Stepwise Ethanol-Water Fractionation of Enzymatic Hydrolysis Lignin to Improve Its Performance as a Cationic Dye Adsorbent.

In this work, lignin fractionation is proposed as an effective approach to reduce the heterogeneity of lignin and improve the adsorption and recycle performances of lignin as a cationic dye adsorbent. By stepwise dissolution of enzymatic hydrolysis lignin in 95% and 80% ethanol solutions, three lignin subdivisions (95% ethanol-soluble subdivision, 80% ethanol-soluble subdivision, and 80% ethanol-insoluble subdivision) were obtained. The three lignin subdivisions were characterized by gel permeation chromatography (GPC), FTIR, 2D-NMR and scanning electron microscopy (SEM), and their adsorption capacities for methylene blue were compared. The results showed that the 80% ethanol-insoluble subdivision exhibited the highest adsorption capacity and its value (396.85 mg/g) was over 0.4 times higher than that of the unfractionated lignin (281.54 mg/g). The increased adsorption capacity was caused by the enhancement of both specific surface area and negative Zeta potential. The maximum monolayer adsorption capacity of 80% ethanol-insoluble subdivision by adsorption kinetics and isotherm studies was found to be 431.1 mg/g, which was much higher than most of reported lignin-based adsorbents. Moreover, the 80% ethanol-insoluble subdivision had much higher regeneration yield (over 90% after 5 recycles) compared with the other two subdivisions. Consequently, the proposed fractionation method is proved to be a novel and efficient non-chemical modification approach that significantly improves adsorption capacity and recyclability of lignin.

Bioinspired multiscale cellulose/lignin-silver composite films with robust mechanical, antioxidant and antibacterial properties for ultraviolet shielding.

Constructing a high-performance ultraviolet shielding film is an effective way for addressing the growing problem of ultraviolet radiation. However, it is still a great challenge to achieve a combination of multifunctional, excellent mechanical properties and low cost. Here, inspired by the multiscale structure of biomaterials and features of lignin, a multifunctional composite film (CNF/CMF/Lig-Ag) is constructed via a facile vacuum-filtration method by introducing micron-sized cellulose fibers (CMF) and lignin-silver nanoparticles (Lig-Ag NPs) into the cellulose nanofibers (CNF) film network. In this composite film, the microfibers interweave with nanofibers to form a multiscale three-dimensional network, which ensures satisfactory mechanical properties of the composite film. Meanwhile, the Lig-Ag NPs are employed as a multifunctional filler to enhance the composite film's antioxidant, antibacterial and ultraviolet shielding abilities. As a result, the prepared CNF/CMF/Lig-Ag composite film demonstrates excellent mechanical properties (with tensile strength of 133.8 MPa and fracture strain of 7.4 %), good biocompatibility, high thermal stability, potent antioxidant and antibacterial properties. More importantly, such composite film achieves a high ultraviolet shielding rate of 98.2 % for ultraviolet radiation A (UVA) and 99.4 % for ultraviolet radiation B (UVB), respectively. Therefore, the prepared CNF/CMF/Lig-Ag composite film shows great potential in application of ultraviolet protection.

Fabrication modulation of lignin-derived carbon nanosphere supported Pd nanoparticle via lignin fractionation for improved catalytic performance in vanillin hydrodeoxygenation.

Nano-lignin presents great potential in advanced carbon materials preparation since it integrates the advantages of nanomaterials as well the preferable properties of lignin (e.g. high carbon content and highly aromatic structure). Herein, lignin-derived carbon nanosphere supported Pd catalysts (Pd@LCNS) were prepared via a two-step carbonization of Pd2+ adsorbed lignin nanospheres (LNS) and applied in vanillin hydrodeoxygenation. The effect lignin heterogeneity on the synthesis of Pd@LCNS as well as its catalytic performance was further investigated through the synthesis of Pd@LCNS using three lignin fractions with different molecular weight. The results showed that the three Pd@LCNSs exhibited significant differences in the morphology of both carbon support and Pd nanoparticles. Pd@LCNS-3 prepared from high molecular weight lignin fraction (L-3) presented stable carbon nanosphere support with the smallest particle size (∼150 nm) and the highest Pd loading amount (3.78 %) with the smallest Pd NPs size (∼1.6 nm). Therefore, Pd@LCNS-3 displayed superior catalytic activity for vanillin hydrodeoxygenation (99.34 % of vanillin conversion and 99.47 % of 2-methoxy-4-methylphenol selectivity) at 90 °C without H2. Consequently, this work provides a sustainable strategy to prepare uniformly dispersed lignin-based carbon-supported Pd catalyst using high molecular weight lignin as the feedstock and further demonstrate its superior applicability in the selective transfer hydrogenation of vanillin.

