Effects of lignin syringyl to guaiacyl ratio on cottonwood biochar adsorbent properties and performance.

Lignin syringyl to guaiacyl ratio (S/G) has long been suspected to have measurable impacts on biochar formation, but these effects are challenging to observe in biochars formed from whole biomass. When the model bioenergy feedstock Populus trichocarpa (cottonwood), with predictable lignin macromolecular structure tied to genetic variation, is used as feedstock for biochar production, these effects become visible. In this work, two P. trichocarpa variants having lignin S/G of 1.67 and 3.88 were ground and pyrolyzed at 700 °C. Water-demineralization of feedstock was used to simultaneously evaluate any synergistic influences of S/G and naturally-occurring potassium on biochar physicochemical properties and performance. The strongest effects of lignin S/G were observed on specific surface area (SBET) and oxygen-content, with S/G of 1.67 improving SBET by 11% and S/G of 3.88 increasing total oxygen content in demineralized biochars. Functional performance was evaluated by breakthrough testing in 1% NH3. Breakthrough times for biochars were nearly double that of a highly microporous activated carbon reference material, and biochar with S/G of 3.88 had 10% longer breakthrough time than its lower S/G corollary. Results support a combination of pore structure and oxygen-functionalities in controlling ammonia breakthrough for biochar.

An integrated biorefinery strategy for Eucalyptus fractionation and co-producing glucose, furfural, and lignin based on deep eutectic solvent/cyclopentyl methyl ether system.

A novel biphasic system containing water-soluble deep eutectic solvent (DES) and cyclopentyl methyl ether (CPME) was developed to treat Eucalyptus for furfural production, extracting lignin and enhancing cellulose enzymatic hydrolysis. Herein effect of DES type, water content in DES, temperature and time on furfural yield in water-soluble DES/CPME pretreatment process was firstly evaluated. A maximum furfural yield of 80.6 % was attained in 10 min at 150 °C with choline chloride (ChCl)/citric acid monohydrate (CAM)/CPME system containing 30 wt% water and 2.5 wt% SnCl4·5H2O, which was higher than that obtained from ChCl/CAM/CPME system without water (55.5 %) and H2O/CPME system (49.7 %). These results demonstrated that the water-soluble DES/CPME system was a powerful method enhancing the furfural production. Under the optimal pretreatment conditions, the delignification and glucose yield were reached to 72.7 % and 94.3 %, respectively. The extracted lignin showed low molecular weight and ß-aryl-ether was obviously cleaved. Additionally, water-soluble DES/CPME pretreatment led to a significant removal of hemicelluloses (100.0 %) and lignin (72.7 %) and introduced morphological changes on cell walls, especially from the cell corner (CC) and secondary wall (SW) layers. Overall, this work proposed a practical one-step fractionation strategy for co-producing furfural, lignin and fermentable sugar, providing a way to biorefinery.

Regulating phenol tar in pyrolysis of lignocellulosic biomass: Product characteristics and conversion mechanisms.

The utilization of biomass pyrolysis is a crucial approach for sustainable development. This study used the typical biomass of pine (PI), rice husk (RH), and corn straw (ST) as feedstocks to evaluate the pyrolysis mechanisms, features and conversion mechanisms of the phenol tar product. The phenolic gaseous products were more trailing in ST, which mostly concentrated around 320-500 °C. Primary phenol tar is produced from lignin through the homolytic cleavage of ß-O and α-O, and C-C bond breakage, primarily occurring before 550 °C. As the degree of aromatization increases, the oxygenates progressively deoxygenate, and the primary tar demethoxylates to form secondary tar as the temperature increases. The pyrolysis of cellulose produces H radicals, which aid the transformation of lignin into phenol tar. This study can provide a theoretical basis for biomass pyrolysis to select the appropriate process parameters to improve the quality of bio-oil and regulate phenol tar products.

Functional characterization of WsPR-1 reveals its interplay with cytokinin and gibberellin signaling pathways.

