Depolymerization Of Cellulose Research Articles

Juncus rigidus high biomass and cellulose productivity under wastewater salinity stress - A paradigm shift to the valorization of RO reject water

The use of water purifiers is intensively catching up and disposing of reverse osmosis reject water is of great concern. Reject water management using conventional methods is costly and harmful to the environment. To address this issue, the present study aims to utilize reverse osmosis reject wastewater using an eco-friendly approach. Juncus rigidus was treated with reject wastewater containing different salinity levels. Wastewater-treated plant dry biomass increased with increasing reject water salinity, and 625.3 g dry biomass recovered in treatment-B (~18,520 ppm). However, ~23,220 ppm wastewater salinity was lethal to the plants. The cellulose was extracted by alkali hydrolysis. The cellulose content in the wastewater-treated biomass was significantly higher in Treatment-B compared to both the control and Treatment-A (~12,744 ppm). The water salinity enhanced the cellulose (26.49 %) production in J. rigidus. Cellulose purity was confirmed using spectroscopic and thermogravimetric means. XRD shows highest crystallinity Index (77.29) with a d-spacing of 4.7 Å and 5.7 nm crystallite size in treatment-B. FTIR results reveal well-defined relevant peaks for OH, CH, CO, CH2, C-O-C, CO groups in treatment-B cellulose. Salinity impacts carboxyl groups in treatment B cellulose with a sharper and intense peak at 1644 cm−1 responsible for water absorption. Treatment-B exhibits higher thermal stability due to increased crystallinity. DSC shows endothermic depolymerization of cellulose with distinct peaks for different treatments. Morphological traits got better with increasing salinity with no adverse effect on cellulose. Salinity moderately affected the water absorption capacity of cellulose. All cellulose samples were devoid of gram-negative bacteria known by microbial test. This pioneering work underscores the plant's remarkable capacity not only to accomplish the circular economy by the valorization of wastewater obtained from various water purifiers for Juncus cultivation for cellulose production for diverse applications but also to generate income from wastewater.

Pure lignin induces overexpression of cytochrome P450 (CYP) encoding genes and brings insights into the lignocellulose depolymerization by Trametes villosa

Trametes villosa is a remarkable white-rot fungus (WRF) with the potential to be applied in lignocellulose conversion to obtain chemical compounds and biofuels. Lignocellulose breakdown by WRF is carried out through the secretion of oxidative and hydrolytic enzymes. Despite the existing knowledge about this process, the complete molecular mechanisms involved in the regulation of this metabolic system have not yet been elucidated. Therefore, in order to understand the genes and metabolic pathways regulated during lignocellulose degradation, the strain T. villosa CCMB561 was cultured in media with different carbon sources (lignin, sugarcane bagasse, and malt extract). Subsequently, biochemical assays and differential gene expression analysis by qPCR and high-throughput RNA sequencing were carried out. Our results revealed the ability of T. villosa CCMB561 to grow on lignin (AL medium) as the unique carbon source. An overexpression of Cytochrome P450 was detected in this medium, which may be associated with the lignin O-demethylation pathway. Clusters of up-regulated CAZymes-encoding genes were identified in lignin and sugarcane bagasse, revealing that T. villosa CCMB561 acts simultaneously in the depolymerization of lignin, cellulose, hemicellulose, and pectin. Furthermore, genes encoding nitroreductases and homogentisate-1,2-dioxygenase that act in the degradation of organic pollutants were up-regulated in the lignin medium. Altogether, these findings provide new insights into the mechanisms of lignocellulose degradation by T. villosa and confirm the ability of this fungal species to be applied in biorefineries and in the bioremediation of organic pollutants.

