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Carboxymethyl cellulose (CMC) and polylactic acid (PLA) are recognized for their environmental friendliness. By merging them into a composite film, packaging solutions can be designed with good performance. Nonetheless, the inherent interface disparity between CMC and PLA poses a challenge, and there may be layer separation issues. This study introduces a straightforward approach to mitigate this challenge by incorporating tannin acid and ferric chloride in the fabrication of the CMC-PLA. The interlayer compatibility was improved by the in situ formation of a cohesive interface. The resulting CMC/TA-PLA/Fe multilayer film, devoid of any layer separation, exhibits exceptional mechanical strength, with a tensile strength exceeding 70 MPa, a high contact angle of 105°, and superior thermal stability. Furthermore, the CMC/TA-PLA/Fe film demonstrates remarkable efficacy in blocking ultraviolet light, effectively minimizing the discoloration of various wood surfaces exposed to UV aging.
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Efficient fractionation of lignocellulosic biomass in usable forms of hemicellulose, cellulose and lignin is very important for the sustainable lignocellulosic biorefinery. Herein, poplar sawdust was pretreated with an integrated process composed of acetic acid pre-hydrolysis (170 °C, 60 min) for xylo-oligosaccharides (XOS) production and mild deep eutectic solvent (90-130 °C, 60 min) post-delignification for recovering lignin fractions, resulting in easily hydrolyzed cellulose fraction. Results showed that, after integrated pretreatment and enzymatic hydrolysis, 51 % of xylan and 92 % of glucan in raw biomass could be converted to XOS (DP 2-6) and glucose, respectively, while 71 % of the original lignin could be recovered in DES solvent. The resulting XOS were proven to ensure the growth of probiotics, Bifidobacterium adolescentis. Besides, the lignin macromolecules recovered from DES solvent showed high-purity (around 95 %), low-molecular weight (Mw around 2000), small particle size (270-170 nm) and high-PhOH (3.08 mmol/g) content, which were likely relevant to the excellent antioxidant activity (RSI = 15.16) and adsorbent activity (Pb(II) 461.89 mg/g lignin). Finally, mass balance and energy analysis revealed that the integrated pretreatment could be used as a promising approach for the production of bio-based chemicals and materials from woody biomass.
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Lignina , Açúcares , Antioxidantes/farmacologia , Solventes Eutéticos Profundos , Ácido Acético , Solventes , Celulose , Oligossacarídeos , Hidrólise , BiomassaRESUMO
Acid pretreatment of biomass decomposed hemicelluloses but could not effectively remove lignin, which hindered biomass saccharification and carbohydrates utilization. In this work, 2-naphthol-7-sulfonate (NS) and sodium bisulfite (SUL) were simultaneously added to acid pretreatment, which was found to synergistically increase hydrolysis yield of cellulose from 47.9 % to 90.6 %. Based on in-depth investigations, strong linear correlations were observed between cellulose accessibility and lignin removal, fiber swelling, CrI/cellulose ratio, cellulose crystallite size, respectively, indicating that some physicochemical characteristics of cellulose played significant roles in improving cellulose hydrolysis yield. After enzymatic hydrolysis, 84 % carbohydrates could be liberated and recovered as fermentable sugars for subsequent utilization. Mass balance illustrated that for 100 kg raw biomass, 15.1 kg xylonic acid and 20.5 kg ethanol could be co-produced, indicating the efficient utilization of biomass carbohydrates.
