. Moreover, this biopolymer film exhibited significantly improved electrochemical properties, water resistance, and thermal stability. This synthesis strategy is facile and eco-friendly and can be easily extended to other material systems.

Nature-Inspired Green Procedure for Improving Performance of Protein-Based Nanocomposites via Introduction of Nanofibrillated Cellulose-Stablized Graphene/Carbon Nanotubes Hybrid.

Soy protein isolate (SPI) provides a potential alternative biopolymer source to fossil fuels, but improving the mechanical properties and water resistance of SPI composites remains a huge challenge. Inspired by the synergistic effect of natural nacre, we developed a novel approach to fabricate high-performance SPI nanocomposite films based on 2D graphene (G) nanosheets and 1D carbon nanotubes (CNTs) and nanofibrillated cellulose (NFC) using a casting method. The introduction of web-like NFC promoted the uniform dispersion of graphene/CNTs in the biopolymer matrix, as well as a high extent of cross-linkage combination between the fillers and SPI matrix. The laminated and cross-linked structures of the different nanocomposite films were observed by field-emission scanning electron microscope (FE-SEM) images. Due to the synergistic interactions of π⁻π stacking and hydrogen bonding between the nanofillers and SPI chains, the tensile strength of SPI/G/CNT/NFC film significantly increased by 78.9% and the water vapor permeability decreased by 31.76% in comparison to neat SPI film. In addition, the ultraviolet-visible (UV-vis) light barrier performance, thermal stability, and hydrophobicity of the films were significantly improved as well. This bioinspired synergistic reinforcing strategy opens a new path for constructing high-performance nanocomposites.

A Low-Cost, Formaldehyde-Free and High Flame Retardancy Wood Adhesive from Inorganic Adhesives: Properties and Performance.

Wood composites used in indoor living environments often pose formaldehyde emission and fire hazard problems. In this study, magnesium oxychloride cement-based (MOC) inorganic adhesives are presented as an effective and sustainable binder for plywood applications. The phase composition, microstructure, and thermal stability of the adhesives prepared with different ratios of MgO/MgCl2 were investigated. In addition, the dry and wet shear strength and the combustion behavior of the plywood were also examined. The results indicated that the limiting oxygen index (LOI) values of the plywood bonded by the MOC adhesives were higher than those of the plywood bonded by urea-formaldehyde resin. The active MgO/MgCl2 molar ratio of 7 was the optimal ratio for the dry and wet shear strength of the plywood with values of 1.02 and 0.88 MPa, respectively, which meet the interior use panel (Type II plywood) requirements. These improvements were ascribed to the increasing ratio of MgO/MgCl2 that facilitated the formation of an excellent microstructure. Meanwhile, the continuous hydration phase strengthened the interaction between the MOC adhesive and the wood. With these improved properties, MOC adhesive is expected to be widely used for industrial applications in plywood fabrication.

A High-Performance Soy Protein Isolate-Based Nanocomposite Film Modified with Microcrystalline Cellulose and Cu and Zn Nanoclusters.

Soy protein isolate (SPI)-based materials are abundant, biocompatible, renewable, and biodegradable. In order to improve the tensile strength (TS) of SPI films, we prepared a novel composite film modified with microcrystalline cellulose (MCC) and metal nanoclusters (NCs) in this study. The effects of the modification of MCC on the properties of SPI-Cu NCs and SPI-Zn NCs films were investigated. Attenuated total reflectance-Fourier transformed infrared spectroscopy analyses and X-ray diffraction patterns characterized the strong interactions and reduction of the crystalline structure of the composite films. Scanning electron microscopy (SEM) showed the enhanced cross-linked and entangled structure of modified films. Compared with an untreated SPI film, the tensile strength of the SPI-MCC-Cu and SPI-MCC-Zn films increased from 2.91 to 13.95 and 6.52 MPa, respectively. Moreover, the results also indicated their favorable water resistance with a higher water contact angle. Meanwhile, the composite films exhibited increased initial degradation temperatures, demonstrating their higher thermostability. The results suggested that MCC could effectively improve the performance of SPI-NCs films, which would provide a novel preparation method for environmentally friendly SPI-based films in the applications of packaging materials.

Preparation and Characterization of Chitosan/Soy Protein Isolate Nanocomposite Film Reinforced by Cu Nanoclusters.

Soy protein isolate (SPI) based films have received considerable attention for use in packaging materials. However, SPI-based films exhibit relatively poor mechanical properties and water resistance ability. To tackle these challenges, chitosan (CS) and endogenous Cu nanoclusters (NCs) capped with protein were proposed and designed to modify SPI-based films. Attenuated total reflectance-Fourier transform infrared spectroscopy and X-ray diffraction patterns of composite films demonstrated that interactions, such as hydrogen bonds in the film forming process, promoted the cross-linking of composite films. The surface microstructure of CS/SPI films modified with Cu NCs was more uniform and transmission electron microscopy (TEM) showed that uniform and discrete clusters were formed. Compared with untreated SPI films, the tensile strength and elongation at break of composite films were simultaneously improved by 118.78% and 74.93%, respectively. Moreover, these composite films also exhibited higher water contact angle and degradation temperature than that of pure SPI film. The water vapor permeation of the modified film also decreased. These improved properties of functional bio-polymers show great potential as food packaging materials.

Improvement in Functional Properties of Soy Protein Isolate-Based Film by Cellulose Nanocrystal⁻Graphene Artificial Nacre Nanocomposite.

A facile, inexpensive, and green approach for the production of stable graphene dispersion was proposed in this study. We fabricated soy protein isolate (SPI)-based nanocomposite films with the combination of 2D negative charged graphene and 1D positive charged polyethyleneimine (PEI)-modified cellulose nanocrystals (CNC) via a layer-by-layer assembly method. The morphologies and surface charges of graphene sheets and CNC segments were characterized by atomic force microscopy and Zeta potential measurements. The hydrogen bonds and multiple interface interactions between the filler and SPI matrix were analyzed by Attenuated Total Reflectance⁻Fourier Transform Infrared spectra and X-ray diffraction patterns. Scanning electron microscopy demonstrated the cross-linked and laminated structures in the fracture surface of the films. In comparison with the unmodified SPI film, the tensile strength and surface contact angles of the SPI/graphene/PEI-CNC film were significantly improved, by 99.73% and 37.13% respectively. The UV⁻visible light barrier ability, water resistance, and thermal stability were also obviously enhanced. With these improved functional properties, this novel bio-nanocomposite film showed considerable potential for application for food packaging materials.