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1.
Carbohydr Polym ; 337: 122112, 2024 Aug 01.
Article En | MEDLINE | ID: mdl-38710545

The growing concerns on environmental pollution and sustainability have raised the interest on the development of functional biobased materials for different applications, including food packaging, as an alternative to the fossil resources-based counterparts, currently available in the market. In this work, functional wood inspired biopolymeric nanocomposite films were prepared by solvent casting of suspensions containing commercial beechwood xylans, cellulose nanofibers (CNF) and lignosulfonates (magnesium or sodium), in a proportion of 2:5:3 wt%, respectively. All films presented good homogeneity, translucency, and thermal stability up to 153 °C. The incorporation of CNF into the xylan/lignosulfonates matrix provided good mechanical properties to the films (Young's modulus between 1.08 and 3.79 GPa and tensile strength between 12.75 and 14.02 MPa). The presence of lignosulfonates imparted the films with antioxidant capacity (DPPH radical scavenging activity from 71.6 to 82.4 %) and UV barrier properties (transmittance ≤19.1 % (200-400 nm)). Moreover, the films obtained are able to successfully delay the browning of packaged fruit stored over 7 days at 4 °C. Overall, the obtained results show the potential of using low-cost and eco-friendly resources for the development of sustainable active food packaging materials.


Cellulose , Food Packaging , Lignin , Lignin/analogs & derivatives , Nanocomposites , Nanofibers , Tensile Strength , Wood , Xylans , Food Packaging/methods , Lignin/chemistry , Nanocomposites/chemistry , Cellulose/chemistry , Cellulose/analogs & derivatives , Wood/chemistry , Nanofibers/chemistry , Xylans/chemistry , Antioxidants/chemistry , Fruit/chemistry
2.
PLoS One ; 19(5): e0304054, 2024.
Article En | MEDLINE | ID: mdl-38776338

This study explores the Hydrothermal Carbonization (HTC) treatment of lignocellulosic biomass blends, delving into the influence of several key parameters: temperature, additive nature and dosage, residence time, and biomass composition. Rapeseeds, Pinus radiata sawdust, oat husks, and pressed olive served as the studied biomasses. One hundred twenty-eight experiments were conducted to assess the effects on mass yield (MY), energy yield (EY), higher heating value (HHV), and final ash content (ASH) by a Factorial Experimental Design. The derived model equations demonstrated a robust fit to the experimental data, averaging an R2 exceeding 0.94, affirming their predictive accuracy. The observed energy yield ranged between 65% and 80%, notably with sawdust and olive blends securing EY levels surpassing 70%, while rapeseed blends exhibited the highest HHV at 25 MJ/kg. Temperature emerged as the most influential factor, resulting in an 11% decrease in MY and a substantial 2.20 MJ/kg increase in HHV. Contrastingly, blend composition and additive presence significantly impacted ASH and EY, with all blends exhibiting increased ASH in the presence of additives. Higher initial hemicellulose and aqueous extractive content in raw biomass correlated proportionally with heightened HHV.


Biofuels , Biomass , Biofuels/analysis , Lignin/chemistry , Temperature , Pinus/chemistry , Olea/chemistry , Brassica rapa/chemistry , Hot Temperature
3.
Molecules ; 29(9)2024 Apr 29.
Article En | MEDLINE | ID: mdl-38731545

Functional Lyocell fibers gain interest in garments and technical textiles, especially when equipped with inherently bioactive features. In this study, Lyocell fibers are modified with an ion exchange resin and subsequently loaded with copper (Cu) ions. The modified Lyocell process enables high amounts of the resin additive (>10%) through intensive dispersion and subsequently, high uptake of 2.7% Cu throughout the whole cross-section of the fiber. Fixation by Na2CO3 increases the washing and dyeing resistance considerably. Cu content after dyeing compared to the original fiber value amounts to approx. 65% for reactive, 75% for direct, and 77% for HT dyeing, respectively. Even after 50 household washes, a recovery of 43% for reactive, 47% for direct and 26% for HT dyeing is proved. XRD measurements reveal ionic bonding of Cu fixation inside the cellulose/ion exchange resin composite. A combination of the fixation process with a change in Cu valence state by glucose/NaOH leads to the formation of Cu2O crystallites, which is proved by XRD. Cu fiber shows a strong antibacterial effect against Staphylococcus aureus and Klebsiella pneumonia bacteria, even after 50 household washing cycles of both >5 log CFU. In nonwoven blends with a share of only 6% Cu fiber, a strong antimicrobial (CFU > log 5) and full antiviral effectiveness (>log 4) was received even after 50 washing cycles. Time-dependent measurements already show strong antiviral behavior after 30 s. Further, the fibers show an increased die off of the fungal isolate Candida auris with CFU log 4.4, and nonwovens made from 6% Cu fiber share a CFU log of 1.7. Findings of the study predestines the fiber for advanced textile processing and applications in areas with high germ loads.