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Celulose , Lignina , Biomassa , PolissacarídeosRESUMO
In this work, 1,4-butanediol (BDO) organosolv pretreatment was modified with different additives for efficient coproduction of fermentable sugars and lignin antioxidants from hardwood poplar and softwood masson pine. It was found additives more greatly improved pretreatment efficacy of softwood than hardwood. 3-hydroxy-2-naphthoic acid (HNA) addition introduced hydrophilic acid groups to lignin structure, while 2-naphthol-7-sulphonate (NS) addition promoted lignin removal, both improving cellulose accessibility for enzymatic hydrolysis. Consequently, BDO pretreatment with 90 mM acid and 2-naphthol-7-sulphonate addition achieved near complete cellulose hydrolysis (97.98%) and maximized sugar yield of 88.23% from masson pine at 2% cellulose and 20 FPU/g enzyme loading. More importantly, the recovered lignin possessed great antioxidant activity (RSI = 2.48), due to increased phenolic OH groups, reduced aliphatic OH groups and molecular weight. Results indicated the modified BDO pretreatment could significantly improve enzymatic saccharification of highly-recalcitrant softwood, while enabling coproduction of high-performance lignin antioxidants for full biomass utilization.
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Antioxidantes , Lignina , Açúcares , Celulose , Hidrólise , BiomassaRESUMO
BACKGROUND: Organosolv pretreatment is one of the most efficient methods for delignification and boosting biomass saccharification. As compared to typical ethanol organosolv pretreatments, 1,4-butanediol (BDO) organosolv pretreatment is a high-boiling-point solvent pretreatment, which can generate low pressure in the reactor during high temperature cooking that improves the operation safety. Although several studies showed that organosolv pretreatment can lead to effective delignification and enhancement in glucan hydrolysis, there has been no studies on acid- and alkali-catalyzed BDO pretreatment, as well as their comparison on promoting biomass saccharification and lignin utilization. RESULTS: It was shown that BDO organosolv pretreatment was more effective in removing lignin from poplar as compared with typical ethanol organosolv pretreatment under the same pretreatment conditions. HCl-BDO pretreatment with 40 mM acid loading led to 82.04% of original lignin removed from biomass, as compared to the lignin removal of 59.66% in HCl-Ethanol pretreatment. Besides, acid-catalyzed BDO pretreatment was more effective in improving the enzymatic digestibility of poplar than alkali-catalyzed BDO pretreatment. As a result, HCl-BDO with acid loading of 40 mM provided a good enzymatic digestibility of cellulose (91.16%) and the maximum sugar yield of 79.41% from original woody biomass. The linear correlations between physicochemical structure (e.g., fiber swelling, cellulose crystallinity, crystallite size, surface lignin coverage and cellulose accessibility) changes of BDO pretreated poplar and enzymatic hydrolysis were plotted to figure out the main factors that influenced biomass saccharification. Moreover, acid-catalyzed BDO pretreatment mainly brought about the phenolic hydroxyl (PhOH) groups formation in lignin structure, while alkali-catalyzed BDO pretreatment mostly led to the lower molecular weight of lignin. CONCLUSIONS: Results indicated that the acid-catalyzed BDO organosolv pretreatment could significantly improve enzymatic digestibility of the highly recalcitrant woody biomass. The great enzymatic hydrolysis of glucan resulted from increased cellulose accessibility, which mostly associated with the higher degree of delignification and hemicellulose solubilization, as well as the more increase in fiber swelling. Besides, lignin was recovered from the organic solvent, which could be used as natural antioxidants. The formation of phenolic hydroxyl groups in lignin structure and the lower molecular weight of lignin contributed to its greater radical scavenging capacity.
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Herein, a novel method for dissolving lignocellulose at room temperature is proposed by combining deep eutectic solvents (DES) pretreatment and subsequent dissolution in AlCl3/ZnCl2 aqueous system. Results showed that DES pretreatment could significantly increase the dissolubility of lignin-containing cellulose (CL) samples in AlCl3/ZnCl2 aqueous system. The dissolution ratio of the CL sample with 15.6 % lignin content in AlCl3/ZnCl2·3H2O solvent was as high as 90 %. Besides, the mechanism for the remarkable dissolution of CL samples in low water AlCl3/ZnCl2 aqueous solvent was also proposed. Moreover, the dissolved CL sample was regenerated for the production of lignocellulose films, which have excellent ultraviolet (UV) blocking, hydrophobic, mechanical strength, and natural degradation properties. In particular, the films could be completely naturally degraded after 10 days, which provided a promising way to prepare biodegradable lignocellulose materials, and to encourage the potential utilization of renewable lignocellulose in packaging industry.