Pathogenesis-related protein 1 (PR-1) is an antimicrobial protein involved in systemic acquired resistance (SAR) in plants, but its regulatory role and interactions with other pathways remain unclear. In this study, we functionally characterize WsPR-1 gene of Withania somnifera in Nicotiana tabacum to elucidate its role in plant defense, growth, and development. Interestingly, transgenic tobacco plants with increased levels of cytokinin (CK) and decreased gibberellins (GAs) exhibited stunted shoot growth, an underdeveloped root system, modified leaf morphology, reduced seed pod production, and delayed leaf senescence. Transcriptional analysis revealed that WsPR-1 overexpression downregulated the GA 20-oxidase (GA20ox) gene involved in GA biosynthesis while upregulating GA 2-oxidase (GA2ox), a GA catabolic enzyme. Moreover, transcript levels of FRUITFULL (FUL) and LEAFY (NFL2) flowering genes exhibited a decrease in WsPR-1 plants, which could explain the delayed flowering and reduced seed pod development in transgenic plants. Confocal microscopy confirmed increased lignin deposition in stem cross-sections of WsPR-1 transgenic plants, supported by gene expression analysis and lignin content quantification. Additionally, our findings also suggest the involvement of Knotted1-like homeobox (KNOX) gene in enhancing cytokinin levels. This study highlights PR-1's regulatory role in plant growth and development, with potential to boost crop yields and enhance resilience.

Formation of Nanodiamonds during Pyrolysis of Butanosolv Lignin.

The preparation of artificial diamonds has a long history driven by decreased costs compared to naturally occurring diamonds and ethical issues. However, fabrication of diamonds in the laboratory from readily available biomass has not been extensively investigated. This work demonstrates a convenient method for producing nanodiamonds from biopolymer lignin at ambient pressure. Lignin was extracted from Douglas Fir sawdust using a butanosolv pretreatment and was pyrolyzed in N2 at 1000 °C, followed by a second thermal treatment in 5% H2/Ar at 1050 °C, both at ambient pressure. This led to the formation of nanodiamonds embedded in an amorphous carbon substrate. The changes occurring at various stages of the pyrolysis process were monitored by scanning electron microscopy, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy. High resolution transmission electron microscopy revealed that nanodiamond crystallites, 4 nm in diameter on average, formed via multiple nucleation events in some carbon-containing high density spheres. It is proposed that highly defected graphene-like flakes form during the pyrolysis of lignin as an intermediate phase. These flakes are more deformable with more localized π electrons in comparison with graphene and join together face-to-face in different manners to form cubic or hexagonal nanodiamonds. This proposed mechanism for the formation of nanodiamonds is relevant to the future fabrication of diamonds from biomass under relatively mild conditions.

In-Depth Investigation of Role of -BCO2 in the Degradation of Sulfamethazine by Metal-Free Biochar/Persulfate: The Mechanism of Occurrence of Nonradical Process.

The remediation of organic wastewater through advanced oxidation processes (AOPs) based on metal-free biochar/persulfate systems has been extensively researched. In this work, boron-doped alkali lignin biochar (BKC1:3) was utilized to activate peroxymonosulfate (PMS) for the removal of sulfamethazine (SMZ). The porous structure and substantial specific surface area of BKC1:3 facilitated the adsorption and thus degradation of SMZ. The XPS characterization and density functional theory (DFT) calculations demonstrated that -BCO2 was the main active site of BKC1:3, which dominated the occurrence of nonradical pathways. Neither quenching experiments nor EPR characterization revealed the generation of free radical signals. Compared with KC, BKC1:3 possessed more electron-rich regions. The narrow energy gap (ΔEgap = 1.87 eV) of BKC (-BCO2) promoted the electron transfer to the substable complex (BKC@PMS*) on SMZ, driving the electron transfer mechanism. In addition, the adsorption energy of BKC(-BCO2)@PMS was lower (-0.75 eV → -5.12 eV), implying a more spontaneous adsorption process. The O-O (PMS) bond length in BKC(-BCO2)@PMS increased significantly (1.412 Š→ 1.481 Å), which led to the easier decomposition of PMS during adsorption and facilitated the generation of 1O2. More importantly, a combination of Gaussian and LC-MS techniques was hypothesized regarding the attack sites and degradation intermediates of the active species in this system. The synergistic T.E.S.T software and toxicity tests predicted low or even no toxicity of the intermediates. Overall, this study proposed a strategy for the preparation of metal-free biochar, aiming to inspire ideas for the treatment of organic-polluted wastewater through advanced oxidation processes (AOPs).