Anti-Bacterial Agents , Antifungal Agents , Antiviral Agents , Copper , Antifungal Agents/pharmacology , Antifungal Agents/chemistry , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Antiviral Agents/pharmacology , Antiviral Agents/chemistry , Copper/chemistry , Copper/pharmacology , Cellulose/chemistry , Cellulose/pharmacology , Staphylococcus aureus/drug effects , Textiles , Microbial Sensitivity Tests , Klebsiella pneumoniae/drug effects , Lignin/chemistry , Lignin/pharmacology , Humans
4.
Anal Methods ; 16(19): 2983-2996, 2024 May 16.
Article En | MEDLINE | ID: mdl-38717259

We have successfully developed a validated high-throughput analysis method for the identification and quantification of native and oxifunctionalized monolignols using direct infusion electrospray ionization tandem mass spectrometry (DI-ESI-MS/MS). Oxifunctionalized monolignols generated through unspecific peroxygenase catalysis present a sustainable alternative to fossil aromatic hydrocarbons. This study emphasizes a sustainable analytical approach for these renewable biocatalytic precursors, addressing challenges such as matrix effects, accuracy, precision, and sensitivity of the method. Our findings demonstrate the potential of overcoming quantification difficulties using DI-ESI-MS. Notably, this analytical methodology represents a novel utilization of DI-ESI-MS/MS in examining monolignols and their functionalization, thereby advancing the exploration of lignin as a valuable and sustainable bioresource.


Lignin , Spectrometry, Mass, Electrospray Ionization , Tandem Mass Spectrometry , Spectrometry, Mass, Electrospray Ionization/methods , Tandem Mass Spectrometry/methods , Lignin/chemistry
5.
Int J Biol Macromol ; 268(Pt 1): 131619, 2024 May.
Article En | MEDLINE | ID: mdl-38692998

The plant cell wall is a complex, heterogeneous structure primarily composed of cellulose, hemicelluloses, and lignin. Exploring the variations in these three macromolecules over time is crucial for understanding wood formation to enhance chemical processing and utilization. Here, we comprehensively analyzed the chemical composition of cell walls in the trunks of Pinus tabulaeformis using multiple techniques. In situ analysis showed that macromolecules accumulated gradually in the cell wall as the plant aged, and the distribution pattern of lignin was opposite that of polysaccharides, and both showed heterogenous distribution patterns. In addition, gel permeation chromatography (GPC) results revealed that the molecular weights of hemicelluloses decreased while that of lignin increased with age. Two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR) analysis indicated that hemicelluloses mainly comprised galactoglucomannan and arabinoglucuronoxylan, and the lignin types were mainly comprised guaiacyl (G) and p-hydroxyphenyl (H) units with three main linkage types: ß-O-4, ß-ß, and ß-5. Furthermore, the C-O bond (ß-O-4) signals of lignin decreased while the C-C bonds (ß-ß and ß-5) signals increased over time. Taken together, these findings shed light on wood formation in P. tabulaeformis and lay the foundation for enhancing the processing and use of wood and timber products.


Cell Wall , Cellulose , Lignin , Pinus , Polysaccharides , Lignin/chemistry , Pinus/chemistry , Cell Wall/chemistry , Polysaccharides/chemistry , Cellulose/chemistry , Molecular Weight , Trees/chemistry , Magnetic Resonance Spectroscopy/methods , Wood/chemistry
6.
Molecules ; 29(10)2024 May 16.
Article En | MEDLINE | ID: mdl-38792198

Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H2, CO, CO2, and CH4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H2 yield with a test R2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH4, CO, and CO2, with test R2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H2, CH4, CO, and CO2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields.