Microplastic pollutants in water: A comprehensive review on their remediation by adsorption using various adsorbents.

Microplastics (MPs), as emerging pollutants, have attracted the attention of environmentalists, statespersons, and the scientific community over the last few decades. To address the spread of MPs in the environment, it is imperative to develop various removal techniques and materials that are effective, scalable, and ecologically benign. However, to the best of our knowledge, no review has systematically examined the removal of MPs using adsorption or provided an in-depth discussion on various adsorbents. Adsorption is an inexpensive and effective technology for wastewater treatment. Recently, many researchers have conducted studies on MP remediation using diverse adsorbent materials, such as biochar, activated carbon, sponges, carbon nanotubes, metal-layered oxides, metal-organic frameworks (MOFs), and zeolites. Each adsorbent has advantages and disadvantages. To overcome their disadvantages, researchers have been designing and developing hybrid adsorbents for MP remediation. This review provides insights into these individual adsorbents and also discusses hybrid adsorbents for MP removal. Finally, the review elaborates on future possibilities and ways to enable more efficient, scalable, and environmentally friendly MP cleanup. Overall, this review bridges the gap between contemporary MP remediation using adsorption techniques and adsorbent development.

Green potassium fertilizer from enzymatic hydrolysis lignin: Effects of lignin fractionation on wheat seed germination and seedling growth.

Sustainably sourced lignin presents great potential as a green feedstock for fertilizer production but commercial fulfillment is still challenging owing to the mediocre fertilizer activity of lignin. To address this issue, an effective strategy to enhance the activity of lignin-based potassium fertilizer (LPF) is proposed through lignin fractionation. Three lignin fractions subdivided from enzymatic hydrolysis lignin (EHL) were adopted as the feedstock for LPF preparation, and the effect of lignin fractionation on wheat seed germination and seedling growth was investigated. Compared with the potassium fertilizer from unfractionated lignin, LPF-F1 showed significantly improved effects on promoting seed germination and seedling growth, which can be attributed to the high potassium content resulted from its abundant phenolic hydroxyl and carboxyl contents. Under the optimal treatment concentration (100 mg/L), LPF-F1 showed comparable promotion effect to commercial fulvic acid potassium on wheat seedling growth, suggesting the potential of LPF-F1 as commercial potassium fertilizer. Overall, this work reveals that lignin heterogeneity presents critical effects on the wheat seed germination and seedling growth of LPF, and the fertilizer activity of LPF can be substantially improved using fractionated lignin with low molecular weight as the raw material.

Custom-designed polyphenol lignin for the enhancement of poly(vinyl alcohol)-based wood adhesive.

Adhesives are used extensively in the wood industry. As resource and environmental issues become increasingly severe, the development of green and sustainable biomass-based adhesives has attracted increasing attention. In this work, a green wood adhesive is developed from poly(vinyl alcohol) and lignin with molecular designs of lignin extending beyond those in nature. The lignin undergoes extraction from corncob residue, aldehydration, and phenolisation (phenol, resorcinol, and catechol) to significantly increase the phenolic hydroxyl groups (over 7.92 mmol/g), which has the effect of enhancing the hydrogen bonding force between the adhesive and the wood, thereby greatly improving adhesive performance. Compared with pure PVA, polyphenol lignin-containing PVA showed improved adhesion strength and hydrophobicity. PVA/resorcinol-lignin has the significantly improved wood lap shear strength (6.27 MPa, 77.6 % improvement) and hydrophobicity (almost 100 % increase in wet shear strength). This research not only provides a green and high-performance alternative raw material for wood adhesives but also broadens the path for large-scale application of biomass.