Lignin and green solvent extracted phenolic compounds from date palm leaves as functional ingredients for the formulation of soy protein isolate biocomposite packaging materials: A circular packaging concept.

The current study investigated valorization of lignin nanoparticles (LNPs) and phenolic compounds loaded in chitosan (DLECNPs) extracted from date palm leaves into the soy protein isolate (SPI) biocomposite films. The mechanical, structural, barrier, physiochemical, thermal, optical, antioxidant, and antimicrobial properties of the formulated composite films were investigated. The findings showed that the incorporation of DLECNPs into the SPI films significantly improved the film's antioxidant properties by >3 times and showed antibacterial inhibition zone in the range of 10-15 mm against six pathogenic bacteria. Further, incorporating LNPs into SPI-DLECNPs films notably improved the mechanical properties from 4.32 MPa and 29.27 % tensile strength and elongation at break, respectively to 10.13 MPa and 54.94 %, the water vapor permeability from 7.38 g/Pa s m to 5.59 g/Pa s m, and the antibacterial inhibition zone from a range of 10.2 mm to 15.0-21.5 mm as well as making the films more heterogeneous and stronger than control SPI film. Moreover, LNPs changed the initial films' color from light yellow to dark red and reduced the films' transparency. The results indicated that LNPs reinforced SPI composite films showed significant improvements in several properties and thus can be used as a potential ingredient for formulation of biodegradable packaging films.

Hydrophobic, ultraviolet radiation-shielding, and antioxidant functionalities of TEMPO-oxidized cellulose nanofibril film coated with modified lignin nanoparticles.

In this study, lignin nanoparticles (LN) and octadecylamine-modified LN (LN-ODA) were utilized as coating materials to enhance the hydrophobic, antioxidant, and ultraviolet radiation-shielding (UV-shielding) properties of a TEMPO-oxidized nanocellulose film (TOCNF). The water contact angle (WCA) of the TOCNF was approximately 53° and remained stable for 1 min, while the modified LN-ODA-coated TOCNF reached over 130° and maintained approximately 85° for an hour. Pure TOCNF exhibited low antioxidant properties (4.7 %), which were significantly enhanced in TOCNF-LN (81.6 %) and modified LN-ODA (10.3 % to 27.5 %). Modified LN-ODA-coated TOCNF exhibited antioxidant properties two to six times higher than those of pure TOCNF. Modified LN-ODA exhibited thermal degradation max (Tmax) at 421 °C, while pure LN showed the main degradation temperature at approximately Tmax 330 °C. The thermal stability of TOCNF-LN-ODA-coated materials remained consistent with that of pure TOCNF, while the crystallinity index of the sample showed a slight decrease due to the amorphous nature of the lignin structure. The tensile strength of TOCNF was approximately 114.1 MPa and decreased to 80.1, 51.3, and 30.3 MPa for LN-ODA coating at 5, 10, and 15 g/m2, respectively.

Quantitative and Structural Characterization of Native Lignin in Hardwood and Softwood Bark via Solid-State NMR Spectroscopy.

A major factor limiting bark's industrial use is its greater recalcitrance compared to wood. While lignin is widely recognized as a significant contributor, precise characterization of lignin in bark remains sparse, presenting a crucial gap that impedes understanding of its impact. In this study, we employed advanced solid-state nuclear magnetic resonance (NMR) spectroscopy to analyze bark samples from various species, including willow, poplar, and pine. We established and verified that lignin methoxy peak at 56 ppm serves as a reliable quantitative metric to assess lignin content, with which we calculated the lignin contents in bark are significantly reduced by more than 70% compared to those in wood. Furthermore, in situ characterization revealed significant reduction of ß-ether linkage in bark lignin across species, revealing a more condensed and resistant structural configuration. Our results have substantially advanced our comprehension of the composition and structure of native lignin in tree bark.

