Efficient fractionation of lignocellulosic components is essential for sustainable biomass valorization. Herein, a visible-light-assisted ionic liquid (IL) composite system composed of 30% 2-hydroxy-N-(2-hydroxyethyl)-N-methylethanaminium methanesulfonate ([BHEM]mesy) and 70% ethylene glycol, containing 0.1 wt% photocatalyst g-C3N4, was developed to achieve low temperature photothermal fractionation of corn stalk. The IL provides protonic sites and hydrogen-bonding capability for lignin solubilization, while the dispersed photocatalyst absorbs light energy to accelerate mass transfer and enhance solvation selectivity between lignin and cellulose. Under the optimized conditions (80 ℃, 4 h), 83.03% of lignin is removed while 84.68% of cellulose is retained. The regenerated lignin exhibits reduced molecular weight, while the purified cellulose phase enables aerogel fabrication. Compared to conventional hydrothermal pretreatment, visible-light coupling enhances the pretreatment process, reduces the reaction temperature and maintains cellulose crystallinity, confirming its superior pretreatment efficiency. This study establishes an integrated photothermal biomass fractionation strategy that offers a novel and highly efficient method for biomass utilization.
To overcome the economic bottlenecks of second-generation biorefineries, this study develops a full-component valorization platform for sugarcane bagasse (SCB). Utilizing a mild triethylene glycol (TEG)/water alkaline pretreatment, SCB was efficiently fractionated into active lignin, oligosaccharides, and ethanol. Crucially, the process was validated at a 1,000-tonne pilot scale, achieving 90.2% cellulose retention and 95.3% oligosaccharide recovery. This pilot performance underpinned a commercial simulation for processing one million tonne annually. The subsequent techno-economic analysis (TEA) revealed a total capital investment of CNY 5,233.72 million ($747.67 million) with a 10-year payback period. Significantly, high-value oligosaccharides accounted for 78.2% of total revenue, demonstrating a decisive shift away from ethanol-dependent models. Sensitivity and Monte Carlo analyses further confirmed the project’s financial robustness against market fluctuations. This research provides a rigorously validated industrial blueprint, establishing a new techno-economic benchmark for sustainable, high-profit agro-industrial residue valorization.
Photocatalysis is a green, mild, efficient and promising advanced oxidation technology. Lignin biomass, as a natural aromatic biomass resource, is difficult to be effectively utilized due to its complex structure, resulting in a huge waste of biomass resources. Utilizing photocatalytic technology to depolymerize lignin into small molecular aromatic compounds is a new way for economic, green and sustainable high-value utilization of biomass resources. MgIn2S4, as a ternary metal sulfide based on indium, has advantages such as visible light responsiveness, tunable structure and chemical stability. However, the carrier recombination rate of a single MgIn2S4 photocatalyst is relatively high, requiring optimization and modification. In this paper, by using carbon quantum dots as a co-catalyst and adopting the strategy of constructing heterojunction loading, the photocatalytic performance of MgIn2S4 was optimized. Firstly, a series of binary heterojunction Nb2O5/MgIn2S4 (named yN/MIS, where y is the molar ratio of Nb to Mg) photocatalysts were prepared, and the optimal composite ratio of Nb/Mg was determined to be 0.25 through photocatalytic performance tests. Then, a series of ternary heterojunction Nb2O5/ N-CQDs/MgIn2S4 (named 0.25 N/zC/MIS, where z is the loading amount of N-CQDs) photocatalysts were prepared. The results of photocatalytic performance tests confirmed that the optimal loading amount of N-CQDs was 0.4%. The optimized photocatalyst could degrade 77.8% of sodium lignin sulfonate (SLS) within 150 min. After three consecutive photocatalytic cycles, the degradation rate of SLS by the 0.25 N/0.4%C/MIS composite material remained at 74.2%, and the crystal structure of the 0.25 N/0.4%C/MIS composite material did not undergo any significant changes after three consecutive photocatalytic cycle tests. This result can prove that the crystal structure of the 0.25 N/0.4%C/MIS composite material is relatively stable. The decomposition products were analyzed by GC-MS tests. By comparing the total ion current graph with the NIST database, it can be known that the main products of photocatalytic decomposition include aromatic hydrocarbons, benzyl alcohol, phenols and phthalates, etc.