Dendritic cell-targeting polymer nanoparticle-based immunotherapy for cancer: A review.

Cancer immunity is dependent on dynamic interactions between T cells and dendritic cells (DCs). Polymer-based nanoparticles target DC receptors to improve anticancer immune responses. In this paper, DC surface receptors and their specific coupling natural ligands and antibodies are reviewed and compared. Moreover, reaction mechanisms are described, and the synergistic effects of immune adjuvants are demonstrated. Also, extracellular-targeting antigen-delivery strategies and intracellular stimulus responses are reviewed to promote the rational design of polymer delivery systems.

Novel metal-lignin assembly strategy for one-pot fabrication of lignin-derived heteroatom-doped hierarchically porous carbon and its application in high-performance supercapacitor.

The conversion of renewable lignin with low-cost and high carbon content properties into porous carbon materials for supercapacitor applications has caught considerable interest. Herein, two dimensional lignin-derived carbon nanosheets (N-LHPC) with hierarchically porous structures were facilely synthesized via a novel metal-lignin assembly strategy and their performances for supercapacitor applications were investigated. During the carbonization process, the uniformly distributed Zn facilitates the coordinating development of micropores structure and the generated MgO embedded in the carbon matrix acts as a template to produce mesoporous structure after acid washing. Moreover, the melamine addition promotes the development of mesopores by formation of lamellae structure and realizes the N doping in the carbon materials. Therefore, the obtained N-LHPC presents an excellent specific capacitance of 235.75 F/g at 0.5 A/g owing to its hierarchical pore structure as well as the N/O functional groups. Moreover, at the power density of 450 W/kg, the N-LHPC achieves a maximum energy density of 14.75 Wh/kg, showing great application potential in energy storage. The metal-lignin assembly strategy followed by N-doping proposed in this paper provides N-LHPC materials with hierarchical nanostructure, good electron/ion transfer properties, and abundant pseudocapacitive active species, which improve the capacitance performances of the N-LHPC.

Strong, conductive, and freezing-tolerant polyacrylamide/PEDOT:PSS/cellulose nanofibrils hydrogels for wearable strain sensors.

Hydrogels with prominent flexibility, versatility, and high sensitivity play an important role in the design and fabrication of wearable sensors. In particular, these flexible conductive hydrogels exhibit elastic modulus that is highly compatible with human skin, demonstrating the great potential for flexible sensing. However, the preparation of high-performance hydrogel-based sensors that can restrain extreme cold conditions is still challenging. Herein, a novel anti-freezing composite hydrogel with superior conductivity based on polyacrylamide (PAM), LiCl, and PEDOT:PSS coated cellulose nanofibrils (PAM/PEDOT:PSS/CNF) is constructed. The addition of CNF increased the hydrogen bonding sites of the molecular chains in the micro, thus improving the mechanical strength and the conductivity of the hydrogel in the macro. The hydrogels achieve a high tensile strength of 0.19 MPa, compressive strength of 0.92 MPa, and dissipation energy of 41.9 kJ/m3. Otherwise, LiCl increases the interactions between the colloidal phase and water molecules, endowing the hydrogels with excellent freezing tolerance. Specifically, the optimized hydrogel of 45 % LiCl exhibited stable mechanical properties at -40 °C. Finally, the composite hydrogel was used to assemble flexible sensors with high sensitivity of 10.3 MPa-1, which can detect a wide range of human movements and physiological activities.

Lignin-coordinated highly dispersed PdZn alloy nanocluster supported on N-doped nanolayer carbon and its application in hexavalent chromium detoxification.

