Confinement-Modulated Clusterization-Triggered Time-Dependent Phosphorescence Color from Xylan-Carbonized Polymer Dots.

Achieving time-dependent phosphorescence color (TDPC) in organic materials is attractive but extremely challenging due to the nonradiative decay and modulation puzzle of triplet state. Herein, xylan, a hemicellulose waste from the paper mill, was used to construct carbonized polymer dots (CPDs) with clusterization-triggered room-temperature phosphorescence (RTP). CPDs were endowed with tuneable triplet energy levels by through-space conjugation of heteroatom groups, which could be confined in silica to simultaneously activate surface oxide-related low-energy and cross-linked core N-related high-energy emissive centers. Thus, the blue emissive center with a lifetime of 425.6 ms and green emissive center with a longer lifetime of 1506 ms coexisted in the confined CPDs; the former was the dominant contribution to RTP at first, and the latter became dominant over time, leading to a typical TDPC evolution with large color contrast from blue to blue-green and then to green. Meanwhile, the TDPC could remain unobstructed after the confined CPDs were soaked in water for more than a month. The CPDs were successfully applied in location and deformation imaging of hydrogel and advanced dynamic information encryption and anticounterfeiting. The work may shed new light on the design of TDPC materials and broaden the high-value use of paper-mill waste xylan.

Facile Preparation of Full-Color Tunable Room Temperature Phosphorescence Cellulose via Click Chemistry.

Sustainable long-lived room temperature phosphorescence (RTP) materials with color-tunable afterglows are attractive but rarely reported. Here, cellulose is reconstructed by directed redox to afford ample active hydroxyl groups and water-solubility; arylboronic acids with various π conjugations can be facilely anchored to reconstructed cellulose via click chemistry within 1 min in pure water, resulting in full-color tunable RTP cellulose. The rigid environment provided by the B─O covalent bonds and hydrogen bonds can stabilize the triplet excitons, thus the target cellulose displays outstanding RTP performances with the lifetime of 2.67 s, phosphorescence quantum yield of 9.37%, and absolute afterglow luminance of 348 mcd m-2. Furthermore, due to the formation of various emissive species, the smart RTP cellulose shows excitation- and time-dependent afterglows. Taking advantages of sustainability, ultralong lifetime, and full-color tunable afterglows, et al, the environmentally friendly RTP cellulose is successfully used for nontoxic afterglow inks, delay lighting, and afterglow display.

Effects of the Structure and Molecular Weight of Alkali-Oxygen Lignin Isolated from Rice Straw on the Growth of Maize Seedlings.

The abundant and low-cost features of lignin in combination with its natural activities make it a fascinating biopolymer for valorization, especially, in agriculture as an active plant growth regulator. However, the structure-activity relationship of lignin in regulating plant growth and metabolism remains unclear. In this work, rice-straw-based low-molecular-weight (LWM, 1860 Da) and high-molecular-weight (HMW, 6840 Da) alkali-oxygen lignins are structurally and comparatively investigated to understand their effects on the growth and metabolism of maize seedlings. The results indicate that LMW lignin at 150 mg·L-1 displays early growth stimulation in maize. Under the optimal concentration of LMW lignin (25 mg·L-1), the growth of maize shoot is ∼83% higher than that of the control one. Furthermore, LMW lignin also has a positive effect on the upregulation of photosynthetic pigment, carbohydrate, and protein synthesis. In contrast, HMW lignin shows an overall inhibitory effect on the above-mentioned biochemical parameters. Based on the structural characterization, LMW lignin contains a higher syringyl/guaiacyl ratio (0.78) and carboxyl content (1.64 mmol·g-1) than HMW lignin (0.43 and 1.27 mmol·g-1, respectively), which demonstrates that methoxyl and carboxyl content of lignin may play a decisive role in seedling growth.

Wood Ionic Cable.

