Surface Doping of Anionic Clusters Facilitated Direct Fabrication of Commercial Cellulose Nanofibrils for Long-Range Ordered Layer Structures.

The fabrication of commercial cellulose nanofibrils (CNFs) into arrays with long-range ordering is of great significance for their extended applications, which, however, is severely hindered by their high disorder, aggregation, and hornified features. Herein, sub-nanoscale anionic metal oxide clusters (phosphotungstic acid, H3PW12O40, PTA) are applied to complex with commercial CNFs (dried powder DCNF and aqueous suspension WCNF) in aqueous media, and a long-range ordered layer structure can be facilely fabricated via typical unidirectional freezing. The surface complexation of the commercial CNFs and PTA can be confirmed through the small-angle scattering studies of the complex hydrogels. The hydrogels present similar correlation lengths in small-angle X-ray and neutron scattering measurements, suggesting the homogeneous distribution of PTA along the commercial CNFs. This gives rise to the negatively charged surface feature and further leads to strong repulsion among the commercial CNFs. Due to the disparity in sizes, the influence of PTA on the density of hydrogel networks is suppressed, and the network density is mainly dependent on the mass content of CNFs. The studies provide guidance to fabricate hydrogels with catalytic and photosensitive properties and also to design and stabilize long-range ordered structured aerogels during the removal of the nonfreezing bound water absorbed by the commercial CNFs after unidirectional freezing. This facile strategy shows great potential to broaden the application of commercial CNFs in thermal insulators, super-adsorbent materials, and supercapacitors in electrical devices.

Polyoxometalate/Cellulose Nanofibrils Aerogels for Highly Efficient Oxidative Desulfurization.

Polyoxometalate (POM) presents great potential in oxidative desulfurization (ODS) reaction. However, the high dissolubility of POM in common solvents makes it difficult to recycle. Besides, the small specific surface area of POM also limits the interaction between them and the substrate. Depositing polyoxometalates onto three-dimensional (3D) network structured materials could largely expand the application of POM. Here, the surfaces of cellulose nanofibrils (CNFs) were modified with very few (3-Aminopropyl) trimethoxysilane (APTS) to endow positive charges on the surfaces of CNFs, and then phosphotungstic acid (PTA) was loaded to obtain the aerogel A-CNF/PTA as the ODS catalyst. FT-IR indicated the successful deposition of PTA onto aminosilane modified CNF surfaces. UV-VIS further suggested the stability of PTA in the aerogels. BET and SEM results suggested the increased specific surface area and the relatively uniform 3D network structure of the prepared aerogels. TGA analysis indicated that the thermal stability of the aerogel A-CNF/PTA50% was a little higher than that of the pure CNF aerogel. Most importantly, the aerogel A-CNF/PTA50% showed good catalytic performance for ODS. Catalysis results showed that the substrate conversion rate of the aerogel A-CNF/PTA50% reached 100% within 120 min at room temperature. Even after five cycles, the substrate conversion rate of the aerogel A-CNF/PTA50% still reached 91.2% during the dynamic catalytic process. This work provides a scalable and facile way to stably deposit POM onto 3D structured materials.

Facial Synthesis of Adsorbent from Hemicelluloses for Cr(VI) Adsorption.

It is challenging work to develop a low-cost, efficient, and environmentally friendly Cr(VI) adsorbent for waste water treatment. In this paper, we used hemicelluloses from chemical fiber factory waste as the raw material, and prepared two kinds of carbon materials by the green hydrothermal method as adsorbent for Cr(VI). The results showed that hemicelluloses hydrothermally treated with citric acid (HTC) presented spherical shapes, and hemicelluloses hydrothermally treated with ammonia solution (HTC-NH2) provided spongy structures. The adsorption capacity of the samples can be obtained by the Langmuir model, and the adsorption kinetics could be described by the pseudo-second-order model at pH 1.0. The maximum adsorption capacity of HTC-NH2 in the Langmuir model is 74.60 mg/g, much higher than that of HTC (61.25 mg/g). The green hydrothermal treatment of biomass with ammonia solution will provide a simple and feasible way to prepare adsorbent for Cr(VI) in waste water treatment.