As a renewable and low-cost biomacromolecule with high aromaticity and carbon content, lignin is a promising raw material for preparation of versatile carbon materials. Herein, we present a facile one-pot approach to prepare PdZn alloy nanocluster catalysts supported on N-doped lignin-derived nanolayer carbon through facile pyrolysis of melamine-mixed lignin-Pd-Zn complex. The dispersion of the PdZn alloy nanoclusters could be effectively modulated by varying the addition of melamine and the molar ratio of Pd and Zn salts. PdZn alloy nanocluster catalysts (Pd-Zn29@N10C) with ultra-small particle size (about 0.47 nm) were prepared when 10 times of melamine (relative to lignin weight) was added and the molar ratio of Pd and Zn salts was 1:29. Thereby, the catalyst presented superior catalytic activity for reduction of Cr(VI) to harmfulless Cr(III), significantly better than the two references Zn@N10C (without Pd addition) and Pd-Zn29@C (without N doping), as well as the commercial Pd/C. In addition, thanks to the strong anchoring of the PdZn alloy on the N-doped nanolayer support, the Pd-Zn29@N10C catalysts also exhibited good reusability. Consequently, the current study provides a straightforward and feasible method for producing highly dispersed PdZn alloy nanoclusters by lignin coordination, and further demonstrates its excellent applicability in hexavalent chromium reduction.

A cascade valorization of Kenaf stalk for the preparation of lignin sunscreens and papermaking.

Lignin has been regarded as a potential natural sun screening agent. However, the dark color of traditional industrial lignin hinders its application in the field of skincare. In this study, a green and facile approach was developed to extract light-colored lignin. p-Toluenesulfonic acid (p-TsOH) was used to separate lignin and fibers from Kenaf stalks. During the isolation of lignin, formaldehyde was added to preserve the ß-O-4 bonds of lignins in the form of stable acetals. The obtained lignin was further employed to prepare nanoparticles (LNPs) as sunscreen additives. After adding 4 wt% LNPs, the SPF values of the cream increased from 7.05 to 27.84. The residual fibers from the Kenaf stalks can be utilized for papermaking as the raw materials. by mixing them with softwood pulp to reduce the consumption of commercial pulp. With the addition of 5 wt% residual fibers in commercial softwood pulp, the produced paper showed better mechanical properties. The ring crush strength index and tear index of the samples increased from 2.49 N·m/g and 4.63 mN·m2/g to 2.62 N·m/g and 4.75 mN·m2/g, respectively. This study paved a way for the comprehensive utilization of Kenaf stalks towards not only papermaking but also daily chemical products.

A Rapid and Reversible pH Control Process for the Formation and Dissociation of Lignin Nanoparticles.

As a new and green type of nanomaterials, lignin nanoparticles (LNPs) have been considered as high-value renewable materials for application in many fields. However, the industrialization of LNPs faces many challenges, such as high manufacturing costs and small-scale production. Here, a simple but rapid and reversible approach for the fabrication of LNPs was provided via switching pH environments. The LNPs were regularly shaped in the acetonitrile/water system, and their size appeared to be very homogeneous. The alternation of forming and dissolving of LNPs could be repeated many times simply by alternately adding acid and alkaline solutions. There was little difference in the molecular structures between the original and regenerated LNPs. In addition, the consumption of solvents for LNPs production was only 200 mL g-1 , reduced by more than 10 times compared with conventional solvent exchange methods. The concentration of LNPs in the solution also improved to 5.0 g L-1 . This study not only provides a new, simple, and effective strategy for the fabrication of LNPs but also paves the way towards their real green production and application.

Interaction of lignin and xylan in the hydrothermal synthesis of lignocellulose-based carbon quantum dots and their application in in-vivo bioimaging.

The complex interaction of lignin, cellulose, and hemicellulose in the hydrothermal degradation progress of lignocellulose, has led to uncertainty in the hydrothermal synthesis of lignocellulose-based CQDs (LC-CQDs). This makes it difficult to identify the specific formation mechanism of LC-CQDs. To simplify the reaction system and comprehensively describe the formation of LC-CQDs, both lignin and hemicellulose, the main hydrothermal degradation products of lignocellulose, were used as precursor to simulate and explore the synthesis of LC-CQDs at different time intervals (2-12 h). First, different lignin models were employed for preparing CQDs to determine the key lignin structure that govern CQDs formation. G-type lignin-model based CQDs were shown to have higher fluorescence intensity than H- and S-type. Then, G-type lignin model and hemicellulose model (xylan) were used simultaneously hydrothermal to prepare LC-CQDs. The analysis shows that the carbon nucleus preferentially formed by the lignin provides growth sites for small molecules degraded from hemicellulose, which gradually grow around the carbon core over time, thus forming a "sunflower" structure of CQDs. The presence of a lignin model could effectively guide the small molecules toward CQDs formation instead of carbonization. Additionally, the CQDs exhibit good in-vivo imaging performance.