Biomass , Hydrogen , Lignin , Machine Learning , Water , Lignin/chemistry , Water/chemistry , Hydrogen/chemistry , Hydrogen/analysis , Gases/chemistry , Gases/analysis , Algorithms , Neural Networks, Computer , Carbon Dioxide/chemistry , Carbon Dioxide/analysis , Support Vector Machine , Methane/chemistry , Methane/analysis
7.
Molecules ; 29(10)2024 May 16.
Article En | MEDLINE | ID: mdl-38792212

Lignanoids are an active ingredient exerting powerful antioxidant and anti-inflammatory effects in the treatment of many diseases. In order to improve the efficiency of the resource utilization of traditional Chinese medicine waste, Magnolia officinalis Rehder & E.H.Wilson residue (MOR) waste biomass was used as raw material in this study, and a series of deep eutectic solvents (ChUre, ChAce, ChPro, ChCit, ChOxa, ChMal, ChLac, ChLev, ChGly and ChEG) were selected to evaluate the extraction efficiency of lignanoids from MORs. The results showed that the best conditions for lignanoid extraction were a liquid-solid ratio of 40.50 mL/g, an HBD-HBA ratio of 2.06, a water percentage of 29.3%, an extract temperature of 337.65 K, and a time of 107 min. Under these conditions, the maximum lignanoid amount was 39.18 mg/g. In addition, the kinetics of the extraction process were investigated by mathematic modeling. In our antioxidant activity study, high antioxidant activity of the lignanoid extract was shown in scavenging four different types of free radicals (DPPH, ·OH, ABTS, and superoxide anions). At a concentration of 3 mg/mL, the total antioxidant capacity of the lignanoid extract was 1.795 U/mL, which was equal to 0.12 mg/mL of Vc solution. Furthermore, the antibacterial activity study found that the lignanoid extract exhibited good antibacterial effects against six tested pathogens. Among them, Staphylococcus aureus exerted the strongest antibacterial activity. Eventually, the correlation of the lignanoid extract with the biological activity and physicochemical properties of DESs is described using a heatmap, along with the evaluation of the in vitro hypoglycemic, in vitro hypolipidemic, immunomodulatory, and anti-inflammatory activity of the lignanoid extract. These findings can provide a theoretical foundation for the extraction of high-value components from waste biomass by deep eutectic solvents, as well as highlighting its specific significance in natural product development and utilization.


Antioxidants , Biomass , Magnolia , Magnolia/chemistry , Antioxidants/pharmacology , Antioxidants/chemistry , Antioxidants/isolation & purification , Deep Eutectic Solvents/chemistry , Lignin/chemistry , Lignin/pharmacology , Lignin/isolation & purification , Plant Extracts/chemistry , Plant Extracts/pharmacology , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/isolation & purification , Anti-Inflammatory Agents/pharmacology , Anti-Inflammatory Agents/chemistry , Anti-Inflammatory Agents/isolation & purification , Animals
8.
J Biotechnol ; 389: 78-85, 2024 Jun 20.
Article En | MEDLINE | ID: mdl-38718873

In a bid to explore the on-site biorefinery approach for conversion of forestry residues, lignocellulosic biomass into value-added products was studied. The bark white pine wood was subjected to the microwave technique of fast and slow hydrolysis under varying acid and biomass concentrations to produce levulinic acid (LA). The HCl (2% v/v) and plant biomass (1% w/v) were identified as the optimum conditions for fast wood hydrolysis (270 ºC for 12 sec), which led to maximum LA yield of 446.68 g/kgPB. The proposed sustainable approach is mild, quick, and utilized a very low concentration of the HCl for the production of LA. The hydrolysate was used as a medium for Kluyveromyces marxianus growth to produce 2-phenylethanol (2-PE). K. marxianus used 74-95% of furfural from hydrolysate as a co-substrate to grow. The proposed model of the integrated biorefinery is an affordable on-site approach of using forest waste into localized solutions to produce LA and 2-PE.


