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1.
Int J Biol Macromol ; 268(Pt 1): 131619, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38692998

RESUMEN

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.


Asunto(s)
Pared Celular , Celulosa , Lignina , Pinus , Polisacáridos , Lignina/química , Pinus/química , Pared Celular/química , Polisacáridos/química , Celulosa/química , Peso Molecular , Árboles/química , Espectroscopía de Resonancia Magnética/métodos , Madera/química
2.
Sci Rep ; 14(1): 12387, 2024 05 29.
Artículo en Inglés | MEDLINE | ID: mdl-38811644

RESUMEN

Chemical processing is among the significant keys to tackle agro-residues utilization field, aiming to obtain value-added materials. Extraction of cellulose nanocrystals (CNCs) is an emerging route to valorize lignocellulosic wastes into high value particles. In this investigation, effect of acidic hydrolysis duration was monitored on size and morphology of obtained crystals; namely: CNCs from Nile roses fibers (NRFs) (Eichhornia crassipes). Different acidic hydrolysis duration range or different characterization techniques set this article apart from relevant literature, including our group research articles. The grinded NRFs were firstly subjected to alkaline and bleaching pretreatments, then acid hydrolysis process was carried out with varied durations ranging from 5 to 30 min. Microcrystalline cellulose (MCC) was used as reference for comparison with NRFs based samples. The extracted CNCs samples were investigated using various techniques such as scanning electron microscopy (SEM), Atomic force microscopy (AFM), Raman spectroscopy, and thermogravimetric (TGA) analysis. The figures gotten from SEM and AFM depicted that NRFs based CNCs appeared as fibril-like shapes, with reduced average size when the NRFs underwent pulping and bleaching processes. This was indicated that the elimination of hemicellulose and lignin components got achieved successfully. This outcome was proven by chemical composition measurements and TGA/DTG curves. On the other hand, AFM-3D images indicated that CNCs topology and surface roughness were mostly affected by increasing hydrolysis durations, besides smooth and homogeneous surfaces were noticed. Moreover, Raman spectra demonstrated that the particle size and crystallinity degree of NRFs based CNCs can be affected by acidic hydrolysis durations and optimum extraction time was found to be 10 min. Thermal stability of extracted CNCs-NRFs and CNCs-MCC was measured by TGA/DTG and the kinetic models were suggested to identify the kinetic parameters of the thermal decomposition of CNCs for each acid hydrolysis duration. Increasing hydrolysis duration promoted thermal stability, particularly for NRFs based CNCs. Results showcased in this article add new perspective to Nile rose nanocellulose and pave down the way to fabricate NRFs based humidity nano-sensors.


Asunto(s)
Celulosa , Eichhornia , Nanopartículas , Celulosa/química , Nanopartículas/química , Eichhornia/química , Eichhornia/metabolismo , Hidrólisis , Microscopía de Fuerza Atómica , Espectrometría Raman , Microscopía Electrónica de Rastreo , Termogravimetría , Lignina/química
3.
Rapid Commun Mass Spectrom ; 38(14): e9716, 2024 Jul 30.
Artículo en Inglés | MEDLINE | ID: mdl-38738638

RESUMEN

RATIONALE: This study overcomes traditional biomass analysis limitations by introducing a pioneering matrix-free laser desorption/ionization (LDI) approach in mass spectrometry imaging (MSI) for efficient lignin evaluation in wood. The innovative acetic acid-peracetic acid (APA) treatment significantly enhances lignin detection, enabling high-throughput, on-site analysis. METHODS: Wood slices, softwood from a conifer tree (Japanese cypress) and hardwood from a broadleaf tree (Japanese beech), were analyzed using MSI with a Fourier transform ion cyclotron resonance mass spectrometer. The developed APA treatment demonstrated effectiveness for MSI analysis of biomass. RESULTS: Our imaging technique successfully distinguishes between earlywood and latewood and enables the distinct visualization of lignin in these and other wood tissues, such as the radial parenchyma. This approach reveals significant contrasts in MSI. It has identified intense ions from ß-O-4-type lignin, specifically in the radial parenchyma of hardwood, highlighting the method's precision and utility in wood tissue analysis. CONCLUSIONS: The benefits of matrix-free LDI include reduced peak overlap, consistent sample quality, preservation of natural sample properties, enhanced analytical accuracy, and reduced operational costs. This innovative approach is poised to become a standard method for rapid and precise biomass evaluation and has important applications in environmental research and sustainable resource management and is crucial for the effective management of diverse biomass, paving the way towards a sustainable, circular society.