The combination of good stability, biocompatibility, and high mechanical strength is attractive for bio-related material applications, but it remains challenging to simultaneously achieve these properties in a single, ionically conductive material. Here a "wood" ionic cable, made of aligned wood nanofibrils, demonstrating a combination of biocompatibility, high mechanical strength, high ionic conductivity, and excellent stability is reported. The wood ionic cable possesses excellent flexibility and exhibits high tensile strength up to 260 MPa (in the dry state) and ≈80 MPa (in the wet state). The nanochannels within the highly aligned cellulose nanofibrils and the presence of negative charges on the surfaces of these nanochannels, originating from the cellulose hydroxyl groups, provide new opportunities for ion regulation at low salt concentrations. Ion regulation in turn enables the wood ionic cable to have unique nanofluidic ionic behaviors. The Na+ ion conductivity of the wood ionic cable can reach up to ≈1.5 × 10-4 S cm-1 at low Na+ ion concentration (1.0 × 10-5 mol L-1 ), which is an order of magnitude higher than that of bulk NaCl solution at the same concentration. The scalable, biocompatible wood ionic cable enables novel ionic device designs for potential ion-regulation applications.

Constructing a Novel Xylan-Based Film with Flexibility, Transparency, and High Strength.

Xylan-based films have great potential to replace petroleum-based polymers used for packaging and coatings due to their excellent biocompatibility, biodegradability, and good gas barrier properties. However, fabricating a xylan-based film with flexible, transparent, water-proof, and excellent mechanical properties is an enormous challenge. Herein, we manufactured a series of degradable films with adjustable properties via solution-casting using a water-soluble xylan derivative. This is the first report of a pure xylan-based film with high performance, requiring no additives. The tensile strength of the xylan-based film could be controlled by adjusting the aldehyde content, which varied from 105.0 to 132.6 MPa. The smallest initial water contact angle of the xylan-based films is 93.26°, indicating that these films are hydrophobic. This work shows a simple and viable route toward manufacturing xylan-based films with high tensile strength, flexibility, and transparency, which can be used for packaging materials and coatings.

Lignin-Based Direct Ink Printed Structural Scaffolds.

3D printing of lignocellulosic biomass (cellulose, hemicellulose, and lignin) has attracted increasing attention by using this abundant, sustainable, and ecofriendly material. While cellulose can be easily tailored into a highly viscous ink for 3D printing, after solvent evaporation, the final printed structures become highly porous, fragile, and easily fall apart in water due to its hydrophilic nature. Lignin, another crucial component of natural lignocellulose, has not yet been reported for ink printing due to its unfavorable rheological behavior. Herein, a low-cost direct ink printing strategy is developed to fabricate lignin-based 3D structures with lignin no further refined and a more compact microstructure as well as different functionalities compared with printed cellulose. By using a soft triblock copolymer as the crosslinking agent, the rheology of lignin-based inks can be adjusted from soft to rigid, and even enables vertical printing which requires stiff and self-supporting features. The lignin-based inks contain less water (≈40 wt%) and exhibit a much denser, stiffer structure, resulting in a wet tensile strength of ≈30 MPa, compared to only ≈0.6 MPa for printed cellulose. In addition, the unique macromolecular structure of lignin also demonstrates significantly improved stability in water and under heat, as well as UV-blocking performance.

3D Printed Room Temperature Phosphorescence Materials Enabled by Edible Natural Konjac Glucomannan.

Shaping room temperature phosphorescence (RTP) materials into 3D bodies is important for stereoscopic optoelectronic displays but remains challenging due to their poor processability and mechanical properties. Here, konjac glucomannan (KGM) is employed to anchor arylboronic acids with various π conjugations via a facile B─O covalent reaction to afford printable inks, using which full-color high-fidelity 3D RTP objects with high mechanical strength can be obtained via direct ink writing-based 3D printing and freeze-drying. The doubly rigid structure supplied by the synergy of hydrogen bonding and B─O covalent bonding can protect the triplet excitons; thus, the prepared 3D RTP object shows a striking lifetime of 2.14 s. The printed counterparts are successfully used for 3D anti-counterfeiting and can be recycled and reprinted nondestructively by dissolving in water. This success expands the scope of printable 3D luminescent materials, providing an eco-friendly platform for the additive manufacturing of sophisticated 3D RTP architectures.