Biomass , Levulinic Acids , Phenylethyl Alcohol , Wood , Levulinic Acids/metabolism , Wood/chemistry , Wood/metabolism , Hydrolysis , Phenylethyl Alcohol/metabolism , Kluyveromyces/metabolism , Kluyveromyces/growth & development , Lignin/metabolism , Lignin/chemistry , Pinus/metabolism , Pinus/chemistry
9.
Bioresour Technol ; 402: 130804, 2024 Jun.
Article En | MEDLINE | ID: mdl-38718904

Lignin, a complex phenolic polymer crucial for plant structure, is mostly used as fuel but it can be harnessed for environmentally friendly applications. This article explores ozonation as a green method for lignin extraction from lignocellulosic biomass, aiming to uncover the benefits of the extracted lignin. A pilot-scale ozonation reactor was employed to extract lignin from Miscanthus giganteus (a grass variety) and vine shoots (a woody biomass). The study examined the lignin extraction and modification of the fractions and identified the generation of phenolic and organic acids. About 48 % of lignin was successfully extracted from both biomass types. Phenolic monomers were produced, vine shoots yielding fewer monomers than Miscanthus giganteus. Ozonation generated homogeneous lignin oligomers, although their molecular weight decreased during ozonation, with vine shoot oligomers exhibiting greater resistance to ozone. Extracted fractions were stable at 200 °C, despite the low molecular weight, outlining the potential of these phenolic fractions.


Lignin , Ozone , Plant Shoots , Poaceae , Lignin/chemistry , Poaceae/chemistry , Ozone/chemistry , Ozone/pharmacology , Pilot Projects , Plant Shoots/chemistry , Biomass , Bioreactors , Molecular Weight , Phenols
10.
Bioresour Technol ; 402: 130802, 2024 Jun.
Article En | MEDLINE | ID: mdl-38718902

A cost-effective, and low-energy room-temperature cascade catalytic carbonization strategy is demonstrated for converting lignin into graphite with a high yield of 87 %, a high surface potential of -37 eV and super-hydrophilicity. This super-hydrophilic feature endows the lignin-derived graphite to be dispersed in a variety of polar solvents, which is important for its future applications. Encapsulating of liquid metals with the graphite for electrical circuit patterning on flexible substrates is also advocated. These written patterns show superb conductivity of 4.9 × 106 S/m, offering good performance stability and reliability while being repeatedly stretched, folded, twisted, and bent. This will offer new designs for flexible electronic devices, sensors, and biomedical devices.


Graphite , Hydrophobic and Hydrophilic Interactions , Lignin , Temperature , Lignin/chemistry , Graphite/chemistry , Catalysis , Carbon/chemistry , Electric Conductivity
11.
Bioresour Technol ; 402: 130840, 2024 Jun.
Article En | MEDLINE | ID: mdl-38750829

The constant ammonia gas (NH3) and greenhouse gases (GHG) emissions were considered as a deep-rooted problem in composting which caused air pollution and global climate change. To achieve the mitigation of NH3 and GHG, a novel additive derived from wasted straw, with modified structure and functional groups, has been developed. Results showed that the adsorption capacity of modified lignin (ML) for both ammonium and nitrate was significantly increased by 132.5-360.8 % and 313.7-454.3 % comparing with biochar (BC) and phosphogypsum (PG) after reconstructing porous structure and grafting R-COOH, R-SO3H functional groups. The application of ML could reduce 36.3 % NH3 emission during composting compared with control. Furthermore, the synergetic mitigation NH3 and GHG in ML treatment resulted in a reduction of global warming potential (GWP) by 31.0-64.6 % compared with BC and PG. These findings provide evidence that ML can be a feasible strategy to effectively alleviate NH3 and GHG emissions in composting.


Ammonia , Composting , Greenhouse Gases , Lignin , Composting/methods , Lignin/chemistry , Charcoal/chemistry , Adsorption , Soil/chemistry , Greenhouse Effect
12.
Food Chem ; 451: 139479, 2024 Sep 01.
Article En | MEDLINE | ID: mdl-38696939

Lignocellulose constitutes the primary component of dietary fiber. We assessed how fermenting bamboo shoot residue with the medicinal white-rot fungus Inonotus obliquus affected the yield, composition, and functional attributes of dietary fiber by altering bamboo shoot residue lignocellulose's spatial structure and composition. I. obliquus secretes lignocellulolytic enzymes, which effectively enhance the degradation of holocellulose and lignin by 87.8% and 25.5%, respectively. Fermentation led to a more porous structure and reduced crystallinity. The yield of soluble dietary fiber increased from 5.1 g/100 g raw BSR to 7.1 g/100 g 9-day-fermented bamboo shoot residue. The total soluble sugar content of dietary fiber significantly increased from 9.2% to 13.8%, which improved the hydration, oil holding capacity, in vitro cholesterol, sodium cholate, and nitrite adsorption properties of dietary fiber from bamboo shoot residue. These findings confirm that I. obliquus biotransformation is promising for enhancing dietary fiber yield and quality.