Asunto(s)
Biomasa , Lignina , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción , Madera , Madera/química , Lignina/análisis , Lignina/química , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción/métodos , Fagus/química
4.
Molecules ; 29(9)2024 Apr 29.
Artículo en Inglés | MEDLINE | ID: mdl-38731545

RESUMEN

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.


Asunto(s)
Antibacterianos , Antifúngicos , Antivirales , Cobre , Antifúngicos/farmacología , Antifúngicos/química , Antibacterianos/farmacología , Antibacterianos/química , Antivirales/farmacología , Antivirales/química , Cobre/química , Cobre/farmacología , Celulosa/química , Celulosa/farmacología , Staphylococcus aureus/efectos de los fármacos , Textiles , Pruebas de Sensibilidad Microbiana , Klebsiella pneumoniae/efectos de los fármacos , Lignina/química , Lignina/farmacología , Humanos
5.
PLoS One ; 19(5): e0304054, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38776338

RESUMEN

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.


Asunto(s)
Biocombustibles , Biomasa , Biocombustibles/análisis , Lignina/química , Temperatura , Pinus/química , Olea/química , Brassica rapa/química , Calor
6.
Bioresour Technol ; 402: 130840, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38750829

RESUMEN

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.


Asunto(s)
Amoníaco , Compostaje , Gases de Efecto Invernadero , Lignina , Compostaje/métodos , Lignina/química , Carbón Orgánico/química , Adsorción , Suelo/química , Efecto Invernadero
7.
Food Chem ; 451: 139479, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-38696939

RESUMEN

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.


Asunto(s)
Fibras de la Dieta , Fermentación , Inonotus , Lignina , Lignina/metabolismo , Lignina/química , Fibras de la Dieta/metabolismo , Fibras de la Dieta/análisis , Inonotus/metabolismo , Inonotus/química , Brotes de la Planta/química , Brotes de la Planta/metabolismo , Sasa/química , Sasa/metabolismo
8.
Anal Methods ; 16(19): 2983-2996, 2024 May 16.
Artículo en Inglés | MEDLINE | ID: mdl-38717259

RESUMEN

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.


Asunto(s)
Lignina , Espectrometría de Masa por Ionización de Electrospray , Espectrometría de Masas en Tándem , Espectrometría de Masa por Ionización de Electrospray/métodos , Espectrometría de Masas en Tándem/métodos , Lignina/química
9.
Molecules ; 29(10)2024 May 16.
Artículo en Inglés | MEDLINE | ID: mdl-38792198

RESUMEN

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.


Asunto(s)
Biomasa , Hidrógeno , Lignina , Aprendizaje Automático , Agua , Lignina/química , Agua/química , Hidrógeno/química , Hidrógeno/análisis , Gases/química , Gases/análisis , Algoritmos , Redes Neurales de la Computación , Dióxido de Carbono/química , Dióxido de Carbono/análisis , Máquina de Vectores de Soporte , Metano/química , Metano/análisis
10.
Molecules ; 29(10)2024 May 16.
Artículo en Inglés | MEDLINE | ID: mdl-38792212

RESUMEN

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.


Asunto(s)
Antioxidantes , Biomasa , Magnolia , Magnolia/química , Antioxidantes/farmacología , Antioxidantes/química , Antioxidantes/aislamiento & purificación , Disolventes Eutécticos Profundos/química , Lignina/química , Lignina/farmacología , Lignina/aislamiento & purificación , Extractos Vegetales/química , Extractos Vegetales/farmacología , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/aislamiento & purificación , Antiinflamatorios/farmacología , Antiinflamatorios/química , Antiinflamatorios/aislamiento & purificación , Animales
11.
Int J Biol Macromol ; 269(Pt 2): 132147, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38719007

RESUMEN

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.