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Celulose , Lignina , Lignina/química , Solubilidade , Celulose/química , Solventes , Água , HidróliseRESUMO
Most studies about the influence of lignin on enzymatic digestibility of lignocellulose have focused on the content and properties, but less on the detaching behavior of lignin. The samples were prepared from Pinus massoniana wood chips by kraft cooking followed by delignification using oxygen/alkali (KP-O) and chlorine dioxide (KP-D), respectively. Two oxidative delignified samples with a similar lignin content were subject to enzymatic hydrolysis at both pH of 5.0 and 5.5 to investigate the effects of lignin detached rate (LDR) on substrate enzymatic digestibility (SED). The LDRs and the SEDs from both samples increased with the enzymatic hydrolysis time, and the situations of KP-D were much higher than those of KP-O under the same enzymatic hydrolysis time. The results of enzymatic hydrolysis at an elevated pH of 5.5 and the changes in concentration of free cellulase of the two samples indicated that the lignin detaching increased the free cellulase concentration, and thus promoted the enzymatic digestibility. Moreover, lignin distribution analysis by X-ray photoelectric spectroscopy and confocal laser scanning microscopy indicated surface lignin being preferentially detached. This work provided a reference for rationally designing pretreatment strategies, which can improve the efficiency of enzyme hydrolysis of lignocellulosic biomass.
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Celulase , Lignina , Lignina/química , Hidrólise , Celulase/química , Carboidratos , Estresse OxidativoRESUMO
Volatile flavor of edible oils is an important quality index and factor affecting consumer choice. The purpose of this investigation was to characterize virgin Camellia oleifera seed oil (VCO) samples from different locations in southern China in terms of their volatile compounds to show the classification of VCO with respect to geography. Different samples from 20 producing VCO regions were collected in 2020 growing season, at almost the same maturity stage, and processed under the same conditions. Headspace solid-phase microextraction (HS-SPME) with a gas chromatography-mass spectrometer system (GC-MS) was used to analyze volatile compounds. A total of 348 volatiles were characterized, including aldehydes, ketones, alcohols, acids, esters, alkenes, alkanes, furans, phenols, and benzene; the relative contents ranged from 7.80-58.68%, 1.73-12.52%, 2.91-37.07%, 2.73-46.50%, 0.99-12.01%, 0.40-14.95%, 0.00-27.23%, 0.00-3.75%, 0.00-7.34%, and 0.00-1.55%, respectively. The VCO geographical origins with the largest number of volatile compounds was Xixiangtang of Guangxi (L17), and the least was Beireng of Hainan (L19). A total of 23 common and 98 unique volatile compounds were detected that reflected the basic and characteristic flavor of VCO, respectively. After PCA, heatmap and PLS-DA analysis, Longchuan of Guangdong (L8), Qingshanhu of Jiangxi (L16), and Panlong of Yunnan (L20) were in one group where the annual average temperatures are relatively low, where annual rainfalls are also low. Guangning of Guangdong (L6), Yunan of Guangdong (L7), Xingning of Guangdong (L9), Tianhe of Guangdong (L10), Xuwen of Guangdong (L11), and Xiuying of Hainan (L18) were in another group where the annual average temperatures are relatively high, and the altitudes are low. Hence, volatile compound distributions confirmed the differences among the VCO samples from these geographical areas, and the provenance difference evaluation can be carried out by flavor.
