Surface engineering on cholesteric cellulose nanocrystals films inducing emulsification, organic pollutants detection and separation.

Nowadays, organic pollutants have been major concerns in many fields. Production of functional materials based on renewable and sustainable resources for organic pollutants detection and removal was of much interest. Herein, multi-functional nanocomposite films based on cellulose nanocrystals (CNCs) with high optical haze, organic pollutant detection and emulsion separation capabilities, have been successfully fabricated based on hydrophobically-modified CNCs suspensions by 2-dodecen-1-succinic anhydride (DDSA) followed by radical polymerization with tridecafluorooctyl (TFMA). The suspensions displayed satisfying oil-in-water emulsion stabilization capabilities and the vacuum-dried films showed birefringence, high transparency, and optical haze (~85 %), due to the ordered arrangements of cellulose nanocrystals. The organic pollutant can be detected through the iridescent colors disappearing by Polarizing Optical Microscope observation. In addition of improved mechanical strength for application (27 MPa) and high contact angle of 131.6°, the hydrophobic films performed as high separation efficiency as >90 % of emulsion, due to the successfully grafting of hydrophobic molecules on the surface of CNCs. Thus, the surface modification for CNCs provide a facile approach of emulsification, pollutants detection and separation properties, which would widen the application potentials of renewable cellulosic resources in fields of environmental protection, engineering control and petroleum industry.

Layer-by-layer assembly induced strong, hydrophobic and anti-bacterial TEMPO oxidized cellulose nanofibrils films for highly efficient UV-shielding and oil-water separation.

Anti-ultraviolet material with cost-effectiveness, environmental friendliness, and multifunction is urgently needed to address the serious problem of ultraviolet radiation. However, traditional anti-ultraviolet products based on plastics are unsustainable and harmful to the environment. Herein, the cellulose films with a sandwich structure using a surface assembly technique were reported. Natural L-phenylalanine was grafted onto cellulose nanofibrils via amidation to enhance their UV-shielding property. To address the hydrophilic nature and limited mechanical strength of cellulose films, we employed octadecyltrichlorosilane and 4ARM-PEG-NH2 for hydrophobic coating and mechanical reinforcement, respectively. In addition to providing complete UV resistance in the wavelength range of 200-320 nm, sample OPT5 exhibited significantly improved tensile stress, Young's modulus, and toughness, measuring 174.09 MPa, 71.11 MPa, and 295.33 MJ/m3, respectively. Furthermore, due to the presence of antibacterial amine groups, the modified film demonstrated a satisfactory inhibitory effect on the growth of Escherichia coli and Bacillus subtilis. Compared to natural cellulose films, the hydrophobically modified material achieved a contact angle of up to 121.1°, which enabled efficient separation of oil-water mixtures with a maximum separation efficiency of 93.87 %. In summary, the proposed TOCNF-based UV-shielding film with multifunctionality holds great potential for replacing petrochemical-derived plastics and serving as an applicable and sustainable membrane material.

Grafting natural nicotinamide on tempo-oxidized cellulose nanofibrils to prepare flexible and transparent nanocomposite films with fascinating mechanical strength and UV shielding performance.

Light pollution from ultraviolet (UV) radiation is gaining growing concerns, as the emissions and burning of fossil fuels destroyed the ozone layer. Seeking a solution against skin exposure to excessive radiation is an urgent requirement. In this study, nicotinamide (NA), the main component of vitamin B3, was introduced as a new modifier into Tempo-oxidized cellulose nanofibrils (TOCNFs) together with the physical cross-linking with tannin acid (TA) to improve anti-UV performance of the nanocomposite films. Incorporation of NA into the films presents distinguished UV shielding capability UVB wavelength range from 200 nm to 320 nm (NTA1-5) due to the introduced functional groups like CO and benzene rings. Moreover, mechanical properties were notably enhanced, which overcome the low strength of common nanocellulosic materials. The stress increased from 69.8 MPa to 116.3 MPa, and the toughness can reach 131.58 MJ/m3 by tuning the additional amount of NA. Meanwhile, TGA and DTG analysis demonstrated that the incorporation of amide bonds and TA into the composite films greatly improved the thermal stability. Thus, the proposed materials fabricated from natural biomolecules show great potential in serving as new kinds of UV-resistant products in the application areas of sunscreen, protective clothing, and building materials.

Facile adjustment on cellulose nanocrystals composite films with glycerol and benzyl acrylate copolymer for enhanced UV shielding property.

In the present work, cellulose nanocrystals (CNCs) composite films with suitable applicable capabilities were prepared by facilely incorporating glycerol (Gly) and poly(benzyl acrylate) (PBA). Chemical and morphological variations during the fabrication of the films were systematically characterized. The properties of modified CNCs composite films including UV blocking ability, mechanical strength and thermal properties were characterized to assess their applicable potentials. As a result, the composite films have good UV shielding property in UVC (220-280 nm) region and UVB (280-320 nm) region. The shielding performance of the modified film in the ultraviolet absorption region reached 92.77% to 95.49% respectively, without damaging the original chiral nematic structure of the films. Along with the modification, BACNC film improved the mechanical properties, presenting the tensile strength 16 times higher compared to pure CNCs film. The nanocomposite films proposed in this work showed promising potentials in broad fields, such as food preservation, medical protection, and surface coating applications.

Allomorphic regulation of bamboo cellulose by mild alkaline peroxide for holocellulose nanofibrils production.