Shape-Memory and Anisotropic Carbon Aerogel from Biomass and Graphene Oxide.

Biomass, as the most abundant and sustainable resource on the earth, has been regarded as an ideal carbon source to prepare various carbon materials. However, manufacturing shape-memory carbon aerogels with excellent compressibility and elasticity from biomass remains an open challenge. Herein, a cellulose-derived carbon aerogel with an anisotropic architecture is fabricated with the assistance of graphene oxide (GO) through a directional freeze-drying process and carbonization. The carbon aerogel displays excellent shape-memory performances, with high stress and height retentions of 93.6% and 95.5% after 1000 compression cycles, respectively. Moreover, the carbon aerogel can identify large ranges of compression strain (10-80%), and demonstrates excellent current stability during cyclic compression. The carbon aerogel can precisely capture a variety of biological signals in the human body, and thus can be used in wearable electronic devices.

Acetylation of Microcrystalline Cellulose by Transesterification in AmimCl/DMSO Cosolvent System.

Recently, IL/cosolvent systems have generated a lot of interest as cellulose-dissolving solvents and reaction media for various kinds of cellulose modification. In the present study, both 1-allyl-3-methylimidazolium chloride (AmimCl)/dimethyl sulfoxide (DMSO) and AmimCl/N,N-dimethylformamide (DMF) systems were employed to synthesize cellulose acetate by transesterification. Microcrystalline cellulose, 1,8-diazabicyclo[5.4.0]undec-7-ene and isopropenyl acetate were chosen as the raw material, catalyst and acetylation reagent, respectively. The results revealed that DMSO was a suitable cosolvent for the transesterification in the homogeneous solution. Moreover, DMSO had a positive effect on the reaction as the cosolvent under the given conditions and the degree of the substitution of cellulose acetate could be significantly enhanced through increasing the molar ratio of DMSO. The synthesized products were characterized by Fourier transform infrared (FT-IR) spectroscopy, ¹H and 13C nuclear magnetic resonance spectroscopy (¹H-NMR and 13C-NMR), correlation spectroscopy (COSY), heteronuclear single quantum correlation (HSQC) spectroscopy, and X-ray diffraction (XRD) to confirm the chemical and physical structure of the cellulose acetate generated. The thermal properties were also evaluated using thermogravimetric analysis (TGA)/derivative thermogravimetry (DTG).

Analysis of cuticular wax constituents and genes that contribute to the formation of 'glossy Newhall', a spontaneous bud mutant from the wild-type 'Newhall' navel orange.

Navel orange (Citrus sinensis [L.] Osbeck) fruit surfaces contain substantial quantities of cuticular waxes, which have important eco-physiological roles, such as water retention and pathogen defense. The wax constituents of ripe navel orange have been studied in various reports, while the wax changes occurring during fruit development and the molecular mechanism underlying their biosynthesis/export have not been investigated. Recently, we reported a spontaneous bud mutant from the wild-type (WT) 'Newhall' Navel orange. This mutant displayed unusual glossy fruit peels and was named 'glossy Newhall' (MT). In this study, we compared the developmental profiles of the epicuticular and intracuticular waxes on the WT and MT fruit surfaces. The formation of epicuticular wax crystals on the navel orange surface was shown to be dependent on the accumulation of high amounts of aliphatic wax components with trace amounts of terpenoids. In sharp contrast, the underlying intracuticular wax layers have relatively low concentrations of aliphatic wax components but high concentrations of cyclic wax compounds, especially terpenoids at the late fruit developmental stages. Our work also showed that many genes that are involved in wax biosynthesis and export pathways were down-regulated in MT fruit peels, leading to a decrease in aliphatic wax component amounts and the loss of epicuticular wax crystals, ultimately causing the glossy phenotype of MT fruits.

Ring-opening graft polymerization of propylene carbonate onto xylan in an ionic liquid.