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Camellia/química , Óleos de Plantas/química , Sementes/química , Compostos Orgânicos Voláteis/química , Cromatografia Gasosa-Espectrometria de Massas , Geografia , Óleos de Plantas/análise , Microextração em Fase Sólida , Compostos Orgânicos Voláteis/análiseRESUMO
BACKGROUND: Ethanol organosolv (EOS) pretreatment is one of the most efficient methods for boosting biomass saccharification as it can achieve an efficient fractionation of three major constituents in lignocellulose. However, lignin repolymerization often occurs in acid EOS pretreatment, which impairs subsequent enzymatic hydrolysis. This study investigated acid EOS pretreatment assisted by carbocation scavenger (2-naphthol, 2-naphthol-7-sulfonate, mannitol and syringic acid) to improve biomass fractionation, coproduction of fermentable sugars and lignin adsorbents. In addition, surface barrier effect of lignin on cellulose hydrolysis was isolated from unproductive binding effect of lignin, and the analyses of surface chemistry, surface morphology and surface area were carried out to reveal the lignin inhibition mitigating effect of various additives. RESULTS: Four different additives all helped mitigate lignin inhibition on cellulose hydrolysis in particular diminishing surface barrier effect, among which 2-naphthol-7-sulfonate showed the best performance in improving pretreatment efficacy, while mannitol and syringic acid could serve as novel green additives. Through the addition of 2-naphthol-7-sulfonate, selective lignin removal was increased up to 76%, while cellulose hydrolysis yield was improved by 85%. As a result, 35.78 kg cellulose and 16.63 kg hemicellulose from 100 kg poplar could be released and recovered as fermentable sugars, corresponding to a sugar yield of 78%. Moreover, 22.56 kg ethanol organosolv lignin and 17.53 kg enzymatic hydrolysis residue could be recovered as lignin adsorbents for textile dye removal, with the adsorption capacities of 45.87 and 103.09 mg g-1, respectively. CONCLUSIONS: Results in this work indicated proper additives could give rise to the form of less repolymerized surface lignin, which would decrease the unproductive binding of cellulase enzymes to surface lignin. Besides, the supplementation of additives (NS, MT and SA) resulted in a simultaneously increased surface area and decreased lignin coverage. All these factors contributed to the diminished surface barrier effect of lignin, thereby improving the ease of enzymatic hydrolysis of cellulose. The biorefinery process based on acidic EOS pretreatment assisted by carbocation scavenger was proved to enable the coproduction of fermentable sugars and lignin adsorbents, allowing the holistic utilization of lignocellulosic biomass for a sustainable biorefinery.
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In this work, the beneficial effect of carbocation scavenger additives on hardwood pretreatment was revealed by significantly improved biomass saccharification: cellulose hydrolysis yield was increased by over 15% after steam pretreatment of poplar, while that was enhanced by more than 48% after dilute acid pretreatment. Besides, the relative contributions of lignin towards enzyme binding and physical barrier effect for proposed mechanisms were quantified. Results indicated that the addition of carbocation scavenger, 2-naphthol-7-sulfonate, resulted in acid groups incorporation of 62.36â¯mmol/kg to lignin, which mitigated enzyme non-productive binding. Moreover, enlarged biomass porosity and reduced surface lignin coverage were detected through BET and XPS analysis, respectively, which mostly related to the diminished physical barrier effect of lignin. As a result, the lignin inhibitions were significantly suppressed through the addition of carbocation scavenger, giving rise to significantly improved enzymatic hydrolysis of hardwood.
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Celulose , Lignina , Biomassa , Hidrólise , VaporRESUMO
This study aims to enhance the quality of biofuel through microwave torrefaction pretreatment for lignin. Low density polyethylene (LDPE) was added as a hydrogen source during microwave co-pyrolysis along with the microwave-torrefied lignin (MTL). The thermal degradation behavior and kinetic study of MTL co-pyrolysis with LDPE by microwave-assisted heating was investigated as well. The results indicated that the hydrocarbon content in the bio-oil obtained from microwave co-pyrolysis of MTL and LDPE increased significantly (about 80%). It was also noticed that the aromatic hydrocarbon content increased from 1.94% to 22.83% with the addition of LDPE. Thermal behavior analysis and reaction kinetic study showed that the addition of LDPE into MTL had the effect of promoting thermal degradation and improving reaction rate during microwave-assisted pyrolysis.