Xylan Plastic.

The increasing accumulation of plastic waste has brought serious environmental issues. Biodegradable plastics are promising candidates to solve the problem but still remain a scientific challenge. Here, xylan plastic (XP) was fabricated by a strategy of double cross-linking through etherification combined with hot pressing. The mechanical properties, particularly the toughness of XP, were significantly enhanced by the incorporation of chemical and physical cross-linking domains. The tensile strength, toughness, and modulus of XP can reach up to 55 MPa, 2.2 MJ/m3, and 1.7 GPa, respectively, which are superior to most traditional plastics. Dynamic mechanical analysis (DMA) characterizations confirmed that XP is thermoplastic and can be hot formed. Additionally, the reversible hydrogen bond interaction between xylan chains could be simply regulated by water molecules, rendering XP readily transformed and repeatedly reprogrammed into versatile 2D/3D shapes. Moreover, XP showed a low thermal expansion coefficient and excellent optical properties. Cytotoxicity and degradability tests demonstrated that XP had excellent nontoxicity and can be biodegraded in 60 days. This work thus suggests an avenue for the scalable production of high-performance xylan-based plastics, in which the raw material comes from industrial wastes and exhibits great potential in response to plastic pollution.

Microencapsulated phase change material via Pickering emulsion based on xylan nanocrystal for thermoregulating application.

Phase change materials (PCM) are promising for thermal regulation and energy storage, but suffer from the deformation and leakage of capsules. Herein, inspired by cellulose nanocrystal (CNC), xylan nanocrystal (XNC) with a dimension of 25-60 nm was successfully prepared through oxalic acid hydrolysis of high-crystalline xylan as raw materials via a top-down approach. With the introduction of hydrophobic groups, compared to XNC, succinylated XNC showed more remarkable emulsifying property over 7 days of storage at room temperature. Microencapsulated PCM composite consisting of sodium alginate (SA) as "matrix" and succinylated xylan nanocrystal (XNC) stabilized paraffin-based Pickering capsule (PCM beads) as "core" was facilely fabricated. PCM composite with the latent heat of 105.59 J·g-1 showed excellent thermoregulating performance. Our work suggests a new pathway toward sustainability of hemicelluloses in the application of food emulsion and thermal energy management.

Large-Scale Preparation for Multicolor Stimulus-Responsive Room-Temperature Phosphorescence Paper via Cellulose Heterogeneous Reaction.

The large-scale preparation of sustainable room-temperature phosphorescence (RTP) materials, particularly those with stimulus-response properties, is attractive but remains challenging. This study develops a facile heterogeneous B─O covalent bonding strategy to anchor arylboronic acid chromophores to cellulose chains using pure water as a solvent, resulting in multicolor RTP cellulose. The rigid environment provided by the B─O covalent bonds and hydrogen bonds promotes the triplet population and suppresses quenching, leading to an excellent lifetime of 1.42 s for the target RTP cellulose. By increasing the degree of chromophore conjugation, the afterglow colors can be tuned from blue to green and then to red. Motivated by this finding, a papermaking production line is built to convert paper pulp reacted with an arylboronic acid additive into multicolor RTP paper on a large scale. Furthermore, the RTP paper is sensitive to water because of the destruction of hydrogen bonds, and the stimuli-response can be repeated in response to water/heat stimuli. The RTP paper can be folded into 3D afterglow origami handicrafts and anti-counterfeiting packing boxes or used for stimulus-responsive information encryption. This success paves the way for the development of large-scale, eco-friendly, and practical stimuli-responsive RTP materials.

Lignin-Based Materials for Additive Manufacturing: Chemistry, Processing, Structures, Properties, and Applications.