The amidine organocatalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst. Biocomposites with tuneable properties were successfully synthesized by ring-opening graft polymerization (ROGP) of propylene carbonate (PC) onto xylan using DBU as a catalyst in the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The effects of reaction temperature, reaction time and the molar ratio of PC to anhydroxylose units (AXU) in xylan were investigated. The physico-chemical properties of xylan-graft-poly(propylene carbonate) (xylan-g-PPC) copolymers were characterised by FT-IR, NMR, TGA/DTG, AFM and tensile analysis. The FT-IR and NMR results indicated the successful attachment of PPC onto xylan. TGA/DTG suggested the increased thermal stability of xylan after the attachment of PPC side chains. AFM analysis revealed details about the molecular aggregation of xylan-g-PPC films. The results also showed that with the increased DS of xylan-g-PPC copolymers, the tensile strength and Young's modulus of the films decreased, while the elongation at break increased.

Cellulose nanocrystal/graphene oxide one-dimensional photonic crystal film with excellent UV-blocking and transparency.

Achieving excellent ultraviolet (UV) blocking properties and maintaining high light transmittance are highly challenging. In this study, a facile and green polymer-assisted vacuum filtration strategy was used to prepare cellulose nanocrystal (CNC) one-dimensional photonic crystal (1DPhC) films with excellent UV-blocking performance and good transparency. The polymer-assisted self-assembly behaviors of CNC and the hydrogen bonding interaction between CNC, polyethylene glycol (PEG), and graphene oxide (GO) drive the homogeneous distribution and parallel alignment of GO. The UV absorption of GO and high reflection of UV resulting from the chiral nematic structure of CNCs result in excellent UV-blocking and high visible light transmission. Besides, the strong hydrogen bonding interaction among CNC, PEG, and GO endows the films with obviously increased mechanical properties. The UV-blocking and the transparency of the CNC composite films could reach 98.3 % and 60.5 %, respectively. Besides, the strain at break of the composite film reached 1.72 ± 0.11 %, which was 535.94 % of neat CNC films. The CNC composite films present great potential in the field of UV-blocking glass, sensors, anti-counterfeiting measures, radiation protection, and so on.

Improving the Monophenolic Yield of Lignin Depolymerization in Dualistic Aprotic Solvent System by Organic Solvent Fractionation.

Converting lignin into aromatic chemicals is a promising strategy for the high-value utilization of lignocellulosic feedstock. However, the inherent heterogeneity of lignin poses a significant obstacle to achieving efficient conversion and optimal product yields within bio-refinery systems. Herein, we employed a one-step fractionation method to enhance lignin homogeneity and utilized the THF/DMSO-EtONa (tetrahydrofuran/dimethyl sulfoxide-sodium ethoxide) system to depolymerize the fractionated lignin. Three protic and three aprotic solvents were used for fractionation. The impact of the solvent properties on the structure and the depolymerization efficiency of the fractionated lignin was investigated. Methanol-fractionated lignin generated the benzoic acid compounds with a yield of 30 wt%, 50 % higher than that of the unfractionated lignin. The polarities (δP), hydrogen bonding abilities (δH), and viscosities (η) of selected protic solvents showed strong linear correlation with molecular weight (Mw), polymer dispersity index (PDI), and syringyl/guaiacyl ratio (S/G ratio) of the fractionated lignin, as well as the total yield of benzoic acid compounds derived from the ß-O-4 bond cleavage. This study elucidates the relationship between solvent properties and lignin structure and proposes a promising approach for refining lignin to enhance utilization efficiency, thereby presenting a potential strategy for value-added application of complex lignin polymers.

Hemicelluloses-based sprayable and biodegradable pesticide mulch films for Chinese cabbage growth.