Sustainable preparation of surface functionalized cellulose nanocrystals and their application for Pickering emulsions.

Herein, a highly efficient and sustainable approach, namely HCl-catalyzed para-toluene sulfonic acid/Formic acid (p-TsOH/FA) hydrolysis was reported to produce surface functionalized cellulose nanocrystals (CNCs). The optimized CNCs showed a high yield (79.6 %), high crystallinity (70.6 %) and high thermal stability (maximal weight loss temperature around 350 °C). In addition, the as-prepared CNCs possess excellent ability to stabilize oil-water due to the introduction of functional formyl groups, which could be promising stabilizers for Pickering emulsions (PEs). At a fixed oil-water ratio (2:8, v:v), the CNCs with the concentration of 0.5 wt% to 2.0 wt% could stabilize peanut oil to make PEs, and the emulsion droplets were <5 µm in diameter. In addition, the stability of the PEs at different temperature, pH, ionic strength, and long storage time were studied. The results indicated that the obtained CNCs could be sustainable and superior stabilizers for PEs.

Green and stable lignin-based nanofillers reinforced poly(l-lactide) with supertough and strong performance.

Lignin nanoparticles (LNPs), as a new type of green nanomaterial, initiate many promising applications in polymer composites. However, their heterogeneity, dissolution in organic solvents, and poor compatibility in the polymer matrix greatly limited the applications of LNPs fillers. Herein, we proposed an antisolvent precipitation of the fractionations by combining a hydrothermal treatment-assisted synthesis to fabricate self-crosslinked LNPs (ScLNPs), which have good stability in the organic solvent and controllable sizes. After surface grafting modification with d-lactide, ScLNPs-graft-poly(d-lactide) (ScLNPs-g-PDLA) exhibited excellent dispersion and compatibility in PLLA matrix. Using the rational design and addition of ScLNPs-g-PDLA fillers, the strength and toughness of the generated PLLA composite reached 31.6 MPa and 396 % (the highest value among the PLLA materials), respectively. Furthermore, the mechanical performance can also be well-tuned by the sizes and amounts of LNPs fillers. This strategy involving only green and recyclable materials provides an effective route to producing sustainable polymeric plastics with integrated strength and super-toughness.

Hydrothermal method-assisted synthesis of self-crosslinked all-lignin-based hydrogels.

Lignin, as the most abundant aromatic biopolymer, is being widely studied to replace phenol and some other petroleum-based materials in the polymer industry. However, the low substitution of lignin and high levels of additives greatly limited the applications of lignin-based materials. Herein, we first propose a simple but effective hydrothermal method assisted synthesis for the fabrication of self-crosslinked lignin-based hydrogels (Lig-Scgel) with super-high-contents (75 wt%) of lignin and controllable mechanical properties. The self-crosslink mechanism was inspired by the repolymerization of lignins under a hydrothermal environment. The employment of self-condensation of lignin subunits in the synthesis of Lig-Scgel can significantly improve the degree of crosslinking, thereby greatly reducing the addition of toxic crosslinkers. The appearances, microstructures, crosslink densities, and mechanical properties of Lig-Scgels can be well controlled by simply altering the hydrothermal temperatures. This strategy not only promotes green and large-scale applications of lignin but also provides insights in the development of environment-friendly polymeric materials.

High-efficiency separation of hemicellulose from bamboo by one-step freeze-thaw-assisted alkali treatment.