Efficient lignin valorization into high-performance materials is hindered by cleavage of β–O–4 linkages and condensation during acidic fractionation. Here, an amino acid–assisted molecular design using histidine and aspartic acid stabilizes and functionalizes dilute-acid sugarcane bagasse lignin, enabling integrated conversion into functional carbon materials and reinforced three-dimensional (3D)-printed poly(lactic acid) (PLA) composites. Structural and interfacial analyses showed that histidine produced a less-condensed, β–O–4-rich lignin structure, with the β–O–4 content increasing from 35.8/100 Ar in unmodified dilute-acid lignin to 49.3/100 Ar in histidine-lignin and 43.6/100 Ar in aspartic acid-lignin, while condensed S-unit content decreased from 6.3
Alkaline-surfactant pretreatment effectively fractionates lignocellulose but commonly requires high chemical/ thermal severity and can promote lignin repolymerization, limiting downstream lignin valorization. Here, we integrate choline chloride into a NaOH/Triton-X 100 system to enable efficient sugarcane bagasse (SCB) deconstruction at reduced severity while producing a more reactive, less-condensed lignin. Relative to the salt-free benchmark, choline chloride enabled effective selective fractionation at a lower NaOH charge (3.0 vs 4.5 g per 10 g dry SCB) and lower temperature (150 vs 175 degrees C), improving carbohydrate preservation while maintaining substantial delignification. This improved substrate accessibility supported enzymatic hydrolysis at 50% lower enzyme loading than the salt-free benchmark (3.0 vs 6.0 FPU g-1), while increasing monomeric sugar production to 211 g glucose and 53 g xylose per kg SCB. Two-dimensional HSQC NMR showed that choline chloride suppressed lignin condensation and preserved ether linkages, yielding ether-rich lignin (beta-O-4: 27.4 per 100 Ar; beta-O-4 ': 12.9 per 100 Ar) with low condensed S-unit content (4.1%). Density functional theory further indicated that Triton-X 100 limits fragment re-association and chloride-rich ionic environments stabilize reactive intermediates, collectively disfavoring repolymerization. Upon pyrolysis, choline chloride-derived lignin produced 52.7% bio-oil, enriched in phenolic aromatics (e.g., phenol and syringol), and a porous biochar with high surface area (357.1 m2 g-1). Overall, the integrated process increases carbohydrate utilization while upgrading lignin into renewable aromatics and value-added carbon materials.
Sugarcane bagasse (SCB) represents a typical biomass resource, with China producing approximately 33 million tons annually. This study explored an integrated biorefinery process that converts SCB into value-added biofuels and co-products, incorporating a surfactant-tailored glycerol organosolv pretreatment, high-solids enzymatic hydrolysis, and lignin pyrolysis for valorization. The Triton-X 100-tailored glycerol pretreatment achieved a favorable trade-off between component selectivity and subsequent enzymatic hydrolyzability of substrates, resulting in 91.7% cellulose retention and 81.8% hemicellulose retention, along with 75.3% delignification. Encouragingly, the easily hydrolyzable substrates released 230.2 g L-1 of fermentable sugars from 30% (w/v) high-solids enzymatic hydrolysis at a low enzyme loading of 5 FPU g-1 in combination with surfactants and auxiliary enzymes. Thereafter, the fed-batch co-fermentation of these fermentable sugars yielded 102.2 g L-1 of ethanol, corresponding to 0.25 g of ethanol per gram of raw biomass. In addition to ethanol production, lignin valorization resulted in a bio-oil yield of 54.3%, with phenolic compounds accounting for 66.1% of the bio-oil. The biochar yield was 30.7%, exhibiting a surface area of 274.9 m2 g-1 and a pore size of 3.89 nm. A well-to-wheel environmental assessment of the refinery process revealed that for each ton of SCB processed, 247.9 kg of ethanol, 121.2 kg of bio-oil, and 68.5 kg of biochar were produced, emitting 1213.82 kg of CO2-eq. The process reduced greenhouse gas emissions by 400.98 kg CO2-eq. per ton of SCB, resulting in a reduction in the social cost of carbon emission by US$18.58 per ton. These findings demonstrate that the integrated biorefinery not only enhances the production of ethanol and co-products but also offers significant environmental benefits through the valorization of SCB into high-value products.