Genome-Wide Identification of Expansins in Rubus chingii and Profiling Analysis during Fruit Ripening and Softening

Improving fruit size or weight, firmness, and shelf life is a major target for horticultural crop breeding. It is associated with the depolymerization and rearrangement of cell components, including pectin, hemicellulose, cellulose, and other structural (glyco)proteins. Expansins are structural proteins to loosen plant cell wall polysaccharides in a pH-dependent manner and play pivotal roles in the process of fruit development, ripening, and softening. Rubus chingii Hu, a unique Chinese red raspberry, is a prestigious pharmaceutical and nutraceutical dual-function food with great economic value. Thirty-three RchEXPs were predicted by genome-wide identification in this study, containing twenty-seven α-expansins (EXPAs), three β-expansins (EXPBs), one expansin-like A (EXPLA), and two expansin-like B (EXPLBs). Subsequently, molecular characteristics, gene structure and motif compositions, phylogenetic relationships, chromosomal location, collinearity, and regulatory elements were further profiled. Furthermore, transcriptome sequencing (RNA-seq) and real-time quantitative PCR assays of fruits from different developmental stages and lineages showed that the group of RchEXPA5, RchEXPA7, and RchEXPA15 were synergistically involved in fruit expanding and ripening, while another group of RchEXPA6 and RchEXPA26 might be essential for fruit ripening and softening. They were regulated by both abscisic acid and ethylene and were collinear with phylogenetic relationships in the same group. Our new findings laid the molecular foundation for improving the fruit texture and shelf life of R. chingii medicinal and edible fruit.

Acetic acid as a protic solvent for reducing sulphuric acid concentrations in the production of cellulose nanocrystals alongside transition metal co-catalysts

Cellulose nanocrystals (CNC) conventionally involve highly concentrated sulphuric acid, which typically resulted in the formation of undesirable by-products. Although less corrosive mineral acids have been explored as alternatives, high concentrations are still required. In this study, CNC was successfully isolated from Leucaena leucocephala wood using mild sulphuric acid with acetic acid as protic solvent, and it was further studied with the addition of Lewis acids in the form of multivalent transition metal salts as co-catalyst. Selected divalent and trivalent transition metal salts including (Cr(NO3)3, Fe(NO3)3, Co(NO3)2, and Ni(NO3)2) were investigated. The morphology, chemical structure, particle size, and physicochemical properties of the CNCs were determined. Controlled depolymerization of cellulose was observed using transmission electron microscopy (TEM). Rod-like morphology for all CNCs was obtained during the hydrolysis process with the smallest CNC particles found at an average length of 278.1 ± 35.1 nm and a diameter of 13.4 ± 3.0 nm. The results showed that higher valence state metal ions resulted in better cellulose hydrolysis efficiency. In addition, the use of transition metal salt as a co-catalyst improved production efficiency and minimised carbonization of CNC while maintaining desired crystallinity and thermal properties.

Molecular mechanism of cellulose depolymerization by the two-domain BlCel9A enzyme from the glycoside hydrolase family 9

Carbohydrate-active enzymes from the glycoside hydrolase family 9 (GH9) play a key role in processing lignocellulosic biomass. Although the structural features of some GH9 enzymes are known, the molecular mechanisms that drive their interactions with cellulosic substrates remain unclear. To investigate the molecular mechanisms that the two-domain Bacillus licheniformis BlCel9A enzyme utilizes to depolymerize cellulosic substrates, we used a combination of biochemical assays, X-ray crystallography, small-angle X-ray scattering, and molecular dynamics simulations. The results reveal that BlCel9A breaks down cellulosic substrates, releasing cellobiose and glucose as the major products, but is highly inefficient in cleaving oligosaccharides shorter than cellotetraose. In addition, fungal lytic polysaccharide oxygenase (LPMO) TtLPMO9H enhances depolymerization of crystalline cellulose by BlCel9A, while exhibiting minimal impact on amorphous cellulose. The crystal structures of BlCel9A in both apo form and bound to cellotriose and cellohexaose were elucidated, unveiling the interactions of BlCel9A with the ligands and their contribution to substrate binding and products release. MD simulation analysis reveals that BlCel9A exhibits higher interdomain flexibility under acidic conditions, and SAXS experiments indicate that the enzyme flexibility is induced by pH and/or temperature. Our findings provide new insights into BlCel9A substrate specificity and binding, and synergy with the LPMOs.