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Hidrocarbonetos/química , Lignina/química , Óleos de Plantas/química , Polietileno/química , Polifenóis/química , Temperatura Alta , Cinética , Micro-Ondas , PiróliseRESUMO
This work proposed an integrated process based on alkali-sulfite (AlkSul) pretreatment to coproduce fermentable sugars and lignin adsorbents from hardwood. Different from conventional liquid hot water (LHW) pretreatment, this pretreatment improved cellulose accessibility through selective lignin removal and modification, resulting in significantly enhanced biomass saccharification. Over 75% of the original cellulose and hemicellulose was released and could be recovered as fermentable sugars after pretreatment and subsequent enzymatic hydrolysis. Meanwhile, lignin residues from pretreatment hydrolysate and enzymatic hydrolysate showed lead ions adsorption capacities of 156.25 and 68.49â¯mg/g, respectively, indicating both streams of lignin residues were favorable adsorbents for heavy metal ions. The improved adsorption capacity of lignin residues was primarily due to the lignin modification as sulfur-containing functional groups incorporation during the integrated pretreatment. Results demonstrated the integrated alkali-sulfite pretreatment improved biomass saccharification, while coproducing lignin adsorbents for wastewater treatment, which can promote the sustainability of lignocellulosic biorefinery.
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Lignina , Açúcares , Biomassa , Celulose , HidróliseRESUMO
Converting lignin into value-added products in current lignocellulosic biorefineries has been challenging, which in turn restricts the commercialization of many lignocellulosic biorefineries. In this work, a two-stage alkali-oxygen assisted liquid hot water pretreatment (AlkOx) was proposed as the first step of biorefinery. This alkali-oxygen pretreatment facilitated biomass fractionation by solubilizing majority of lignin in water-soluble fraction, while remaining most of cellulose and hemicellulose in water-insoluble fraction. As a result, biomass saccharification was significantly improved by selective removal and oxidative modification of lignin through alkali-oxygen pretreatment. Moreover, lignin residues from both pretreatment hydrolysate and enzymatic hydrolysate were shown to be favorable adsorbents for Pb(II) ions, with adsorption capacity of 263.16 and 90.91â¯mg/g, respectively. Results demonstrated that this integrated process could not only improve biomass saccharification but also enable lignin valorization, which encouraged the holistic utilization of lignin residues as part of an integrated biorefinery.
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Biomassa , Celulose/metabolismo , Lignina/metabolismo , Metais Pesados/farmacologia , Oxigênio/química , Álcalis , Lignina/química , Açúcares/metabolismoRESUMO
An inhibitor-tolerance strain, Bacillus coagulans GKN316, was developed through atmospheric and room temperature plasma (ARTP) mutation and evolution experiment in condensed dilute-acid hydrolysate (CDH) of corn stover. The fermentabilities of other hydrolysates with B. coagulans GKN316 and the parental strain B. coagulans NL01 were assessed. When using condensed acid-catalyzed steam-exploded hydrolysate (CASEH), condensed acid-catalyzed liquid hot water hydrolysate (CALH) and condensed acid-catalyzed sulfite hydrolysate (CASH) as substrates, the concentration of lactic acid reached 45.39, 16.83, and 18.71 g/L by B. coagulans GKN316, respectively. But for B. coagulans NL01, only CASEH could be directly fermented to produce 15.47 g/L lactic acid. The individual inhibitory effect of furfural, 5-hydroxymethylfurfural (HMF), vanillin, syringaldehyde and p-hydroxybenzaldehyde (pHBal) on xylose utilization by B. coagulans GKN316 was also studied. The strain B. coagulans GKN316 could effectively convert these toxic inhibitors to the less toxic corresponding alcohols in situ. These results suggested that B. coagulans GKN316 was well suited to production of lactic acid from undetoxified lignocellulosic hydrolysates.