Nanozymes are powerful alternatives to natural enzymes, yet the sustainable design of hydrolase nanozymes using renewable ligands remains underexplored. Lignin, as an abundant aromatic biopolymer, offers a promising and green ligand for constructing sustainable nanozymes. In this work, a Ce-doped lignin-based hydrolase nanozyme (Ce-AL) is synthesized using Ce ions coordinated with aminated industrial lignin. The resulting Ce-Nx centered Ce-AL enable the hydrolysis of phosphate esters and even stable protein amide bonds. Notably, the hydrolase-like activity of Ce-AL at 100°C is 2.03 times that at 40°C, attributable to the thermally optimized Ce-Nx sites within the protective lignin scaffold. The Ce-AL effectively combats stubborn biofilms formed by Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria by selectively hydrolyzing key proteinaceous and nucleotide components of the extracellular polymeric substances and bacterial cell walls. This work highlights lignin as a renewable platform for designing advanced, stimuli-responsive nanozymes.
In this study, nitrogen doped carbon quantum dots (NLCQDs) were synthesized by hydrothermal method using alkaline lignin as the carbon source and ethylenediamine as the nitrogen source. Subsequently, a BiOCl/WO3 heterojunction was constructed through a solvothermal approach. By optimizing the molar mass ratio of BiOCl to WO3, BiOCl/WO3-2 composite (BiOCl: WO3 = 5:1) was proved to possess the best catalytic activity. When BiOCl, WO3 and NLCQDs jointly construct the ternary composite catalytic system BiOCl/WO3-2/NLCQDs-Z (Z is the loading amount of NLCQDs, Z = 5, 10, 15 mL), the catalytic activity is significantly improved. Using CO yield as the indicator, BiOCl/WO3-2/NLCQDs-10 was determined to have the best photocatalytic activity. TEM and XPS measurements show that a Z-type heterojunction is formed between BiOCl and WO3, and a built-in electric field is established at the interface. BiOCl/WO3-2/NLCQDs-10 maintained stable catalytic activity for CO2 reduction within 3 h, with a final CO yield of 47.02 mu mol center dot g- 1 center dot h- 1, which was 13.3 and 4.2 times higher than BiOCl and BiOCl/WO3-2, respectively. In this study, the separation and transfer path of photo-generated charge were optimized by reasonably constructing BiOCl composite catalytic system, and the photocatalytic performance of CO2 reduction was significantly improved.
Monensin, a polyether ionophore antibiotic produced by Streptomyces cinnamonensis, is widely used in the livestock industry. To address the yield bottleneck caused by insufficient intracellular reducing power (NADPH/NADH) during industrial fermentation, we employed a multi-pathway collaborative metabolic engineering strategy. We fused the genes zwf (encoding glucose-6-phosphate dehydrogenase) and gnd (encoding 6-phosphogluconate dehydrogenase) from the pentose phosphate pathway with fadB (encoding 3-hydroxyacyl-ACP dehydratase) from the fatty acid β-oxidation pathway to construct a synthetic expression cassette. This cassette was cloned into the integrative vector pSET152 under the control of the strong ermE promoter and fd terminator and then introduced into S. cinnamonensis SDSL6002 (WT) via intergeneric conjugation, yielding the recombinant strain S-zwf-gnd-fadB. Shake-flask fermentation demonstrated that the engineered strain achieved the intracellular NADPH/NADH level 1.8 folds of that in the wild type, with a monensin titer of 22.6 g/L (a 51.7% increase). The yield remained stable after five generations of antibiotic-free subculturing. Further scale-up validation in 50 L and 5 m3 industrial fermenters demonstrated that the engineered strain achieved monensin titers of 37.2 g/L and 40.4 g/L, which represented 16.3% and 18.8% improvements, respectively, over that of the control strain. These results highlight the exceptional scalability and industrial production potential of the engineered strain. This study establishes a multi-gene co-expression system to reinforce the reducing power network, providing a high yield engineered strain and a feasible metabolic engineering approach for industrial biosynthesis of monensin.