Dietary Fiber , Fermentation , Inonotus , Lignin , Lignin/metabolism , Lignin/chemistry , Dietary Fiber/metabolism , Dietary Fiber/analysis , Inonotus/metabolism , Inonotus/chemistry , Plant Shoots/chemistry , Plant Shoots/metabolism , Sasa/chemistry , Sasa/metabolism
13.
Molecules ; 29(10)2024 May 11.
Article En | MEDLINE | ID: mdl-38792135

The hydrolysis and biotransformation of lignocellulose, i.e., biorefinery, can provide human beings with biofuels, bio-based chemicals, and materials, and is an important technology to solve the fossil energy crisis and promote global sustainable development. Biorefinery involves steps such as pretreatment, saccharification, and fermentation, and researchers have developed a variety of biorefinery strategies to optimize the process and reduce process costs in recent years. Lignocellulosic hydrolysates are platforms that connect the saccharification process and downstream fermentation. The hydrolysate composition is closely related to biomass raw materials, the pretreatment process, and the choice of biorefining strategies, and provides not only nutrients but also possible inhibitors for downstream fermentation. In this review, we summarized the effects of each stage of lignocellulosic biorefinery on nutrients and possible inhibitors, analyzed the huge differences in nutrient retention and inhibitor generation among various biorefinery strategies, and emphasized that all steps in lignocellulose biorefinery need to be considered comprehensively to achieve maximum nutrient retention and optimal control of inhibitors at low cost, to provide a reference for the development of biomass energy and chemicals.


Biomass , Lignin , Lignin/chemistry , Hydrolysis , Fermentation , Biofuels , Nutrients/metabolism
14.
Int J Biol Macromol ; 269(Pt 2): 132147, 2024 Jun.
Article En | MEDLINE | ID: mdl-38719007

Lignin in biomass plays significant role in substitution of synthetic polymer and reduction of energy expenditure, and the lignin content was usually determined by wet chemical methods. However, the methods' heavy workload, low efficiency, huge consumption of chemicals and use of toxic reagents render them unsuitable for sustainable development and environmental protection. Chinese fir, a prevalent angiosperm tree, holds immense importance for various industries. Since our previous work found that Raman spectroscopy could accurately predict the lignin content in poplar, we propose that the lignin content of Chinese fir can be estimated by similar strategy. The results suggested that the peak at 2895 cm-1 is the optimal choice of internal standard peak and algorithm of XGBoost demonstrates the highest accuracy among all algorithms. Furthermore, transfer learning was successfully introduced to enhance the accuracy and robustness of the model. Ultimately, we report that a machine learning algorithm, combining transfer learning with XGBoost or LightGBM, offers an accurate, high-efficiency and environmental friendly method for predicting the lignin content of Chinese fir using Raman spectra.


Algorithms , Cunninghamia , Lignin , Machine Learning , Spectrum Analysis, Raman , Lignin/chemistry , Lignin/analysis , Spectrum Analysis, Raman/methods , Cunninghamia/chemistry
15.
Int J Biol Macromol ; 269(Pt 2): 132141, 2024 Jun.
Article En | MEDLINE | ID: mdl-38723809

To enhance the flame retardancy and mechanical performance of PLA, a polyelectrolyte complex predicated on lignin was obtained by electrostatic mutual adsorption of ammonium polyphosphate (APP), polyethyleneimine (PEI), and copper ions as raw materials. The FT-IR spectra and EDX analysis confirmed the successful synthesis of a lignin-based flame retardant hybrid (APL-Cu2+) containing copper, phosphorus, and nitrogen elements. The combustion test results showed that the peak heat release rate and total heat release of the PLA composite containing 12 wt% APL-Cu2+ were decreased by 15.1 % and 18.2 %, respectively, as compared to those of pure PLA. The char residue morphology observation revealed that the addition of APL-Cu2+ could promote the formation of a highly dense and stable graphitized char layer, while TG-MS detected the emission of refractory gases such as ammonia gas, carbon dioxide, and water during combustion. The strong hydrogen bonding between APL-Cu2+ and the PLA matrix kept the composite maintaining good strength and toughness. The tensile strength and impact strength of PLA/6APL-Cu2+ increased by 4.73 % and 65.71 %, respectively, due to its high crystallinity and good interfacial compatibility. This work provides a feasible method to develop biobased flame retardant hybrids for PLA composites with better fire safety and improved mechanical properties.