The utilization of lignin, the most abundant aromatic biomass component, is at the forefront of sustainable engineering, energy, and environment research, where its abundance and low-cost features enable widespread application. Constructing lignin into material parts with controlled and desired macro- and microstructures and properties via additive manufacturing has been recognized as a promising technology and paves the way to the practical application of lignin. Considering the rapid development and significant progress recently achieved in this field, a comprehensive and critical review and outlook on three-dimensional (3D) printing of lignin is highly desirable. This article fulfils this demand with an overview on the structure of lignin and presents the state-of-the-art of 3D printing of pristine lignin and lignin-based composites, and highlights the key challenges. It is attempted to deliver better fundamental understanding of the impacts of morphology, microstructure, physical, chemical, and biological modifications, and composition/hybrids on the rheological behavior of lignin/polymer blends, as well as, on the mechanical, physical, and chemical performance of the 3D printed lignin-based materials. The main points toward future developments involve hybrid manufacturing, in situ polymerization, and surface tension or energy driven molecular segregation are also elaborated and discussed to promote the high-value utilization of lignin.

Self-Standing, Photothermal-Actuating, and Motion-Monitoring Janus Films One-Pot Synthesized by Green Carboxymethyl Glucomannan/Liquid Metal Nanoinks.

Downsizing bulk liquid metals (LM) at the nanometer scale with biocompatibility and multifunction is a key process for electronic or medical applications. Here, we report a stable and green LM aqueous colloidal ink by wrapping eutectic gallium-indium alloys (EGaIn) with carboxymethyl glucomannan (CGM) derived from radiata pine chip, which is capable of being prepared into a free-standing, photothermal-actuating, and motion-monitoring Janus film. With the assistance of CGM, the bulk EGaIn was ultrasonicated into stable nanodroplets (∼500 nm) with a typical "core-shell" structure, in which the colloidal inks can be stored for more than 1 week under room temperature. The stable CGM/EGaIn inks can be patterned on different substrates to form coating layers or self-assembled into free-standing Janus films with high mechanical strength and modulus (∼94 MPa and ∼3.8 GPa) by density deposition. Such a Janus film with anisotropic thermal conductivity made it a potential photothermal actuator. In addition, the biocompatible film demonstrated both high conductivity and large resistance variation in response to strain change (gauge factor >500), allowing for human motion monitoring. This work provides a new prospect for the development of biocompatible and high-performance nano-LM materials.

Fabrication of flexible composite film based on xylan from pulping process for packaging application.

To realize the application of xylan based film in food and drug packaging, the poor mechanical property and film-forming property of xylan based film must be overcome. Herein, a good oxygen barrier composite film with desired mechanical properties was prepared based on carboxymethly xylan (CMX), chitosan (CS), and graphene oxide (GO). The results of scanning electron microscope revealed the composite film had a dense and continuous structure, which will endow the composite film with excellent mechanical property. As expected, the composite film with the 0.5% mass fraction of GO exhibited best mechanical property, among which the tensile stress, tensile strain, and Young's modulus of the composite film reached 50.81 MPa, 47.61%, and 1.39 GPa, respectively. The oxygen barrier properties of the composite films significantly increased with the addition of graphene oxide due to the dense, stacked multilayer structure. In addition, these composite films exhibited good antibacterial properties. Therefore, these films show great promise in the field of food packaging and wound dressing due to their excellent mechanical, oxygen barrier and antibacterial properties.

Scalable Wood Hydrogel Membrane with Nanoscale Channels.

Many efforts have been dedicated to exploring nanofluidic systems for various applications including water purification and energy generation. However, creating robust nanofluidic materials with tunable channel orientations and numerous nanochannels or nanopores on a large scale remains challenging. Here, we demonstrate a scalable and cost-effective method to fabricate a robust and highly conductive nanofluidic wood hydrogel membrane in which ions can transport across the membrane. The ionically conductive balsa wood hydrogel membrane is fabricated by infiltrating poly(vinyl alcohol) (PVA)/acrylic acid (AA) hydrogel into the inherent bimodal porous wood structure. The balsa wood hydrogel membrane demonstrates a 3 times higher strength (52.7 MPa) and 2 orders of magnitude higher ionic conductivity compared to those of natural balsa both in the radial direction (coded as R direction) and along the longitudinal direction (coded as L direction). The ionic conductivity of the balsa wood hydrogel membrane is 1.29 mS cm-1 along the L direction and nearly 1 mS cm-1 along the R direction at low salt concentrations (up to 10 mM). In addition, the surface-charge-governed ion transport also renders the balsa wood hydrogel membrane able to harvest electrical energy from salinity gradients. A current density of up to 17.65 µA m-2 and an output power density of 0.56 mW m-2 are obtained under a 1000-fold salt concentration gradient, which can be further improved to 2.7 mW m-2 by increasing the AA content from 25 wt % to 50 wt %. These findings make contributions to develop energy-harvesting systems and other nanofluidic devices from sustainable wood materials.