Formation of the emerging disinfection byproducts halocyclopentadienes from phenolic compounds after chlorination.

Halocyclopentadienes (HCPDs) are an emerging class of alicyclic disinfection by-products (DBPs) with high toxicity in disinfected drinking water. However, their potential precursors remain unclear, which hinders the understanding of their formation and further development of control strategies. In this study, two HCPDs, 1,2,3,4-tetrachloro-1,3-cyclopentadiene (TCC) and 1,2,3,4,5,5-hexachloro-1,3-cyclopentadiene (HCC), were identified in chlorinated lignin and tannic acid samples for the first time. The chlorination of four lignin-like and two tannic-like phenolic model compounds confirmed that guaiacol and digallic acid can produce HCPDs. According to their structures, ortho-substituents of phenolic compounds were speculated to be crucial for HCPDs formation. The simulated disinfection of catechol, 2-ethoxyphenol (2-EOP), 2-propoxyphenol (2-POP) and 3,4-dihydroxy-5-methoxybenzoic acid (DH-5-MBA) with different ortho-substituents demonstrated that three of these compounds can generate HCPDs, except catechol, which further indicates that ortho-substituents, such as the methoxy, ethoxy and propoxy groups, contribute to HCPDs generation. Guaiacol was the simplest compound for generating HCPDs, and possible formation pathways during chlorination were proposed. Seven hydroxy-chlorocyclopentadienes were tentatively identified and are likely important intermediates of HCPDs formation. Additionally, TCC and HCC were confirmed in tap water and chlorinated SRNOM samples with total concentrations up to 11.07 ng/L and 65.66 ng/L, respectively, further demonstrating the wide existence of HCPDs and their precursors. This study reports the clear precursors of HCPDs and provides a theoretical foundation for controlling HCPDs formation in disinfected drinking water.

Construction of a hollow heterojunction interface to accelerate the photocatalytic cleavage of lignin Cß-O bonds.

Photocatalytic splitting of the Cß-O bond is regarded as a prospective strategy for transforming lignin, and it is imperative to develop novel photocatalysts with effective photogenerated charges separation and solar absorption capacity. Herein, a novel hollow ZIF-8/CdS heterostructure photocatalyst was synthesized for the catalytic splitting of lignin Cß-O bonds. The photocatalytic cleavage rate of Cß-O bond of ligin ß-O-4 reached 30.3∙mmol∙h-1∙g-1 within 20 min under visible light exposure. It is noteworthy that the utilization of intricate natural lignin molecules in this photocatalytic system has yielded successful depolymerization. The DFT and XPS results indicate a potential unidirectional electron migration from ZIF-8 to CdS in ZIF-8/CdS composites transfer. This electron transport path follows the direct Z-scheme heterostructure mechanism, resulting in the generation of an internal electric field between ZIF-8 and CdS. Impressively, the synergistic combination of the hollow structure and Z-scheme heterostructure effectively enhances the efficiency of charge carrier separation and maintains a robust redox potential, thereby facilitating Cα-radical generation. This study proposes a novel photocatalyst design strategy that integrates hollow structures and Z-scheme heterojunctions, with the aim of targeting the depolymerization of the Cß-O bond in lignin.

Recent progresses in bentonite/lignin or polysaccharide composites for sustainable water treatment.