Evaluation of the application of chemically adapted gourd fibre in polyester composite fabrication

Purpose Gourd fibres (GF) are a natural biodegradable fibre material with excellent mechanical properties and high tensile strength. The use of natural fibres in composite materials has gained popularity in recent years due to their various advantages, including renewability, low cost, low density and biodegradability. Gourd fibre is one such natural fibre that has been identified as a potential reinforcement material for composites. However, it has low surface energy and hydrophobic nature, which makes it difficult to bond with matrix materials such as polyester. To overcome this problem, chemically adapted gourd fibre has been proposed as a solution. Chemical treatment is one of the most widely used methods to improve the properties of natural fibres. This research evaluates the feasibility and effectiveness of incorporating chemically adapted gourd fibre into polyester composites for industrial fabrication. The purpose of this study is to examine the application of chemically modified GF in the production of polyester composite engineering materials. Design/methodology/approach This work aims to evaluate the effectiveness of chemically adapted gourd fibre in improving the adhesion of gourd fibre with polyester resin in composite fabrication by varying the GF from 5 to 20 wt.%. The study involves the preparation of chemically treated gourd fibre through surface modification using sodium hydroxide (NaOH), permanganate (KMnO4) and acetic acid (CH3COOH) coupling agents. The mechanical properties of the modified fibre and composites were investigated. It was then characterized using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) to determine the changes in surface morphology and functional groups. Findings FTIR characterization showed that NaOH treatment caused cellulose depolymerization and caused a significant increase in the hydroxyl and carboxyl groups, showing improved surface functional groups; KMnO4 treatment oxidized the fibre surface and caused the formation of surface oxide groups; and acetic acid treatment induced changes that primarily affected the ester and hydroxyl groups. SEM study showed that NaOH treatment changed the surface morphology of the gourd fibre, introduced voids and reduced hydrophilic tendencies. The tensile strength of the modified gourd fibres increased progressively as the concentration of the modification chemicals increased compared to the untreated fibres. Originality/value This work presents the designed composite with density, mechanical properties and microstructure, showing remarkable improvements in the engineering properties. An 181.5% improvement in tensile strength and a 56.63% increase in flexural strength were got over that of the unreinforced polyester. The findings from this work will contribute to the understanding of the potential of chemically adapted gourd fibre as a reinforcement material for composites and provide insights into the development of sustainable composite materials.

Systematic investigation of the mechanocatalytic partial depolymerization of cellulose towards oligomeric glycans

The mechanocatalytic depolymerization of cellulose to oligomeric glycans in a planetary ball mill is systematically studied based on reaction parameters such as acid content, filling level, rotational speed and grinding duration.

Underlying Mechanisms on the Controlled Depolymerization of High-Loading Cellulose in Water Promoted by Cetyltrimethylammonium Bromide

Underlying Mechanisms on the Controlled Depolymerization of High-Loading Cellulose in Water Promoted by Cetyltrimethylammonium Bromide

Pore-scale study of phase transitions and humins coking in cellulose hydrolyzed to levulinic acid

Hydrothermal depolymerization of cellulose has generated tremendous excitement as a promising pathway to sustainable chemistry. Among these biomass products, levulinic acid (LA), as one of the most promising platform chemicals with rich chemistry, can be used as various fuel additives or further refined into sustainable biofuel and high-value chemicals. However, hydrothermal conversion of cellulose into chemicals involves complex physicochemical processes, suffering currently from insufficient understanding of processes coupling mechanisms and carbon deposition caused by coking side reaction. Here, we developed a pore-scale multiphase reactive transport model based on the lattice Boltzmann method (LBM), coupling the multicomponent multiphase flow, heterogeneous reaction, cellulose dissolution, and humins coking, to systematically explore the conversion of cellulose to LA over acid catalyst. A relationship with a monotonic increase between the coking appearance time and H+ concentration has been found when the coking amount shows a linear decrease over acid concentration. Our results underscore the importance of in-depth elucidation of process coupling mechanisms for the establishment of efficient hydrothermal preparation strategies from cellulose to platform chemicals.