Hemicelluloses-based magnetic aerogel as an efficient adsorbent for Congo red.

A renewable, efficient, and low-cost material is essential for adsorbing water pollution, such as dyes and heavy metal ions pollution. Here in, we demonstrate an aerogel to remove the dyes from water based on hemicellulose. The dialdehyde hemicelluloses (DAH) were synthesized by oxidation of hemicellulose extracted from straw with NaIO4. The hydrogels were prepared based on the dialdehyde hemicellulose and chitosan-Fe3O4 composite by the Schiff's base reaction, which were processed with vacuum freeze-drying technique to obtain aerogels. It was found that hydroxyl groups at C2 and C3 of hemicellulose were oxidized to aldehyde groups after modification, and the content of aldehyde group was 5.57 mmol/g. The maximum compress strength of aerogel was 0.37 MPa, and the maximum absorption capacity of Congo red dye was 137.74 mg/g. Aerogels with Fe3O4 exhibited magnetism which enables the aerogels to easily recycle. Meanwhile, the thermal stability, mechanical properties of the aerogels and its adsorption property to Congo red dye could be improved directly by the addition of Fe3O4.

Xylan-based hydrogels for potential skin care application.

Skin care biomaterials from natural compounds are increasingly needed in recent. We demonstrate a simple strategy to fabricate the dialdehyde xylan (DAX) crosslinked hydrogel with skin care potential. The hydrogel mainly consists of dialdehyde xylan, which is used as crosslinker for gelatin (G). Glycerol (Gly) and nicotinamide (NCA) are introduced here for improving the texture, antibacterial property as well as skin care functionality. The in vitro release results demonstrate that NCA can be released smoothly from the xylan-based gel, whereby the xylan-based fabricated gel can be utilized as an ideal matrix gel in skin care with loading and release function. The antibacterial ability is in the following order: Yeast > Bacillus subtilis > Staphylococcus aureus. The cytocompatibility experiments confirm the excellent viability of the gel. These merits demonstrate the fabricated hydrogel as a potential material in skin care.

Highly Elastic Hydrated Cellulosic Materials with Durable Compressibility and Tunable Conductivity.

Anisotropic cellular materials with direction-dependent structure and durable mechanical properties enable various applications (e.g., nanofluidics, biomedical devices, tissue engineering, and water purification), but their widespread use is often hindered by complex and scale-limited fabrication and unsatisfactory mechanical performance. Here, inspired by the anisotropic and hierarchical material structure of tendons, we demonstrate a facile, scalable top-down approach for fabricating a highly elastic, ionically conductive, anisotropic cellulosic material (named elastic wood) directly from natural wood via chemical treatment. The resulting elastic wood demonstrates good elasticity and durable compressibility, showing no sign of fatigue after 10 000 compression cycles. The chemical treatment not only softens the wood cell walls by partially removing lignin and hemicellulose but introduces an interconnected cellulose fibril network into the wood channels. Atomistic and continuum modeling further reveals that the absorbed water can freely and reversibly move inside the elastic wood and therefore helps the elastic wood accommodate large compressive deformation and recover to its original shape upon compression release. In addition, the elastic wood showed a high ionic conductivity of up to 0.5 mS cm-1 at a low KCl concentration of 10-4 M, which can be tuned by changing the compression ratio of the material. The demonstrated elastic, mechanically robust, and ionically conductive cellulosic material combining inherited anisotropic cellular structure from natural wood and a self-formed internal gel may find a variety of potential applications in ionic nanofluidics, sensors, soft robots, artificial muscle, environmental remediation, and energy storage.