Monensin is a polyether antibiotic produced by Streptomyces cinnamonensis. Due to its highly complex biosynthetic pathway, incomplete characterization of key biosynthetic genes has long hindered improvements in industrial-scale monensin production. Based on our previous transcriptomic analysis that key genes involved in monensin biosynthesis were initially identified in a high-yield S. cinnamonensis strain, this study focused on metabolic engineering of this strain through multi-gene integration strategy, targeting primary metabolism, precursor synthesis, ATP supply, stress resistance, and the monensin biosynthetic gene cluster. Results demonstrated that the co-expression of phosphofructokinase (pfk), citrate synthase (cs), methylmalonyl-CoA mutase subunit (3 (mutB), and methylmalonyl-CoA mutase (mcm) rendered the monensin titer from 12.6 g/L to 20.2 g/L, an approximately 60 % increase compared with the original strain. Co-expression of the ATP synthase (3 subunit (ass beta), the fungal thiol-coupled enzyme (mac), and the monensin biosynthetic enzyme (monE) allowed the monensin production from 12.6 g/L to 19.4 g/L, corresponding to an increase of above 50 %. Furthermore, simultaneous co-expression of the seven genes using the novel pKHBT1 system increased the monensin titer to 26.2 g/L in a 5-L fermenter, more than double that of the original strain. These newly identified key metabolic genes were indeed associated closely with the monensin biosynthesis in S. cinnamonensis, which supplied a clue to metabolic engineering of the monensin production strain for efficient biosynthesis.
In this study, lignin-based carbon quantum dots (CQDs) were prepared by a one-step hydrothermal method using alkaline lignin as the carbon source and then further combined with ZnIn2S4 photocatalyst to construct a series of CQDs-X/ZnIn2S4 composite photocatalyst. The experimental results indicated that when the loading amount of CQDs was 20 mL, the composite material exhibited the best photocatalytic hydrogen production performance. Structural characterization revealed that CQDs with a size of 4–6 nm were successfully modified on the surface of flower-like ZnIn2S4 photocatalyst microspheres assembled by nanosheets, forming a tight heterostructure. Optical and electrochemical tests confirmed that the introduction of CQDs effectively broadened the light absorption range, adjusted the band structure and significantly promoted the separation and transfer of photogenerated carriers, while reducing the charge recombination rate. In addition, compared with pure ZnIn2S4 (48.18 m2·g−1), CQDs-20/ZnIn2S4 has a relatively larger specific surface of 79.33 m2·g−1, providing more active sites. This study demonstrated that the composite strategy based on lignin CQDs could significantly enhance the photocatalytic performance of ZnIn2S4 photocatalyst, providing an effective approach for the high-value utilization of lignin and solar hydrogen production.
Inhibitory compounds generated during the acidic pretreatment of lignocellulose (carbohydrate-and lignin-derived byproducts) hinder enzymatic hydrolysis by forming pseudo-lignin and restricting enzyme access to substrate. Enhancing (hemi)cellulase tolerance to these inhibitors could improve hydrolysis efficiency and reduce the need for costly detoxification steps. This study investigates the role of amino acids with diverse physicochemical properties in mitigating these effects, with a particular focus on histidine. Our findings show that charged amino acids-histidine (His), arginine (Arg), aspartic acid (Asp), and glutamic acid (Glu)-were most effective in improving glucose yields, which increased to over 60 % after 48 h of hydrolysis, compared to 46.7 % in the control. These amino acids also reduced pseudo-lignin formation, decreasing lignin content from 35.7 % to 21-25 %. His exhibited the highest inhibitor removal efficiency (91.2 %), followed by Asp (88.4 %), Glu (86.9 %), and Arg (86.5 %). In-depth in vitro and in silico analyses revealed that His's imidazole side chain facilitated multiple synergistic interactions, including electrostatic interactions, hydrogen bonding, pi-pi stacking, and van der Waals forces, contributing to its superior binding characteristics. His demonstrated the highest binding constant (Ka: 69.18) and the most negative free energy (Delta G:-11.4), enhancing the stability of inhibitor-enzyme complexes. These findings position histidine as a promising candidate for engineering next-generation (hemi)cellulases with enhanced inhibitor resistance, thereby improving the efficiency of lignocellulose conversion in sustainable biorefineries.