High Lewis acidity catalyst for direct depolymerization of microcrystalline cellulose to 5- hydroxymethylfurfural: Reaction optimization by central composite design

In direct conversion process of cellulose to 5-hydroxymethylfurfural (5-HMF), undesirable degradation inevitably occurs in the presence of Brønsted acid. Here, a carbonaceous catalyst was synthesized by grafting phosphotungstic acid to directly depolymerize microcrystalline cellulose (MCC) to 5-HMF. This catalyst exhibits high Lewis acidity (43.10 μmol g⁻1) and low Brønsted acidity (4.15 μmol g⁻1) with pyridine as reference compound. To comprehensively analyze the factors affecting MCC depolymerization, central composite design and response surface methodology techniques, incorporating variables such as reaction time, reaction temperature, catalyst dosage and MCC dosage. The highest yield of 5-HMF, 5.88 %, was obtained after 4.90 h at 171 °C using 45 mg of catalyst and 50 mg of MCC in biphasic system consisting of 1-butyl-3-methylimidazole chloride ([BMIM]Cl) and 2-sec-butylphenol. The catalyst was easily recovered and reused five times without a significant loss of catalytic activity. This work highlights the promise of efficient biomass refining by synergizing catalysts with high Lewis acidity and low Brønsted acidity in the biphasic system.

Comparative analysis of Chrysoporthe cubensis exoproteomes and their specificity for saccharification of sugarcane bagasse

The phytopathogenic fungus Chrysoporthe cubensis is a relevant source of lignocellulolytic enzymes. This work aimed to compare the profile of lignocellulose-degrading proteins secreted by C. cubensis grown under semi-solid state fermentation using wheat bran (WB) and sugarcane bagasse (SB). The exoproteomes of the fungus grown in wheat bran (WBE) and sugarcane bagasse (SBE) were qualitative and quantitatively analyzed by liquid chromatography-electrospray ionization tandem mass spectrometry (LC–ESI–MS/MS). Data are available via ProteomeXchange with identifier PXD046075. Label-free proteomic analysis of WBE and SBE showed that the fungus produced a spectrum of carbohydrate-active enzymes (CAZymes) with exclusive characteristics from each extract. While SBE resulted in an enzymatic profile directed towards the depolymerization of cellulose, the enzymes in WBE were more adaptable to the degradation of biomass rich in hemicellulose and other non-lignocellulosic polymers. Saccharification of alkaline pre-treated sugarcane bagasse with SBE promoted glucose release higher than commercial cocktails (8.11 g L−1), while WBE promoted the higher release of xylose (5.71 g L−1). Our results allowed an in-depth knowledge of the complex set of enzymes secreted by C. cubensis responsible for its high lignocellulolytic activity and still provided the identification of promising target proteins for biotechnological applications in the context of biorefinery.

Aspergillus fumigatus Lytic Polysaccharide Monooxygenase AfLPMO9D: Biochemical Properties and Photoactivation of a Multi-Domain AA9 Enzyme

Lytic polysaccharide monooxygenases (LPMOs) are critical players in enzymatic deconstruction of cellulose. A number of LPMOs have been identified at a genomics level; however, they still need to be characterized and validated for use in industrial processes aimed at cellulose deconstruction. In the present study, we biochemically characterized a new LPMO, a member of auxiliary activities family 9 (AA9) from the filamentous fungus Aspergillus fumigatus (AfLPMO9D). This LPMO demonstrated higher efficiency against amorphous cellulose as compared to more recalcitrant forms of cellulose such as bacterial cellulose and Avicel. AfLPMO9D has a capacity to oxidize the substrate at either the C1 or C4 positions, with pH-dependent regioselectivity. Photoactivation experiments demonstrated that light-stimulated chlorophyllin triggers AfLPMO9D activation without requirements of an external electron donor. AfLPMO9D is capable of boosting phosphoric acid-swollen cellulose depolymerization via GH7 endoglucanase and cellobiohydrolase. The results of the present study might help to elucidate the role of different LPMOs in cellulosic fiber deconstruction.

Light-Driven Depolymerization of Cellulosic Biomass into Hydrocarbons.