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Bacillus/metabolismo , Microbiologia Industrial , Ácido Láctico/biossíntese , Zea mays/química , Bacillus/genética , Benzaldeídos/química , Biomassa , Reatores Biológicos , Fermentação , Furaldeído/análogos & derivados , Furaldeído/química , Glucose/química , Hidrólise , Lignina/química , Mutação , Temperatura , Água/química , Xilose/químicaRESUMO
With the goal of enhancing overall carbohydrate recovery and reducing enzyme loading refiner mechanical pulping and steam pretreatment (210°C, 5 min) were used to pretreat poplar wood chips. Neutral sulphonation post-treatment indicated that, although the lignin present in the steam pretreated substrate was less reactive, the cellulose-rich, water insoluble component was more accessible to cellulases and Simons stain. This was likely due to lignin relocation as the relative surface lignin measured by X-ray photoelectron spectroscopy increased from 0.4 to 0.8. The integration of sulphite directly into steam pretreatment resulted in the solubilisation of 60% of the lignin while more than 80% of the carbohydrate present in the original substrate was recovered in the water insoluble fraction after Na2CO3 addition. More than 80% of the sugars present in the original cellulose and xylan could be recovered after 48 h using an enzyme loading of 20 mg protein/g cellulose at a 10% substrate concentration.
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Carboidratos/química , Lignina/química , Populus/química , Vapor , Madeira/química , Celulase/química , Celulose/química , Endopeptidases , Esterases/análise , Hidrólise , Sulfitos/química , Água/análiseRESUMO
An integrated process of enzymatic hydrolysis and fermentation was investigated for high ethanol production. The combination of enzymatic hydrolysis at low substrate loading, liquid fermentation of high sugars concentration and solid state fermentation of enzymatic hydrolysis residue was beneficial for conversion of steam explosion pretreated corn stover to ethanol. The results suggested that low substrate loading hydrolysis caused a high enzymatic hydrolysis yield; the liquid fermentation of about 200g/L glucose by Saccharomyces cerevisiae provided a high ethanol concentration which could significantly decrease cost of the subsequent ethanol distillation. A solid state fermentation of enzymatic hydrolysis residue was combined, which was available to enhance ethanol production and cellulose-to-ethanol conversion. The results of solid state fermentation demonstrated that the solid state fermentation process accompanied by simultaneous saccharification and fermentation.
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Biocombustíveis/análise , Biotecnologia/métodos , Carboidratos/química , Celulase/metabolismo , Etanol/metabolismo , Fermentação , beta-Glucosidase/metabolismo , Metabolismo dos Carboidratos , Hidrólise , Saccharomyces cerevisiae/enzimologia , Soluções , Temperatura , Fatores de TempoRESUMO
Bioconversion of undetoxified hemicellulosic hydrolyzate from steam-exploded corn stover was investigated with a domesticated Pichia stipitis CBS 5776. The countercurrent washing was applied to recover sugars from the steam-exploded corn stover, which could enrich sugars in washing liquor and give an efficient saving of water. Acid concentration, reaction temperature, and time were optimized for the acid post-hydrolysis of oligosaccharides in steam-exploded prehydrolyzate by a central composite design and response surface methodology. The domestication of P. stipitis to the hydrolyzate resulted in improving sugar consumption and ethanol yield by gradually increasing the ratio of hydrolyzate in the medium. Recycling utilization of the domesticated yeast demonstrated that the yeast kept a stable ability of fermenting both hexose and pentose in the undetoxified hydrolyzate. The sugar consumption and ethanol yield were over 90 and 80 %, respectively.