Today, with the growth of the human population, industrial activities have also increased. Different industries such as painting, cosmetics, leather, etc. have broadly developed, and as a result, they also produce a lot of pollutants. These pollutants can enter the environment and pollute water, air, and soil. Organic dyes, nitro compounds, drug residues, pesticides and herbicides are pollutants that should be removed from the environment. Natural polymers or biopolymers are important types of organic materials that are broadly applied for different applications. Among them, polysaccharides and lignin, which are two types of biopolymers, have attracted much consideration owing to their advantages such as biocompatibility, environmental friendly, safety, availability, etc. Polysaccharides include cellulose, gum, starch, alginate (Alg), chitin, and chitosan (CS). On the other hand, bentonite is one of the types of clays, which owing to their properties like large specific surface area, adsorption performance, naturally available, etc., have drawn the interest of many researchers. As a result, the synthesis of a composite including polysaccharide/lignin and bentonite can be very efficient for different applications, especially environmental ones. In this review, we instigated the preparation of these composites as well as the removal performance of them. In fact, we reported recent advancements in the synthesis of lignin- and polysaccharide-bentonite composites for the removal of diverse kinds of contaminants like organic dyes, nitro compounds, and hazardous materials.

Nanolignin-Facilitated Robust Hydrogels.

Recently, certain challenges and accompanying drawbacks have emerged in the preparation of high-strength and tough polymer hydrogels. Insights from wood science highlight the role of the intertwined molecular structure of lignin and crystalline cellulose in contributing to wood's strength. Herein, we immersed prestretched poly(vinyl alcohol) (PVA) polymer hydrogels into a solution of nanosized lignosulfonate sodium (LS), a water-soluble anionic polyelectrolyte, to creatively reconstruct this similar structure at the molecular scale in hydrogels. The nanosized LS effectively fixed and bundled the prestretched PVA polymers while inducing the formation of dense crystalline domains within the polymer matrix. Consequently, the interwoven structure of crystalline PVA and LS conferred good strength to the composite hydrogels, exhibiting a tensile strength of up to ∼23 MPa, a fracture strain of ∼350%, Young's modulus of ∼17 MPa, toughness of ∼47 MJ/m3, and fracture energy of ∼42 kJ/m2. This hydrogel far outperformed previous hydrogels composed directly of lignin and PVA (tensile strength <1.5 MPa). Additionally, the composite hydrogels demonstrated excellent antifreezing properties (<-80 °C). Notably, the LS-assisted reconstruction technology offers opportunities for the secondary fixation of PVA hydrogel shapes and high-strength welding of hydrogel components. This work introduces an approach for the high-value utilization of LS, a green byproduct of pulp production. LS's profound biomimetic strategy will be applied in multifunctional hydrogel fields.

Identification of key genes involved in lignin and flavonoid accumulation during Tilia tuan seed maturation.

KEY MESSAGE: Transcriptomics and phenotypic data analysis identified 24 transcription factors (TFs) that play key roles in regulating the competitive accumulation of lignin and flavonoids. Tilia tuan Szyszyl. (T. tuan) is a timber tree species with important ecological and commercial value. However, its highly lignified pericarp results in a low seed germination rate and a long dormancy period. In addition, it is unknown whether there is an interaction between the biosynthesis of flavonoids and lignin as products of the phenylpropanoid pathway during seed development. To explore the molecular regulatory mechanism of lignin and flavonoid biosynthesis, T. tuan seeds were harvested at five stages (30, 60, 90, 120, and 150 days after pollination) for lignin and flavonoid analyses. The results showed that lignin accumulated rapidly in the early and middle stages (S1, S3, and S4), and rapid accumulation of flavonoids during the early and late stages (S1 and S5). High-throughput RNA sequencing analysis of developing seeds identified 50,553 transcripts, including 223 phenylpropanoid biosynthetic pathway genes involved in lignin accumulation grouped into 3 clusters, and 106 flavonoid biosynthetic pathway genes (FBPGs) grouped into 2 clusters. Subsequent WGCNA and time-ordered gene co-expression network (TO-GCN) analysis revealed that 24 TFs (e.g., TtARF2 and TtWRKY15) were involved in flavonoids and lignin biosynthesis regulation. The transcriptome data were validated by qRT-PCR to analyze the expression profiles of key enzyme-coding genes. This study revealed that there existed a competitive relationship between flavonoid and lignin biosynthesis pathway during the development of T. tuan seeds, that provide a foundation for the further exploration of molecular mechanisms underlying lignin and flavonoid accumulation in T. tuan seeds.

Functional analysis of two caffeoyl-coenzyme 3 a-o-methyltransferase involved in pear lignin metabolism.