Cellulose and hemicellulose are the main constituents of lignocellulosic biomass. Chemical derivatization of lignocellulosic biomass leads to a range of C5 and C6 organic compounds. These C5 and C6 compounds are valuable precursors (or fine chemicals) for developing sustainable chemical processes. Therefore, depolymerization of cellulose and hemicellulose is essential, leading to the development of various materials that have applications in biomaterial industries. However, most depolymerized processes for cellulose have limited success because of its structural quality: crystallinity, high hydrogen-bond networking, and mild solubility in organic and water. As a result, various chemical treatments, acidic (mineral or solid acids) and photocatalysis, have developed. One of the significant shortcomings of acidic treatment is that the requirement for high temperatures increases the commercial end cost (energy) and hampers product selectivity. For example, a catalyst with prolonged exposure to high temperatures damages the catalyst surface over time; therefore, it cannot be used for iterative cycles. Photocatalysts provide ample application to overcome such flaws as they do not require high temperatures to perform efficient catalysis. Various photocatalysts have shown efficient cellulosic biomass conversion into its C6 and C5 hydrocarbons and the production of hydrogen (as a green energy component). For example, TiO2-based photocatalysts are the most studied for biomass valorization. Herein, we discussed the feasibility of a photocatalyst with application to cellulosic biomass hydrolysis.

Effective hydrothermal-enzymatic sequential process of agave bagasse enhances saccharification and methane production

The efficiency of enzymatic saccharification of lignocellulosic biomass is a key step for biofuels production in the biochemical biorefineries. A novel sequential process, hydrothermal pretreatment followed by enzymatic hydrolysis, of agave bagasse was investigated to improve the release of sugars and the methane production. After optimization of the hydrothermal pretreatment by surface response methodology, a hemicellulose removal of 93.6% was obtained at 180 °C/50 min. Hemicellulose removal enhanced cellulose depolymerization during the enzymatic hydrolysis of the pretreated bagasse by 2.3 times as compared to the untreated bagasse. The single-stage batch methane production of the hydrothermal and enzymatic hydrolysates were 0.223 ± 0.02 NL CH4/ g CODadd and 0.305 ± 0.03 NL CH4/g CODadd respectively, indicating a higher biodegradability of the enzymatic hydrolysate. The combined energy recovered from the hydrothermal and enzymatic hydrolysates was 3.4 times greater than that recovered from untreated agave bagasse hydrolysate. Also, the combined energy recovery was higher than the energy recovery reported in the literature for agave bagasse pretreated with other chemical and hydrothermal pretreatments. Overall, this study enhanced the saccharification efficiency and biodegradability of polysaccharides present in agave bagasse through efficient saccharification of cellulose and hemicellulose. This was reflected in a high value of combined energy recovery efficiency (54.1%) in the form of methane.

Assessing the compatibility of choline-based deep eutectic solvents for the structural stability and activity of cellulase: Enzyme sustain at high temperature

As a new generation of ‘green solvents’ deep eutectic solvents (DESs) represents a promising alternative to the conventional solvents. Their environmental-benign nature and designer properties promote their utility in biocatalysis. Enzymes are marginally stable when exposed to physical/chemical disturbances. One such enzyme is cellulase which is a propitious catalyst for the depolymerization of cellulose under mild conditions. Therefore, their stability is a prerequisite condition to match demands of biorefineries. To address this issue of low stability, activity and thermal denaturation of cellulase, there is a need to find a sustainable and suitable co-solvent that is biocompatible with enzymes ultimately to facilitate their application in bio-industries. In this regard, we synthesized three choline-based DESs, choline chloride (ChCl)-glycerol, ChCl-ethylene glycol and ChCl-lactic acid and employed them to analyze their suitability for cellulase. The present study systematically evaluates the influence of the mentioned DESs on stability, activity and thermal stability of cellulase with the help of various spectroscopic techniques. The spectroscopic analysis revealed that the structural stability and activity of the enzyme were improved in presence of ChCl-glycerol and ChCl-ethylene glycol. The thermal stability was also very well maintained in both the DESs. Interestingly, the relative activity of cellulase was >80 % even after incubation at 50 °C after 48 h for both the DESs. This activity preservation behaviour was more pronounced for ChCl-ethylene glycol than ChCl-glycerol. Moreover, temperature variations studies also reveal promising results by maintain conformational intactness. On the other side, ChCl-lactic acid showed a deleterious effect on the enzyme both structurally as well as thermally. The dynamic light scattering (DLS) analysis provides more specific information about the negative influence of ChCl-lactic acid towards cellulase native structure. This DES induces unavoidable alterations in the enzyme structure which leads to the unfolding of enzyme, ultimately, destabilizing it. Overall, our results present a physical insight into how the enzyme stability and activity depend on the nature of DES. Also, the findings will help to facilitate the development and application of DESs as biocatalytic process.