Asunto(s)
Algoritmos , Cunninghamia , Lignina , Aprendizaje Automático , Espectrometría Raman , Lignina/química , Lignina/análisis , Espectrometría Raman/métodos , Cunninghamia/química
12.
Int J Biol Macromol ; 269(Pt 2): 132141, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38723809

RESUMEN

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.


Asunto(s)
Cobre , Retardadores de Llama , Lignina , Poliésteres , Lignina/química , Cobre/química , Poliésteres/química , Incendios/prevención & control , Fenómenos Mecánicos , Resistencia a la Tracción , Espectroscopía Infrarroja por Transformada de Fourier , Polietileneimina/química
13.
Int J Biol Macromol ; 269(Pt 2): 132145, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38723819

RESUMEN

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.


Asunto(s)
Colorantes , Lignina , Lignina/química , Colorantes/química , Ácidos Sulfónicos/química , Tamaño de la Partícula , Temperatura
14.
Int J Biol Macromol ; 269(Pt 2): 132144, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38729476

RESUMEN

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.


Asunto(s)
Disolventes Eutécticos Profundos , Lignina , Vitis , Lignina/química , Vitis/química , Hidrólisis , Disolventes Eutécticos Profundos/química , Fraccionamiento Químico/métodos , Antioxidantes/química , Antioxidantes/farmacología , Biomasa , Celulosa/química , Celulasa/química , Celulasa/metabolismo , Solventes/química , Temperatura
15.
Int J Biol Macromol ; 269(Pt 2): 132156, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38729480

RESUMEN

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.


Asunto(s)
Benzaldehídos , Níquel , Catálisis , Níquel/química , Benzaldehídos/química , Tungsteno/química , Lignina/química , Termodinámica , Estructuras Metalorgánicas/química , Adsorción , Teoría Funcional de la Densidad
16.
Int J Biol Macromol ; 269(Pt 2): 132216, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38729483

RESUMEN

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.


Asunto(s)
Carbón Orgánico , Lignina , Aceite de Sésamo , Lignina/química , Carbón Orgánico/química , Adsorción , Aceite de Sésamo/química , Benzo(a)pireno/química , Cinética
17.
Int J Biol Macromol ; 269(Pt 2): 132146, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38734342

RESUMEN

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.


Asunto(s)
Doxorrubicina , Sistemas de Liberación de Medicamentos , Lignina , Fosfato de Sitagliptina , Doxorrubicina/farmacología , Doxorrubicina/química , Doxorrubicina/administración & dosificación , Humanos , Lignina/química , Lignina/farmacología , Células MCF-7 , Fosfato de Sitagliptina/química , Fosfato de Sitagliptina/farmacología , Liberación de Fármacos , Portadores de Fármacos/química , Polímeros/química , Puntos Cuánticos/química , Concentración de Iones de Hidrógeno , Antioxidantes/farmacología , Antioxidantes/química , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/administración & dosificación , Supervivencia Celular/efectos de los fármacos
18.
Environ Sci Pollut Res Int ; 31(24): 35727-35743, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38740679

RESUMEN

The use of lignocellulosic residues, originating from sawdust, in composting sewage sludge for organic fertilizer production, is a practice of growing interest. However, few studies have explored the effect of the proportion of sawdust and sewage sludge raw materials on composting performance in the humification process. This study assessed the addition of sawdust in the sewage sludge composting process, regarding carbon content, presence of heavy metals, and humification of the organic compost. The experimental design employed was a randomized complete block design with five treatments featuring different proportions of organic residues to achieve C/N ratios between 30-1 (T1: 100% sewage sludge and 0% sawdust, T2: 86% sewage sludge and 14.0% sawdust, T3: 67% sewage sludge and 33% sawdust, T4: 55% sewage sludge and 45% sawdust, and T5: 46.5% sewage sludge and 53.5% sawdust) and five replications, totaling 25 experimental units. The addition of lignocellulosic residue in sewage sludge composting increased the levels of TOC and the C/N ratio, reduced the levels of pH, P, N, Na, Ba, and Cr, and did not interfere with the levels of K, Ca, Mg, S, CEC, labile carbon, and metals Fe, Zn, Cu, Mn, Ni, and Pb. The increase in the proportion of sawdust residue favored the degradation of aliphatic groups, increasing the presence of aromatic structures and reducing humification at the end of composting. The use of sawdust as a lignocellulosic residue in sewage sludge composting is a viable and efficient alternative to produce high-quality organomineral fertilizers.