A light-responsive biohybrid system was constructed by coupling graphitic carbon nitride (g-C3N4) with Lactobacillus reuteri to enhance 1,3-propanediol (1,3-PDO) biosynthesis. Under simulated sunlight, the g-C3N4/L. reuteri biohybrid system achieved a 1,3-PDO titer of 11.3 g/L within 48 h in synthesis medium, representing a 66 % increase compared to dark controls (6.8 g/L). Characterization results confirmed strong interfacial coupling and efficient electron transfer between the photocatalyst and microbial cells. Notably, the light-driven biohybrid system increased the intracellular NADH/NAD+ ratio and ATP levels by 98.3 % and 378.5 %, respectively, highlighting its ability to regulate redox balance and promote energy metabolism. Furthermore, the hybrid system was further applied using enzymatic hydrolysate of glycerol-pretreated hemp straw as the sole carbon source, replacing the synthesis medium. Impressively, the illuminated biohybrid system still achieved a 1,3-PDO titer of 9.6 g/L, significantly outperforming the non-illuminated control (5.9 g/L). Overall, this study demonstrates the feasibility of using g-C3N4-assisted biohybrid systems to enhance microbial bioconversion, especially with enzymatic lignocellulosic hydrolysates, offering a sustainable route for value-added chemical production by integrating biomass and solar energy.
The dense and recalcitrant structure of poplar biomass presented a major obstacle to efficient lignin-carbohydrate separation in biphasic pretreatment systems. In this study, environmentally friendly physical and chemical preprocessing strategies for poplar-freeze-thaw and hydrogen peroxide (H2O2) pre-oxidation-were employed to enhance the fractionation performance of an acid/pentanol biphasic system. Freeze-thaw physically disrupted the compact cell wall matrix of poplar, increasing porosity and acid accessibility, resulting in hemicellulose and lignin removal rates increasing from 88.1% and 78.5% (only acid/pentanol pretreatment) to 89.2-89.4% and 85.2-84.8%, respectively. H2O2 pre-oxidation showed superior performance by initiating oxidative cleavage of lignin-carbohydrate linkages (benzyl ether and ester) and depolymerizing native lignin via disruption of beta-beta and beta-5 interunit bonds. These structural modifications reduced lignin condensation, enhanced hydrophilicity, and facilitated subsequent solvent penetration. As a result, hemicellulose removal and delignification reached 92.6% and 90.2%, respectively, while cellulose saccharification efficiency increased to 89.1%. Moreover, the lignin recovered from the organic phase was enriched in phenolic and carboxylic groups, exhibiting enhanced antioxidant capacity. These findings deepened the mechanistic understanding of how oxidative and physical preprocessing facilitated subsequent biomass fractionation and presented a green, modular strategy with strong industrial potential for scalable lignocellulosic biorefinery applications.