Caffeoyl-coenzyme 3 A-O-methyltransferase (CCoAOMT) plays a crucial role in the lignin synthesis in many higher plants. In this study, nine PbCCoAOMT genes in total were identified from pear, and classified into six categories. We treated pear fruits with hormones abscisic acid (ABA) and methyl jasmonate (MeJA) and salicylic acid (SA) and observed differential expression levels of these genes. Through qRT-PCR, we also preliminarily identified candidate PbCCoAOMT gene, potentially involved in lignin synthesis in pear fruits. Additionally, the overexpression of PbCCoAOMT1/2 in Arabidopsis and pear fruits increased in lignin content. Enzymatic assays showed that recombinant PbCCoAOMT1/2 proteins have similar enzymatic activity in vitro. The Y1H (Yeast one-hybrid) and dual luciferase (dual-LUC) experiments demonstrated that PbMYB25 can bind to the AC elements in the promoter region of the PbCCoAOMT1 gene. Our findings suggested that the PbCCoAOMT1 and PbCCoAOMT2 genes may contribute to the synthesis of lignin and provide insights into the mechanism of lignin biosynthesis and stone cell development in pear fruits.

Lignin and functional polymer-based materials: Synthesis, characterization and application for Cr (VI) and As (V) removal from aqueous media.

In this study, lignin derived from corncobs was chemically modified by substituting the hydroxyl groups present in its structure with methacrylate groups through a catalytic reaction using methacrylic anhydride, resulting in methacrylated lignin (ML). These MLs were incorporated in polymerization reaction of the monomer 2-[(acryloyloxy)ethyl trimethylammonium] chloride (Cl-AETA) and Cl-AETA, Cl-AETA/ML polymers were obtained, characterized (spectroscopic, thermal and microscopic analysis), and evaluated for removing Cr (VI) and As (V) from aqueous media in function of pH, contact time, initial metal concentrations and adsorbent amount. The Cl-AETA/ML polymers followed the Langmuir adsorption model for the evaluated metal anions and were able to remove up to 91 % of Cr (VI) with a qmax (maximum adsorption capacity) of 201 mg/g, while for As (V), up to 60 % could be removed with a qmax of 58 mg/g. The results demonstrate that simple modifications in lignin enhance its functionalization and properties, making it suitable for removing contaminants from aqueous media, showing promising results for potential future applications.

Bio-bleaching of ankara pulp with xylanase-producing bacterial consortium for sustainable handmade paper production.

The paper industry faces two critical challenges: the scarcity of raw materials and the environmental impact of chemical waste pollution. Addressing the first challenge involves harnessing alternative, sustainable raw materials, while the second challenge can be mitigated through the adoption of bio-bleaching processes, which significantly reduce chemical consumption while enhancing paper brightness and quality. This study proposes a solution to both challenges by using non-woody Calotropis procera (Ankara) and a xylanase-producing microbial consortium for sustainable handmade paper production, a combination not extensively explored in prior research. To evaluate this approach, the process was divided into three stages. In stage I, Ankara fibre was pulped through open hot digestion. In stage II, the pulp was subjected to bio-bleaching in two experimental setups: Set I (without sucrose) and Set II (with sucrose) for 5 days. In stage III, chemical bleaching was used to improve the final brightness of the treated pulps. A novel comparison was made between the bio-bleaching efficiency of an individual isolate g5 (BI) and a bacterial consortium (BC). This research highlighted that bio-bleaching with the consortium effectively removed lignin (140±60 mg/l) and colour (1830±50 PCU), especially in the presence of sucrose, compared to using a single xylanase isolate. Pulp residue/filtrate collected at each stage was estimated based on parameters such as colour and lignin content. After stage III (chemical bleaching), the release of colour and lignin in pulp filtrate was higher in BI compared to BC, indicating the consortium's effectiveness during bio-bleaching, which leaves fewer degradable lignin structures for the chemical bleaching stage. Papers crafted from consortium-treated pulp also exhibited higher brightness than those treated with the isolate. This study reveals the synergistic effect of microbial consortia, leading to more efficient lignin degradation and enhanced bio-bleaching capabilities, supporting the development of greener industrial processes. Ultimately, this study demonstrates a unique and eco-friendly approach to papermaking, combining C. procera and enzymatic bio-bleaching to reduce dependency on hazardous chemicals and support sustainable industry practices.