General, Vertical, Three-Dimensional Printing of Two-Dimensional Materials with Multiscale Alignment.

Two-dimensional (2D) materials (e.g., boron nitride (BN), graphene, and MoS2) have great potential in emerging energy, environmental, and electronics applications. Assembly of 2D materials into vertically aligned structures is highly desirable (e.g., low tortuosity for rapid ion transport in fast charging-discharging batteries, guiding thermal transport for efficient thermal management), yet extremely challenging due to the energetically unfavorable in processing. Herein, we reported a general three-dimensional (3D) printing method to fabricate vertically aligned 2D materials in multiscale, using BN nanosheet as the proof-of-concept. The 3D-printed macroscale rods are composed of vertically aligned BN nanosheets at the nanoscale. The formation of the hierarchical aligned structure is enabled by the optimized ink that holds a significant shear-thinning behavior and an ultrahigh storage modulus, as identified at a narrow region in the printability diagram. The resulting vertically aligned multiscale structure with 2D nanosheets demonstrated an outstanding through-plane thermal conductivity, up to 5.65 W m-1 K-1, significantly higher than the value of conventional BN based structures where the sheets are horizontally aligned. The vertical 3D printing of 2D BN nanosheets can be expanded to other 2D materials in constructing hierarchically aligned structures for a range of emerging technologies such as batteries, membranes, and structural materials.

Muscle-Inspired Highly Anisotropic, Strong, Ion-Conductive Hydrogels.

Biological tissues generally exhibit excellent anisotropic mechanical properties owing to their well-developed microstructures. Inspired by the aligned structure in muscles, a highly anisotropic, strong, and conductive wood hydrogel is developed by fully utilizing the high-tensile strength of natural wood, and the flexibility and high-water content of hydrogels. The wood hydrogel exhibits a high-tensile strength of 36 MPa along the longitudinal direction due to the strong bonding and cross-linking between the aligned cellulose nanofibers (CNFs) in wood and the polyacrylamide (PAM) polymer. The wood hydrogel is 5 times and 500 times stronger than the bacterial cellulose hydrogels (7.2 MPa) and the unmodified PAM hydrogel (0.072 MPa), respectively, representing one of the strongest hydrogels ever reported. Due to the negatively charged aligned CNF, the wood hydrogel is also an excellent nanofluidic conduit with an ionic conductivity of up to 5 × 10-4 S cm-1 at low concentrations for highly selective ion transport, akin to biological muscle tissue. The work offers a promising strategy to fabricate a wide variety of strong, anisotropic, flexible, and ionically conductive wood-based hydrogels for potential biomaterials and nanofluidic applications.

Facile synthesis of high strength hot-water wood extract films with oxygen-barrier performance.

Biobased nanocomposite films for food packaging with high mechanical strength and good oxygen-barrier performance were developed using a hot-water wood extract (HWE). In this work, a facile approach to produce HWE/montmorillonite (MMT) based nanocomposite films with excellent physical properties is described. The focus of this study was to determine the effects of the MMT content on the structure and mechanical properties of nanocomposites and the effects of carboxymethyl cellulose (CMC) on the physical properties of the HWE-MMT films. The experimental results suggested that the intercalation of HWE and CMC in montmorillonite could produce compact, robust films with a nacre-like structure and multifunctional characteristics. This results of this study showed that the mechanical properties of the film designated FCMC0.05 (91.5 MPa) were dramatically enhanced because the proportion of HWE, MMT and CMC was 1:1.5:0.05. In addition, the optimized films exhibited an oxygen permeability below 2.0 cm3 µm/day·m2·kPa, as well as good thermal stability due to the small amount of CMC. These results provide a comprehensive understanding for further development of high-performance nanocomposites which are based on natural polymers (HWE) and assembled layered clays (MMT). These films offer great potential in the field of sustainable packaging.