In this study, one high-performance hemicelluloses (HC)-based sprayable and biodegradable pesticide mulch film was developed. Firstly, HC was transesterified with vinyl acetate (VA) to improve its solubility and film-forming ability. Then abamectin (ABA) was encapsulated by ß-cyclodextrin (ß-CD) to endow mulch film persistent anti-pesticide activity. After that, sodium alginate (SA) and gelatin were added to develop the mechanical performances of the mulch film. As a result, the obtained mulch film showed good characteristics, with optimum mechanical strength, elongation at break, water vapor permeability (WVP), swelling ratio (SR), and weight loss (biodegradability) of 7.9 ± 0.3 MPa, 43.6 ± 2.0 %, 2.1 ± 0.1 × 10-11 g mm m-2 s-1 kPa-1, 73.8 ± 2.0 %, and 69.3 %, respectively. After covering with mulch film, the soil moisture and temperature were developed to 90.8 % and 19.3 ± 0.2 °C, respectively, which could facilitate Chinese cabbage growth, with optimum germination rate of 98.6 ± 6.4 %.

Metal oxide cluster-assisted assembly of anisotropic cellulose nanocrystal aerogels for balanced mechanical and thermal insulation properties.

Cellulose nanocrystal (CNC) materials grant abundant possibilities for insulation, however, their extensive application is hindered by the intrinsic tradeoff between their thermal insulating performance and mechanical properties. Here, we show that CNC aerogels with balanced thermal and mechanical performance can be fabricated via a 1 nm metal oxide cluster (phosphotungstic acid, PTA)-assisted unidirectional freeze-drying processing. The as-prepared hybrid aerogels with hierarchical porous structures consisting of layer-by-layer CNC nanosheets enable the decoupling of the strengthening of mechanical properties and the enhancement of thermal insulating capabilities. Within layered structures, the surface-doped nanosized PTA clusters with negative charges behave as dynamic physical cross-linking points, and continuous networks of PTA-doped CNC can be formed via multiple supramolecular interactions (e.g., electrostatic attractions and hydrogen bonds). The afforded stable three-dimensional network structures are able to withstand externally applied forces and large deformations, endowing the aerogels with excellent mechanical performance. Moreover, the inter-layer gap is dominated by nanopores, endowing much lower thermal conductivities along the radial direction in comparison to the axial direction. The addition of PTA clusters also contributes to the obvious enhancements of the fire-retardant properties. Our discoveries provide a facile approach for the design and scalable production of CNC-based insulation materials with optimized mechanical properties and additional fire-retardant properties.

A Liquid Metal Microdroplets Initialized Hemicellulose Composite for 3D Printing Anode Host in Zn-Ion Battery.

Maintaining a steady affinity between gallium-based liquid metals (LM) and polymer binders, particularly under continuous mechanical deformation, such as extrusion-based 3D printing or plating/stripping of Zinc ion (Zn2+ ), is very challenging. Here, an LM-initialized polyacrylamide-hemicellulose/EGaIn microdroplets hydrogel is used as a multifunctional ink to 3D-print self-standing scaffolds and anode hosts for Zn-ion batteries. The LM microdroplets initiate acrylamide polymerization without additional initiators and cross-linkers, forming a double-covalent hydrogen-bonded network. The hydrogel acts as a framework for stress dissipation, enabling recovery from structural damage due to the cyclic plating/stripping of Zn2+ . The LM-microdroplet-initialized polymerization with hemicelluloses can facilitate the production of 3D printable inks for energy storage devices.

A comparison of the ultrastructure and composition of fruits' cuticular wax from the wild-type 'Newhall' navel orange (Citrus sinensis [L.] Osbeck cv. Newhall) and its glossy mutant.