The selectivity of alkali treatment (AT) for hemicellulose separation is reduced due to the alkali solubility of lignin. It was improved using freeze-thaw-assisted alkaline treatment (FT/AT). In this study, bamboo hemicellulose was separated via a one-step freeze-thaw-assisted alkali treatment (OFT/AT). The effects of freezing temperature, freezing time, alkali concentration, and treatment time on bamboo components were studied. The separation yield of hemicellulose was 73.26%, compared to 64.00% using conventional FT/AT. The separation of lignin and cellulose was inhibited as alkali concentration decreased from 7.0% to 5.0%. The extraction yield of hemicellulose increased from 46.35% to 56.12%. Structural analysis of extracted hemicellulose revealed the effective inhibition of the breakage of the xylose backbone and arabinose side chain of hemicellulose. This indicated that the molecular structure of extracted hemicellulose was relatively complete. It provides theoretical support for the efficient separation of hemicellulose by AT.

Alkylation modification for lignin color reduction and molecular weight adjustment.

The application of industrial kraft lignin is limited by its low molecular weight, dark color, and low solubility. In this work, an efficient crosslinking reaction with N,N-Dimethylformamide (DMF) and 1,6-dibromohexane was proposed for adjusting the molecular weight and color of lignin. The chemical structure of alkylation lignin was systematically investigated by gel permeation chromatography (GPC), ultraviolet spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, and 2D heteronuclear single quantum correlation nuclear magnetic resonance (HSQC NMR) spectra. After the alkylation modification, the molecular weights of the lignin were increased to 1643%. The resinol (ß-ß), ß-aryl ether (ß-O-4), and phenylcoumaran (ß-5) linkages were still the main types of the linkages. The formation of ß-ß linkage would be inhibited at high temperatures. The color reduction of lignin can be attributed to the low content of chromophores and low packing density. This alkylation lignin will be a new and general approach for developing molecular weight-controlled and light-colored lignins, which can find more applications in cosmetics, packing, and other fields.

Enhancing thermal conductivity and toughness of cellulose nanofibril/boron nitride nanosheet composites.

Generally, the thermal conductivity (TC) of composite based on cellulose nanofibrils (CNF) is improved by adding thermal conductive filler, which inevitably leads to the loss of its mechanical properties. In this work, it is the first to simultaneously improve the toughness and TC of CNF/boron nitride nanosheets (BNNS) composite from the perspective of thermal conductive filler addition and CNF crystal change. The hydrophilic-modified BNNSs were successfully prepared by xylose-assisted ball-milling prior to adding into CNF. Compared with that of CNF film (1.34 W/(m·K)), the in-plane TC of CNF/BNNS composite (12.68 W/(m·K)) increased significantly by 846 % with loading 30 % BNNS. Afterwards, both toughness (8.0 MJ·m-3, increased ~250 %) and TC (14.7 W/(m·K), increased ~16 %) of CNF/BNNS composite were further enhanced significantly by mercerization with 12.5 % NaOH solution. The simultaneously improvement of toughness and TC is unprecedented in related studies, which contributes to the effective preparation of thermal management materials.

Biomedical Applications of Bacterial Cellulose based Composite Hydrogels.

BACKGROUND: Bacterial cellulose (BC) and its derivatives are a rich source of renewable natural ingredients, which are of great significance for biomedical and medical applications but have not yet been fully exploited. BC is a high-purity, biocompatible, and versatile biomaterial that can be used alone or in combination with other ingredients such as polymers and nanoparticles to provide different structural organization and function. This review briefly introduces the research status of BC hydrogels, focusing on the preparation of BC-based composite hydrogels and their applications in the field of biomedicine, particularly the wound dressings, tissue engineering scaffolds, and drug delivery. METHODS: By reviewing the most recent literature on this subject, we summarized recent advances in the preparation of BC-based composite hydrogels and their advances in biomedical applications, including wound dressings, tissue engineering, and drug delivery. RESULTS: BC composite hydrogels have broadened the field of application of BC and developed a variety of BC-based biomaterials with excellent properties. BC-based hydrogels have good biocompatibility and broad application prospects in the biomedical field. CONCLUSION: BC-based composite hydrogels with the advantages of 3D structure, nontoxicity, high purity, and good biocompatibility, have great prospects in the development of sustainable and multifunctional biomaterials for biomedical applications.