Copper , Flame Retardants , Lignin , Polyesters , Lignin/chemistry , Copper/chemistry , Polyesters/chemistry , Fires/prevention & control , Mechanical Phenomena , Tensile Strength , Spectroscopy, Fourier Transform Infrared , Polyethyleneimine/chemistry
16.
Int J Biol Macromol ; 269(Pt 2): 132145, 2024 Jun.
Article En | MEDLINE | ID: mdl-38723819

Sulfonated lignin-based dye dispersants have intensively attracted attention due to their low cost, renewability and abundant sources. However, their utilization is limited by the low content of sulfonic groups and high content of hydroxyl groups in their complex lignin structure, which results in various problems such as high reducing rate of dye, severe staining of the fibers and uneven dyeing. Here, the multi-site sulfonated lignin-based dispersants were prepared with high sulfonic group content (2.20 mmol/g) and low hydroxyl content (2.43 mmol/g). When using it as the dispersant, the dye uptake rate was improved from 69.23 % to 98.55 %, the reducing rate was decreased from 20.82 % to 2.03 %, the K/S value was reduced from 0.69 to 0.02, and the particle sizes in dye system before and after high temperature treatment were stabilized below 0.5 µm. Besides, the dispersion effect was significantly improved because no obvious separation between dye and water was observed even if without the assistance of grinding process. In short, the multi-site sulfonation method proposed in this work could remarkably improve the performances of the lignin-based dye dispersants, which would facilitate the development of the dye dispersion and the high value utilization of lignin.


Coloring Agents , Lignin , Lignin/chemistry , Coloring Agents/chemistry , Sulfonic Acids/chemistry , Particle Size , Temperature
17.
Int J Biol Macromol ; 269(Pt 2): 132144, 2024 Jun.
Article En | MEDLINE | ID: mdl-38729476

Herein, we investigated the synergistic effects of jet milling (JM) and deep eutectic solvent (DES) pretreatment on the fractionation of grapevine lignin and the consequent enhancement of enzymatic hydrolysis. Grapevine, a substantial byproduct of the wine industry, was subjected to JM pretreatment to produce finely powdered particles (median diameter D50 = 98.90), which were then further treated with acidic ChCl-LA and alkaline K2CO3-EG DESs. The results revealed that the combined JM + ChCl-LA pretreatment significantly increased the cellulose preservation under optimal conditions (110 °C, 4 h, and 20 % water content), achieving removal rates of 74.18 % xylan and 66.05 % lignin, respectively. The pretreatment temperature and inhibitor production were reduced, resulting in a remarkable threefold increase in glucose yield compared to untreated samples. Moreover, the structural analysis of the pretreated lignin indicated an enrichment of phenolic units, leading to enhanced antioxidant and antibacterial activities, particularly in the JM pretreated samples. These findings underscore the promising potential of the synergistic JM and DES pretreatment in facilitating the efficient utilization of grapevine lignocellulosic biomass for sustainable biorefinery technologies.


Deep Eutectic Solvents , Lignin , Vitis , Lignin/chemistry , Vitis/chemistry , Hydrolysis , Deep Eutectic Solvents/chemistry , Chemical Fractionation/methods , Antioxidants/chemistry , Antioxidants/pharmacology , Biomass , Cellulose/chemistry , Cellulase/chemistry , Cellulase/metabolism , Solvents/chemistry , Temperature
18.
Int J Biol Macromol ; 269(Pt 2): 132156, 2024 Jun.
Article En | MEDLINE | ID: mdl-38729480

Reasonable design of non-noble metal catalysts with hollow open structure for hydrodeoxygenation (HDO) of lignin derivatives to value-added chemicals is of great significance but challenging. Herein, a novel MOF-derived multilayer hollow sphere coated nickel­tungsten bimetallic catalyst (Ni2-WOx@CN-700) was fabricated via by confined pyrolysis strategy using bimetallic MOFs as a self-sacrificial template, which exhibits robust activity for the typical model HDO of vanillin to 2-methoxy-4-methylphenol (Yield of 100 % at 140 °C for no less than 10 cycles). The characterizations revealed that WOx facilitated the dispersion of Ni nanoparticles and adjusted the acidic capacity of the catalyst through the formed Ni-WOx heterojunction. Density functional theory (DFT) calculations confirms that WOx species enhanced the electron-rich nature of the active sites, while the adsorption energies of H2 and vanillin on Ni-WOx decreased from -0.572 eV and - 0.622 eV on Ni to -3.969 eV and - 4.922 eV, respectively. These results further indicated that the high activity of Ni2-WOx@CN-700 was attributed to the Ni-WOx heterojunction. Based on the characterizations and the thermodynamic calculations, the reaction mechanism was proposed. In addition, the catalyst shows good substrate universality, which enables its good commercial application prospect.