KEY MESSAGE: The altered ultrastructure and composition of cuticular wax from 'glossy Newhall' (MT) fruits lead to its glossy phenotype. A novel mutant derived from the wild-type (WT) 'Newhall' navel orange (Citrus sinensis [L.] Osbeck cv. Newhall), named 'glossy Newhall' (MT), which produced much more glossy fruits that were easily distinguishable from the WT fruits was characterized in this report. The total wax loads of both WT and MT fruits varied considerably during the fruit development. The most abundant wax fraction of WT mature fruits was triterpenoids, followed by aldehydes, alkanes, fatty acids, primary alcohol and cholesterol. The total wax load in MT mature fruits was reduced by 44.2 % compared with WT. Except for the minor wax components of primary alcohol and cholesterol, the amounts of all major wax fractions in MT mature fruits were decreased in varying degrees. The major reduction occurred in aldehydes that decreased 96.4 % and alkanes that decreased 81.9 %, which was consistent with scanning electron micrographs of MT mature fruit surfaces that showed a severe loss of wax crystals. Hence, aldehydes and alkanes were suggested to be required for wax crystal formation in 'Newhall' navel orange fruits.

Green approach to produce xylo-oligosaccharides and glucose by mechanical-hydrothermal pretreatment.

A pretreatment method combining ball-milling, ultrasound, and hydrothermal treatment was developed to produce xylooligosaccharides (XOS) and glucose with a high yield from corn stover. Under optimal conditions, the yield of XOS reached 80.40%, and the functional XOS (X2-X4) took up to 26.97%. Small amount of inhibitors were formed during the hydrothermal process. Enzymatic hydrolysis of the hydrothermally pretreated residue gave 92.60% yield of glucose, leaving lignin as the final residue which accounted for 66.82% of native lignin. The correlations between the yield of glucose and the physio-chemical properties of corn stover, such as crystalline index, particle size, and the removal of xylan, were established to understand the recalcitrance removal during the pretreatment process. Results demonstrate that this combined pretreatment method is a green and effective process to selectively separate the hemicellulose fractions and improve both production of XOS and glucose yield.

Development of functional hydroxyethyl cellulose-based composite films for food packaging applications.

Cellulose-based functional composite films can be a good substitute for conventional plastic packaging to ensure food safety. In this study, the semi-transparent, mechanical strengthened, UV-shielding, antibacterial and biocompatible films were developed from hydroxyethyl cellulose Polyvinyl alcohol (PVA) and ε-polylysine (ε-PL) were respectively used as reinforcing agent and antibacterial agent, and chemical cross-linking among these three components were constructed using epichlorohydrin The maximum tensile strength and elongation at break were 95.9 ± 4.1 MPa and 148.8 ± 2.6%, respectively. TG-FTIR and XRD analyses indicated that chemical structure of the composite films could be well controlled by varying component proportion. From UV-Vis analysis, the optimum values of the percentage of blocking from UV-A and UV-B and ultraviolet protection factor values were 98.35%, 99.99% and 60.25, respectively. Additionally, the composite films exhibited good water vapor permeability, swelling behavior, antibacterial activity and biocompatibility. In terms of these properties, the shelf life of grapes could be extended to 6 days after packing with the composite film.

Thermo-processable chitosan-based plastic substitute with self-adaptiveness and closed-loop recyclability.

The increasing environmental burden generated by disposable plastic wastes makes the development of sustainable substitute materials an emergent task. As one of the most abundant bioresources, chitosan (CS) has been considered as a potential candidate for plastic substitution. Conventionally, CS-based materials are fabricated through a solution-processing procedure due to the high crystallinity of CS. Herein, we designed a CS-based material via integrating CS into the network of polyimine (PI), which shows thermomechanical processability similar to plastics. Strong interactions were achieved through dynamic imine bond and hydrogen bond and thus formed a thermo-processable dynamic composite network. These CS-based plastic substitutes exhibit exceptional mechanical performances, excellent thermal/chemical stability, and a series of self-adaptiveness, including re-healing, reprocessing and multi-layer laminating. Notably, CPs can be easily degraded and 100% recycled for the production of next-generation materials. This work provides an alternative route to produce green and sustainable biomass materials as a plastic substitute.

A sandwich-like chitosan-based antibacterial nanocomposite film with reduced graphene oxide immobilized silver nanoparticles.