Bio-based production of cis,cis-muconic acid as platform for a sustainable polymers production.

Production of the high industrial value cis,cis-muconic acid (ccMA) from renewable biomasses is of main interest especially when biological (green) processes are used. We recently generated a E. coli strain expressing five recombinant enzymes to convert vanillin (VA, from lignin) into ccMA. Here, we optimized a growing cell approach in bioreactor for the ccMA production. The medium composition, fermentation conditions, and VA addition were tuned: pulse-feeding VA at 1 mmol/h allowed to reach 5.2 g/L of ccMA in 48 h (0.86 g ccMA/g VA), with a productivity 4-fold higher compared to the resting cells approach, thus resulting in significantly lower E-factor and Process Mass Intensity green metric parameters. The recovered ccMA has been used as building block to produce a fully bioderived polymer with rubber-like properties. The sustainable optimized bioprocess can be considered an integrated approach to develop a platform for bio-based polymers production from renewable feedstocks.

A solar-driven nanocellulose Janus aerogel with excellent floating stability and dual functions of oil-water separation and photocatalytic degradation of organic pollutants.

Effective and practical cleanup of viscous crude oil spills is extremely important in real harsh marine environments. Herein, we designed a solar-driven, nanocellulose-based Janus aerogel (Janus-A) with excellent floating stability and dual function of oil-water separation and degradation of aqueous organic pollutants. Janus-A, with its amphiprotic nature, was prepared through polypyrrole (PPy) deposition, freeze-drying, octyltrichlorosilane (OTS) impregnation, TiO2 spraying on the bottom surface, and UV irradiation treatment. The photothermal conversion effect of PPy coating raised the surface temperature of aerogel to 75.8 °C within 6 min under one simulated solar irradiation, which greatly reduced the viscosity of the crude oil and increased the absorption capacity of the aerogel to 36.7 g/g. Benefiting from the balance between the buoyancy generated by the hydrophobic part and water absorption of the hydrophilic part, Janus-A showed excellent floating stability under simulated winds and waves. In addition, Janus-A exhibited high degradation efficiency for organic pollutants in water owing to the synergistic photocatalytic properties of TiO2 and PPy. These excellent performances make Janus-A ideal for integrated water-oil separation and water remediation.

Lignin-based vitrimer containing dynamic borate ester bonds with intrinsic photoconversion and excellent photothermal remoldability.

The development of photoresponsive shape memory materials based on the photothermal conversion properties of lignin and the low activation energy of the dynamic covalent borate bond is of great importance. In this paper, a kind of lignin-based vitrimer polymer (LBP) containing dynamic boronic ester bonds was prepared by a "sulfhydryl-epoxy" click reaction and etherification reaction. The results show that the rigid segment EP-EL (lignin-based epoxy resin) and BDB (2,2'-(1,4-phenylene)-bis-[4-mercapto-1,3,2-dioxaneborane]) with benzene ring structure can impart tensile strength (20.8 MPa) to the LBP, while the flexible segment PEG imparts good elongation at break (15 %). The dynamic binding and dissociation exchange mechanism of the boronic ester bonds enables LBP to exhibit thermal remodelling properties (up to 36.2 %) and water-assisted self-healing properties at room temperature (up to 49.0 %). In addition, LBP exhibits excellent thermal and light-responsive shape memory properties due to its own photothermal conversion performance (photothermal conversion efficiency up to 18.2 %) and the dynamic boronic ester bond thermal activation bond exchange mechanism. The insulating properties of LBP make it suitable for use in high temperature protection circuit devices and light-responsive circuit devices. This study provides new insights into the design and application of Vitrimer and photoresponsive shape memory polymers, and also offers a new avenue for high-value utilization of lignin.