Transparent, thermal stable, water resistant and high gas barrier films from cellulose nanocrystals prepared by reactive deep eutectic solvents.

Nanocellulose-based film, as a novel new type of film mainly made of nanosized cellulose, has demonstrated an ideal combination of renewability and enhanced or novel properties. Considerable efforts have been made to enhance its intrinsic properties or create new functions to expand its applications, such as in food packaging, water treatment or flexible electronics. In this paper, two different types of deep eutectic solvents (guanidine sulfamate-glycerol and guanidine sulfamate-choline chloride) were formulated and applied to prepare cellulose nanocrystals with dialdehyde cellulose (DAC). The effects of reaction conditions including time, temperature and cellulose-DES ratio on the grafting degree and yield were studied. After ultrasonication, two types of CNCs, with an average diameter of 3-5 nm and an average length of 140.7-204.2 nm, were obtained. The synthesized CNCs displayed an enhanced thermal stability compared to pristine cellulose. Moreover, highly transparent (light transmittance higher than 90 %) and water stable nanocellulose based films (a wet tensile strength of higher than 30 MPa after immersing in water for 24 h) were fabricated. Besides, the obtained films exhibited low oxygen transmission rate, showing a good potential application in food packaging.

Fabrication of flame-retardant and water-resistant nanopapers through electrostatic complexation of phosphorylated cellulose nanofibers and chitin nanocrystals.

Biogenic, sustainable two-dimensional architectures, such as films and nanopapers, have garnered considerable interest because of their low carbon footprint, biodegradability, advanced optical/mechanical characteristics, and diverse potential applications. Here, bio-based nanopapers with tailored characteristics were engineered by the electrostatic complexation of oppositely charged colloidal phosphorylated cellulose nanofibers (P-CNFs) and deacetylated chitin nanocrystals (ChNCs). The electrostatic interaction between anionic P-CNFs and cationic ChNCs enhanced the stretchability and water stability of the nanopapers. Correspondingly, they exhibited a wet tensile strength of 17.7 MPa after 24 h of water immersion. Furthermore, the nanopapers exhibited good thermal stability and excellent self-extinguishing behavior, triggered by both phosphorous and nitrogen. These features make the nanopapers sustainable and promising structures for application in advanced fields, such as optoelectronics.

High-Efficiency Photodynamic Antibacterial Activity of NH2-MIL-101(Fe)@MoS2/ZnO Ternary Composites.

Bacterial infections are a serious threat to human health, and the development of effective antibacterial agents represents a critical solution. In this study, NH2-MIL-101(Fe)@MoS2/ZnO ternary nanocomposites are successfully prepared by a facile wet-chemistry procedure, where MoS2 nanosheets are grown onto the MIL-101 scaffold forming a flower-like morphology with ZnO nanoparticles deposited onto the surface. The ternary composites exhibit a remarkable sterilization performance under visible light irradiation toward both Gram-negative and Gram-positive bacteria, eliminating 98.6% of Escherichia coli and 90% of Staphylococcus aureus after exposure to visible light for 30 min, a performance markedly better than that with NH2-MIL-101(Fe)@MoS2 binary composites and even more so than MoS2 nanosheets alone. This is ascribed to the unique electronic band structure of the composites, where the separation of the photogenerated carriers is likely facilitated by the S-scheme mechanism in the NH2-MIL-101(Fe)@MoS2 binary composites and further enhanced by the formation of a p-n heterojunction between MoS2 and ZnO in the ternary composites. This interfacial charge transfer boosts the effective production of superoxide radicals by the reduction of oxygen, and the disproportionation reaction with water leads to the formation of hydroxy radicals, as attested in spectroscopic and microscopic measurements. Results from this study highlight the significance of structural engineering of nanocomposites in the manipulation of the electronic band structure and hence the photodynamic activity.

Preparation and stabilization of Pickering emulsions by cationic cellulose nanocrystals synthesized from deep eutectic solvent.