Bacterial breeding is the main cause of food perishability, which is harmful to human health. Silver nanoparticles (AgNPs) are one of the most widely used antimicrobial agents, but they are easy to release and cause cumulative toxicity. In this work, with corn stalk as green reductant and GO as template, a simple electrostatic self-assembled sandwich-like chitosan (CS) wrapped rGO@AgNPs nanocomposite film (CS/rGO@AgNPs) was synthesized to achieve stabilizing and controlled-release of AgNPs. The results showed that the the CS/rGO@AgNPs film continued releasing AgNPs for up to 14 days, and the final release amount of silver nanoparticles was only about 1.9 %. More importantly, the nanocomposite film showed durable antibacterial effect and good antibacterial activity against E. coli and S. aureus, and they showed no toxicity to cells. Hence, the nanocomposite film has potential application as an effective and safe packaging material to prolong the shelf life of food products.

Co-production of functional xylo-oligosaccharides and fermentable sugars from corn stover through fast and facile ball mill-assisted alkaline peroxide pretreatment.

The aim of this work was to develop a feasible ball mill-assisted alkaline peroxide pretreatment followed by stepwise hydrolysis to improve the yield of xylo-oligosaccharides (XOS) and fermentable sugars. The hydrogen peroxide charge, ball-milling time, and solid-to-liquid ratio affected the compositions, particle sizes, morphology, and crystallinity of the corn stover, directly improving the following hydrolytic efficiency. The optimal pretreatment was with 0.45 g/g (H2O2: substrate) and 1:3 solid-to-liquid ratio (w/v) for 1.0 h ball-milling, resulting in 84.29% delignification. Physicochemical properties of the pretreated samples were characterized and their correlations to the enzymatic hydrolysis were revealed. Compared with one-step cellulase hydrolysis, the two-step xylanase-cellulase hydrolysis of the pretreated corn stover showed significant advance in preparing XOS, producing 69.65% (on the base of xylan content in pretreated sample) of XOS, along with 20.55% xylose, 68.94% glucose, and 21.15% gluco-oligosaccharides. The yield of XOS was 2-7 times higher than those in previous studies.

Functional packaging films originating from hemicelluloses laurate by direct transesterification in ionic liquid.

An alternative transesterification with vinyl laurate (VL) was applied for chemical modification of hemicelluloses (HC) to prepare functional packaging films. Successful transesterification was confirmed by FT-IR and NMR. Semitransparent laurated HC (LHs) films were prepared by solvent casting method. SEM indicated the ordered honeycomb-patterned surface and the dense cross section of LHs films. The LHs films exhibited excellent hydrophobicity with water contact angle about 120° and the enhanced mechanical properties with tensile strength and elongation at break as 33.94 ± 3.09 MPa and 22.41 ± 2.87%, respectively. The water vapor permeability (WVP) and oxygen permeability (OP) values of LHs films ranged from 1.59 ± 0.07 to 2.23 ± 0.11 (10-10·g/m·s·Pa) and 1.21 ± 0.04 to 4.24 ± 0.30 (cm3·µm/m2·d·kPa), respectively. Moreover, the films had acceptable antioxidant activity. In terms of these properties, the shelf life of green chilies could be largely extended to 15 days after packing with LHs films.

Development of functional chitosan-based composite films incorporated with hemicelluloses: Effect on physicochemical properties.

The aim of this study was to investigate the physicochemical properties of chitosan (CS) based composite films with the incorporation of hemicelluloses (HC). Films were obtained via direct immersion method and characterized in terms of structural and morphological properties by FT-IR, XRD, XPS, SEM and EDS. By combining with the increased HC loading efficiency (L) and swelling property (S) of films with the increased HC content to 5%, this study proved the increased hydrogen bond interactions between CS and HC. Films with the tensile strength of 32.81 ± 4.97 MPa and elongation at break of 39.63 ± 4.67% were obtained with 3% HC and 20% glycerol (GC). The water vapor permeability (WVP) of films developed with the increased HC and GC contents, while the oxygen permeability (OP) decreased. Moreover, antibacterial testing indicated that all films exhibited the increased growth inhibition against E. coli and S. aureus as increasing TiO2 content.