The exploration of sustainable lignocellulosic nanomaterials with unique properties and applicable functions is receiving growing interest. In this work, holocellulose nanofibrils (HCNFs) were prepared from moso bamboo using mild alkaline peroxide bleaching method (MAPB) followed by mechanical nanofibrillation. MAPB was proved to effectively remove lignin and retain hemicellulose. Meanwhile, partial allomorphic changes from cellulose I to cellulose II were revealed together with varying degrees of crystallinity. Thermogravimetric analysis (TGA) experiment showed an increasing thermal stability trend due to more allomorphic changes into anti-parallel cellulose II. Well-dispersed HCNFs suspensions were successfully prepared by homogenization and HCNFs films with high transparency and flexibility were fabricated. The films reached the maximum tensile strength of 55.8 MPa and tensile strain of 1.55 % along with a calculated toughness of 25 MJ/m3. Moreover, the prepared materials are biocompatible and completely non-toxic, which will theoretically support the application of HCNFs materials in fields of biology, medicine and food industry.

Bioinspired manufacturing of oriented polysaccharides scaffolds for strong, optical haze and anti-UV/bacterial membranes.

Here, biomimetic dual esterification strategy was proposed on natural polysaccharides cellulose nanocrystals (CNCs) and galactomannan (GM) in combination with tartaric acid (TA) and benzoic anhydride (BA) respectively. Evaporation-induced self-assembly (EISA) formed the oriented quasinematic structure of the nanocomposites membranes. The CNCs crystallites were modified by TA and intercalated by amorphous polysaccharides, building a complex supramolecular network. Thus, it presents excellent light scattering property with the optical haze of ~90%, which was rarely reported previously. TA and BA simultaneously contributed to satisfying UV adsorption capability for the membranes, showing almost whole-spectra UVA/UVB blocking. Super high mechanical strength (>150 MPa) and toughness (~8 kJ/m3) were revealed by the membranes with high addition amount of BA, together with the efficient antibacterial capability on both Gram-positive and negative bacteria. The diverse optical, mechanical and biological functions displayed by the polysaccharides membranes, propose new horizons on application for packaging, optoelectronic and biomonitoring sensors.

All-natural and biocompatible cellulose nanocrystals films with tunable supramolecular structure.

Herein, nanocomposites films were prepared via the facile casting method by incorporating cellulose nanocrystals (CNCs) with arabinogalactan (AG), galactomannan (GM) or konjac glucomannan (KGM) respectively. The introduced polysaccharides maintained the transparency of CNCs films and promoted the UV blocking properties. In addition, mechanical strength of the nanocomposite films was greatly improved after the combination of polysaccharides. The interactions of hydroxyl-abundant macromolecules, smoother and tighter morphological structures, as well as the disturbed crystal structure were proved to be responsible for the improved properties. Hydrophilic lattice planes of cellulose crystallites were determined to interact with polysaccharides resulting in lower crystallite sizes and crystallinity. The cell culture assay revealed that the films had no cytotoxicity and presented a satisfactory cytocompatibility, because of the polysaccharides from plant cell walls introduced into the films. Therefore, the biocompatible nanocomposites films can be tuned by the addition of polysaccharides, which show great potentials for materials modification in optical, packaging and biomedical fields.

Promoting enzymatic hydrolysis of aggregated bamboo crystalline cellulose by fast microwave-assisted dicarboxylic acid deep eutectic solvents pretreatments.

Deep eutectic solvents (DESs) have received considerable interests as pretreatment solvents for biorefinery. In the present work, five kinds of dicarboxylic acids based DESs were introduced to pretreatments on moso bamboo (MB) with microwave irradiation assistance. Factors influencing the enzymatic conversion of MB cellulose to glucose were determined. With the fast heating, pretreated samples all present significant delignification and hemicelluloses matrix removal, thus improving the enzymatic conversion yield from 15% of MB to ~60%. For the DESs, hydrogen donors with less carbon atoms (oxalic acid) and more hydroxyl groups (tartaric acid) displayed higher efficiency due to separation of aggregated cellulose microfibrils. The microwave assisted DESs (MW-DESs) pretreatments also contributed to cellulose crystal variations including decrystallization and more exposure of hydrophobic surfaces, which are beneficial for followed cellulase adsorption and hydrolysis. The exploration of fast MW-DESs pretreatments may expand the potentials of lignocellulose biomass on effective and applicable biorefinery.

Thallium concentrations, sources and ecological risk in the surface sediments of the Yangtze Estuary and its adjacent east China marginal sea: A baseline study.

The distribution characteristics, sources and ecological risk of thallium (Tl) in the surface sediments of Yangtze Estuary and its adjacent sea were studied. Tl concentrations ranged from 0.369 to 1.197 µg g-1 with an average of 0.674 µg g-1, which was slightly higher than the corresponding background values. Tl concentrations were relatively high in sediments of the south bank of Chongming Island and the Hangzhou Bay mouth, and gradually decreased from inner shelf to outer seas. The variation trend of Tl concentrations was controlled by sediment characteristics, hydrodynamic conditions and sources together. The sediment flux of Tl in the study area was 428.6 t/yr. The Yangtze River, the Yellow River and atmospheric inputs of Tl accounted for 52.7%, 10.5%, and 0.15% of the total sediment flux, respectively. The result of potential ecological index indicated that Tl in surface sediments of the study area had no threat to the ecological environment.