Fluorinated compounds and long-chain aliphatic substances are commonly utilized in fabricating superhydrophobic coatings. However, their ecological hazards and lack of long-term stability hinder widespread adoption. In this study, a strategy for synthesizing fully bio-based hydrophobic nanoparticles-rosin-grafted chitosan nanoparticles (RCS)-was developed. Based on these nanoparticles, an innovative superhydrophobic cotton fabric (denoted as RCS-SR@PCF) was successfully fabricated. The modified fabric displayed remarkable water-repellent characteristics, evidenced by a water contact angle of 157.4 +/- 1.2 degrees and a sliding angle of 5.2 +/- 0.2 degrees. Moreover, the RCS-SR@PCF achieved efficient oil/water separation solely under gravitational force, exhibiting both high permeability and separation efficacy. Specifically, the oil flux attained a value of 7782.64 L.m-2.h-1, accompanied by a separation efficiency of 97.48 %. Impressively, following consecutive reuse cycles, the fabric maintained a separation efficiency of 97.43 % for viscous water/oil mixtures, with a flux equal to 7147.43 +/- 106.89 L.m-2.h-1. Furthermore, the superhydrophobicity, self-cleaning function, and water/oil separation capability of the coating remained stable under harsh conditions, including mechanical abrasion, saline water immersion, high temperatures, and organic solvent attacks. Overall, these fully bio-based hydrophobic nanoparticles offer valuable insights into the development of environmentally friendly separation technologies.
Monensin, a polyether ionophore antibiotic produced by Streptomyces cinnamonensis, exhibits notable anticoccidial and antitumor properties. In this study, a fatty acid addition (FAA) strategy significantly enhanced the monensin production capability of S. cinnamonensis, resulting in an unprecedented monensin titer of 17.72 g/L at 192 h, 7.36 times that of the control. Physiological assay showed the FAA markedly altered the cellular morphology, cell membrane fluidity, enzymatic activity and intracellular cofactors, thus indicating of an increased carbon flux. With transcriptional analysis at the product biosynthesis phase, 4 genes in the monensin biosynthesis cluster and 11 genes related to the oxidative stress response were observed to be upregulated. Meanwhile, genes consisting of two sugar transport systems were downregulated. For the precursors supply, genes associated with triacylglycerols (TAG) degradation (lps) and fatty acid degradation genes (fadE, fadB, fadA) were upregulated, while genes to TAG synthesis were downregulated. For the monensin synthetic pathway, 8 polyketide synthase genes, 9 modifier genes and 3 pathway-specific regulatory genes within the monensin biosynthetic gene cluster (mon) were upregulated. Consequently, the physiological and transcriptional response of S. cinnamonensis to the FAA strategy was correlated well with the monensin biosynthesis. The findings not only elucidated the de novo biosynthesis of monensin via FAA, but also offered a strategic framework for efficient production of polyketide natural products.
To address the challenge of efficient removal of anionic dyes from industrial wastewater, this study constructed two adsorbents integrating charge modulation and hierarchical porosity through polyethyleneimine (PEI) grafting onto iron-doped UiO-66-NH2 (Fe-UiO-66-NH2-PEI) and pristine UiO-66-NH2 (UiO-66-NH2-PEI) using cyanuric chloride as cross-linker. Adsorption experiments on the model anionic dye Eosin B (EB) revealed that Fe-UiO-66-NH2-PEI achieved a removal rate of 98 % with a qmax of 1.58 mmol center dot g-1, significantly surpassing those of polyethyleneimine cross-linked with chlorocyanuric acid (PEI-CC) and UiO-66-NH2-PEI under identical conditions. Kinetic fitting indicated that the adsorption followed the pseudo-second-order model, with the of Fe containing sample exhibiting a rate constant (k2) of 0.9346 g center dot mg-1 center dot min-1, which is faster than the one without Fe, suggesting accelerated chemisorption through Fe incorporation. Regeneration experiments showed that Fe-UiO-66-NH2-PEI maintained over 98 % removal efficiency after five adsorption-desorption cycles with structural integrity, whereas PEI-CC exhibited reduced efficiency (76 %). Mechanistic investigations combining FT-IR spectroscopy, zeta potential measurement and XPS analysis confirmed synergistic enhancement of anionic dye capture through electrostatic attraction, metal coordination, and it-it stacking interactions. The composite demonstrates promising potential for practical wastewater treatment applications owing to its straightforward synthesis protocol, exceptional adsorption performance, and excellent reusability.