Asunto(s)
Compostaje , Metales Pesados , Aguas del Alcantarillado , Aguas del Alcantarillado/química , Metales Pesados/análisis , Lignina/química , Espectroscopía Infrarroja por Transformada de Fourier , Fertilizantes , Metales/química
19.
J Hazard Mater ; 472: 134565, 2024 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-38743974

RESUMEN

Biochar shows great potential in soil cadmium pollution treatment, however, the effect and mechanisms of biochar on cadmium passivation (CP) during the long-term process of soil from flooding to natural air-drying are not clear. In this study, a 300-day experiment was conducted to keep the flooded water level constant for the first 100 days and then dried naturally. Mechanisms of CP by lignin biochar (LBC) were analyzed through chemical analysis, FTIR-2D-COS, EEMs-PARAFAC, ultraviolet spectroscopy characterizations, and microbial community distribution of soil. Results showed that application of LBC results in rapid CP ratio in soil within 35 days, mainly in the residual and Fe-Mn bound states (total 72.80%). CP ratio further increased to 90.89% with water evaporation. The CP mechanisms include precipitation, electrostatic effect, humus complexation, and microbial remediation by promoting the propagation of fungi such as Penicillium and Trichoderma. Evaporation of water promoted the colonization of aerobic microorganisms and then increased the degree of soil humification and aromatization, thereby enhancing the cadmium passivation. Simultaneously, the biochar could reduce the relative abundance of plant pathogens in soil from 1.8% to 0.03% and the freshness index (ß/α) from 0.64 to 0.16, favoring crop growth and promoting carbon sequestration and emission reduction.


Asunto(s)
Cadmio , Carbón Orgánico , Lignina , Microbiología del Suelo , Contaminantes del Suelo , Carbón Orgánico/química , Cadmio/química , Contaminantes del Suelo/química , Lignina/química , Inundaciones , Suelo/química , Desecación
20.
Int J Biol Macromol ; 269(Pt 2): 131955, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38692542

RESUMEN

Dyes pollution is well known for their hazardous impacts on human health and the environment. The removal of dyes from wastewater has become an important issue. In this study, magnetic micrometer-sized particles AL-CTS@MNPs were synthesized from alkaline lignin (AL) and chitosan (CTS) by "one-pot method". The adsorbent presented higher selectivity adsorption effect on anionic dyes than amphoteric and cationic dyes, and even no adsorption effect on cationic methylene blue (MB), which showed that the anionic dyes could be better separated from the other two types of dyes. The adsorption isotherms of the dyes were highly consistent with the Langmuir model, and the maximum adsorption capacity was 329.50 mg/g for methyl orange (MO) and 20.00 mg/g for rhodamine B (RhB). AL-CTS@MNPs showed good adsorption of anionic dyes (MO) in the pH range of 3-9. Meanwhile, the adsorbent AL-CTS@MNPs were also characterized, showing rough surface with specific surface areas of 37.38 m2/g, pore diameter of 95.8 nm and porosity of 17.62 %. The particle sizes were ranged from 800 µm to 1300 µm. The electrostatic attraction and π-π* electron donor-acceptor interactions were the main forces between the adsorbent and anionic dyes. While the electrostatic repulsive force between the adsorbent and the cationic dyes resulted in the non-absorption of MB by AL-CTS@MNPs. Subsequently, the adsorbent maintained a removal rate of >95 % after five adsorption-desorption cycles, demonstrating its excellent stability and recoverability. Ultimately, the prepared AL-CTS@MNPs illuminated good prospect on complex components dyes wastewater treatment.


Asunto(s)
Quitosano , Colorantes , Lignina , Contaminantes Químicos del Agua , Quitosano/química , Adsorción , Lignina/química , Colorantes/química , Colorantes/aislamiento & purificación , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/aislamiento & purificación , Aniones/química , Porosidad , Purificación del Agua/métodos , Concentración de Iones de Hidrógeno , Azul de Metileno/química , Azul de Metileno/aislamiento & purificación , Cinética , Aguas Residuales/química , Nanopartículas de Magnetita/química , Compuestos Azo
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