In this work, short rod-like cationic cellulose nanocrystals (AH-CNCs) were prepared by sodium periodate oxidation combined with deep eutectic solvent method. The effects of different content AH-CNCs on the properties of the emulsion were studied. With the increase of AH-CNCs content, the diameter of emulsion droplets decreased and the stabilization time prolonged. The electrostatic attraction between the negative charge accumulated at the oil-water interface and AH-CNCs with positive charge improved the stability of the emulsion. Then, the rheological properties showed the interaction of nanocellulose in the continuous phase increased the viscosity of the emulsion. In addition, the droplet diameter of emulsion of 120 s was smaller at different ultrasonic time, the particle size distribution of emulsion changed from monodisperse to polydisperse with the increase of oil volume, the salt concentration had little effect on the droplet size of emulsion, and the preparation of emulsion under acidic conditions was more stable.

Nanostructured and Advanced Designs from Biomass and Mineral Residues: Multifunctional Biopolymer Hydrogels and Hybrid Films Reinforced with Exfoliated Mica Nanosheets.

Transforming potential waste materials into high-value-added sustainable materials with advanced properties is one of the key targets of the emerging green circular economy. Natural mica (muscovite) is abundant in the mining industry, which is commonly regarded as a byproduct and gangue mineral flowing to waste rock and mine tailings. Similarly, chitin is the second-most abundant biomass resource on Earth after cellulose, extracted as a byproduct from the exoskeleton of crustaceans, fungal mycelia, and mushroom wastes. In this study, exfoliated mica nanosheets were individualized using a mechanochemical process and incorporated into regenerated chitin matrix through an alkali dissolution system (KOH/urea) to result in a multifunctional, hybrid hydrogel, and film design. The hydrogels displayed a hierarchical and open nanoporous structure comprising an enhanced, load-bearing double-cross-linked polymeric chitin network strengthened by mica nanosheets possessing high stiffness after high-temperature curing, while the hybrid films (HFs) exhibited favorable UV-shielding properties, optical transparency, and dielectric properties. These hybrid designs derived from industrial residues pave the way toward sustainable applications for many future purposes, such as wearable devices and tissue engineering/drug delivery.

Efficient Hydrolysis of Chitin in a Deep Eutectic Solvent Synergism for Production of Chitin Nanocrystals.

A deep eutectic solvent (DES) derived from ferric chloride hexahydrate and betaine chloride (molar ratio of 1:1) was used as hydrolytic media for production of chitin nanocrystals (ChNCs) with a high yield (up to 88.5%). The synergistic effect of Lewis acid and released Brønsted acid from betaine hydrochloride enabled the efficient hydrolysis of chitin for production of ChNCs coupled with ultrasonication with low energy consumption. The obtained ChNCs were with an average diameter of 10 nm and length of 268 nm, and a crystallinity of 89.2% with optimal synthesis conditions (at 100 °C for 1 h with chitin-to-DES mass ratio of 1:20). The ChNCs were further investigated as efficient emulsion stabilizers, and they resulted in stable o/w emulsions even at a high oil content of 50% with a low ChNC dosage of 1 mg/g. Therefore, a potential approach based on a DES on the production of chitin-based nanoparticles as emulsifiers is introduced.

Comparison of acidic deep eutectic solvents in production of chitin nanocrystals.

Five different acidic deep eutectic solvents (DESs) composed of choline chloride and organic acids were applied to fabricate chitin nanocrystals (ChNCs). All DESs resulted in high transmittance and stable ChNCs suspensions with very high mass yield ranging from 78 % to 87.5 % under proper reaction conditions. The acidic DESs had a dual role in ChNCs fabrication, i.e. they promoted hydrolysis of chitin and acted as an acylation reagent. Physicochemical characterization of chitin revealed that the removal of amorphous area during DES treatments led to increased crystallinity of ChNCs and a dimension diversity correlated the DES used. The average diameter and length of individual ChNCs ranged from 42 nm to 49 nm and from 257 nm to 670 nm, respectively. The thermal stability of ChNCs was comparable to that of pristine chitin. Thus, acidic DESs showed to be non-toxic and environmentally benign solvents for production of functionalized chitin nanocrystals.

Interfacial Nanoparticle Complexation of Oppositely Charged Nanocelluloses into Functional Filaments with Conductive, Drug Release, or Antimicrobial Property.