Benzaldehydes , Nickel , Catalysis , Nickel/chemistry , Benzaldehydes/chemistry , Tungsten/chemistry , Lignin/chemistry , Thermodynamics , Metal-Organic Frameworks/chemistry , Adsorption , Density Functional Theory
19.
Int J Biol Macromol ; 269(Pt 2): 132216, 2024 Jun.
Article En | MEDLINE | ID: mdl-38729483

Agricultural by-products of sesame are promising bioresources in food processing. This study extracted lignin from the by-products of sesame oil production, namely, the capsules and straw of black and white sesame. Using acid, alkali, and ethanol methods, 12 distinct lignins were obtained to prepare biochar, aiming to investigate both the structural characteristics of lignin-based biochar (LBB) and its ability to remove benzo[a]pyrene (BaP) from sesame oil. The results showed that white sesame straw was the most suitable raw material for preparing biochar. In terms of the preparation method, acid-extracted lignin biochar was more effective in removing BaP than alkaline or ethanol methods. Notably, WS-1LB (white sesame straw acid-extracted lignin biochar) exhibited the highest BaP adsorption efficiency (91.44 %) and the maximum specific surface area (1065.8187 m2/g), characterized by porous structures. The pseudo 2nd and Freundlich models were found to be the best fit for the adsorption kinetics and isotherms of BaP on LBB, respectively, suggesting that a multilayer adsorption process was dominant. The high adsorption of LBB mainly resulted from pore filling. This study provides an economical and highly efficient biochar adsorbent for the removal of BaP in oil.


Charcoal , Lignin , Sesame Oil , Lignin/chemistry , Charcoal/chemistry , Adsorption , Sesame Oil/chemistry , Benzo(a)pyrene/chemistry , Kinetics
20.
Int J Biol Macromol ; 269(Pt 2): 132146, 2024 Jun.
Article En | MEDLINE | ID: mdl-38734342

In this research, a sitagliptin-lignin biopolymer (SL) containing zinc selenide quantum dots (ZnSe QDs) and doxorubicin (doxo) was synthesized. The fabricated polymeric drug delivery system was characterized via FTIR, XRD, SEM, TGA, IR, and DSC. SLQD-Doxo exhibited an irregular surface with a 32 nm diameter and well-defined surface chemistry. Drug loading efficiency was assessed at different concentrations, pH levels, time intervals, and temperatures, and drug kinetics were calculated. Maximum drug release was observed at 6 µmol concentration after 24 h, pH of 6.5 and 45 °C. The maximum drug encapsulation efficiency was 81.75 %. SLQD-Doxo demonstrated 24.4 ± 1.04 % anti-inflammatory activity, and the maximum lipoxygenase inhibition in a concentration-dependent manner was 71.45 ± 2.02 %, compared to indomethacin, a standard anticancer drug. The designed system was applied to breast cancer MCF-7 cells to evaluate anticancer activity. Cytotoxicity of SLQD-Doxo resulted in 24.48 ± 1.64 dead cells and 74.39 ± 4.12 viable cells. Lignin's polyphenolic nature resulted in good antioxidant activity of LLQD-Doxo. The combination of SLQD-Doxo was appropriate for drug delivery at high temperatures and acidic pH of tumor cells compared to healthy cells.


Doxorubicin , Drug Delivery Systems , Lignin , Sitagliptin Phosphate , Doxorubicin/pharmacology , Doxorubicin/chemistry , Doxorubicin/administration & dosage , Humans , Lignin/chemistry , Lignin/pharmacology , MCF-7 Cells , Sitagliptin Phosphate/chemistry , Sitagliptin Phosphate/pharmacology , Drug Liberation , Drug Carriers/chemistry , Polymers/chemistry , Quantum Dots/chemistry , Hydrogen-Ion Concentration , Antioxidants/pharmacology , Antioxidants/chemistry , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/administration & dosage , Cell Survival/drug effects
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