Construction of colloidal nanoparticles (NPs) into advanced functional nanocomposites and hybrids with the predesigned hierarchical structure and high-performance is attractive, especially for natural biological nanomaterials, such as proteins and polysaccharides. Herein, a simple and sustainable approach called interfacial NP complexation (INC) was applied to construct diverse functional (conductive, drug-loaded, or antimicrobial) nanocomposite filaments from oppositely charged colloidal nanocelluloses. By incorporating different additives during the INC process, including multiwalled carbon nanotube, an antitumor drug (doxorubicin hydrochloride), and metal (silver) NPs (Ag NPs), high-performance functional continuous filaments were synthesized, and their potential applications in electronics, drug delivery, and antimicrobial materials were investigated, respectively. This novel INC method based on charged colloidal NPs opens new avenues for building various functional filaments for a diversity of end uses.

Hierarchical Assembly of Nanocellulose-Based Filaments by Interfacial Complexation.

In the present study, interfacial complexation spinning of oppositely charged cellulose-materials is applied to fabricate hierarchical and continuous nanocellulose based filaments under aqueous conditions by using cationic cellulose nanocrystals with different anionic celluloses including soluble sodium carboxymethyl cellulose and insoluble 2,2,6,6-tetramethylpiperidinyl-1-oxy radical-oxidized cellulose nanofibers and dicarboxylated cellulose nanocrystals (DC-CNC). The morphologies of the wet and dry nanocellulose based filaments are further investigated by optical and electron microscopy. All fabricated continuous nanocellulose based filaments display a hierarchical structure similar to the natural cellulose fibers in plant cells. As far as it is known, this is not only the first report about the fabrication of nanocellulose based filaments by interfacial complexation of cationic CNCs with anionic celluloses but also the first demonstration of fabricating continuous fibers directly from oppositely charged nanoparticles by interfacial nanoparticle complexation (INC). This INC approach may provide a new route to design continuous filaments from many other oppositely charged nanoparticles with tailored characteristics.

Facile synthesis of palladium and gold nanoparticles by using dialdehyde nanocellulose as template and reducing agent.

Cellulose nanofibrils (CNFs) were firstly prepared by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidation and further oxidized to 2,3-dialdehyde nanocelluloses (DANCs) by periodate oxidation. Furthermore, by using DANCs as reducing as well as stabilizing agent, palladium (Pd) and gold (Au) nanoparticles (NPs) supported on nanocellulose (PdNPs@NC and AuNPs@NC) were synthesized, respectively. The reduction of Pd or Au ions to its metallic form by DANCs was confirmed by UV-vis spectra, XRD, and XPS. TEM results showed that Pd and Au NPs were homogenously deposited onto cellulose nanofibrils, respectively. The catalytic performance of PdNPs@NC was further investigated by Suzuki coupling reaction. The product yield of the Suzuki coupling reaction between aryl bromides and phenyl boronic acid was more than 90% after 1 h with 0.1 mol% PdNPs@NC catalyst, which demonstrated that the synthesized PdNPs@NC nanohybrid could be successfully applied in Suzuki coupling reaction with an efficient catalytic activity.

Extraction and comparison of carboxylated cellulose nanocrystals from bleached sugarcane bagasse pulp using two different oxidation methods.

Two kinds of carboxylated cellulose nanocrystals (CCNs) were prepared by using ultrasonic assisted 2,2,6,6-tetramethylpiperidinyl-1-oxy radical (TEMPO) mediated oxidation and one-step ammonium persulfate (APS) oxidation, which were denoted as TEMPO-oxidized CCNs (TO-CCNs) and APS-oxidized CCNs (AO-CCNs), respectively. The effects of oxidant content on the yield, carboxyl content, degree of polymerization (DPv) and morphology of the oxidized celluloses in the two oxidation methods were studied. Furthermore, the chemical structure, crystallinity and thermal stability of TO-CCNs and AO-CCNs were evaluated and compared by Fourier transformed infrared spectra, X-ray diffraction and thermogravimetric analyses. The results showed that with increase of oxidant content in the two methods, the carboxyl groups on the surfaces of TO-CCNs and AO-CCNs were both improved. And a remarkable decline of the DPv of cellulose sample also appeared in the two oxidative treatments. In addition, AO-CCNs exhibited a higher crystallinity and an enhanced thermal stability compared with TO-CCNs.