Cellulose‐Assisted Formation of 2D Hybrid Halide Perovskite Nanocrystals with Enhanced Stability for Light‐Emitting Devices

AbstractA common approach to enhance the stability of metal halide perovskites (MHPs) implemented in optical and optoelectronic devices is to incorporate polymer additives into the perovskite layer. A β‐(1,4) cellulose oligosaccharide (COS) synthesized by mechanocatalytic depolymerization of cellulose has been incorporated to films of the BA2MA4Pb5I16 (BA = n‐butylammonium and MA = methylammonium) two‐dimensional (2D) Ruddlesden‐Popper (RP) hybrid perovskite. Scanning Electron Microscopy (SEM) images displayed a three‐fold reduction of the 2D RP perovskite grains (≈30–40 nm), close to the quantum confinement scale. The analysis of the dark J–V curves of single carrier devices by using the space charge limited current (SCLC) method resulted in a rise of the defect concentration. A notable 14‐fold increase in the photoluminescence (PL) signal at high COS content is detected. Moreover, the analysis of the temperature dependence PL measurements (80–300 K) resulted in a larger exciton binding energy, Eb = 180 to 370 meV, at high COS content. Light emitting diodes of the 2D RP perovskites (PeLEDs) are fabricated w/o the COS compound. The stability test performed under operation (5 V) displays 20 times higher operational lifetimes at high COS content while the luminance is also increased in the devices with the COS compound.

The Use of Methanol Vapour for Effective Drying of Cellulose Insulation

The paper deals with a new method of drying cellulose insulation, which uses methanol vapour present in nitrogen as a drying medium. Compared to the insulation drying methods currently used in the industry, the method presented in the article has the following advantages: there is no cellulose depolymerization because there is no need to heat the insulation, there is no need to use large-size and energy-intensive dryers because the whole process takes place in the tank of the transformer. Important parameters of the drying process, such as methanol concentration in the nitrogen, flow rate, and process duration, were determined in four separate experiments. For the purposes of these experiments, a special system was constructed to control and measure the flow of drying medium. Controlling the flow rate of the carrier gas (nitrogen) made it possible to obtain different concentrations of methanol in nitrogen. Such values of concentration and flow rate were determined that allow drying of pressboard and paper in less than 144 h to a level lower than 1%.

Improving the Enzymatic Activity and Stability of a Lytic Polysaccharide Monooxygenase.

Lytic Polysaccharide Monooxygenases (LPMOs) are copper-dependent enzymes that play a pivotal role in the enzymatic conversion of the most recalcitrant polysaccharides, such as cellulose and chitin. Hence, protein engineering is highly required to enhance their catalytic efficiencies. To this effect, we optimized the protein sequence encoding for an LPMO from Bacillus amyloliquefaciens (BaLPMO10A) using the sequence consensus method. Enzyme activity was determined using the chromogenic substrate 2,6-Dimethoxyphenol (2,6-DMP). Compared with the wild type (WT), the variants exhibit up to a 93.7% increase in activity against 2,6-DMP. We also showed that BaLPMO10A can hydrolyze p-nitrophenyl-β-D-cellobioside (PNPC), carboxymethylcellulose (CMC), and phosphoric acid-swollen cellulose (PASC). In addition to this, we investigated the degradation potential of BaLPMO10A against various substrates such as PASC, filter paper (FP), and Avicel, in synergy with the commercial cellulase, and it showed up to 2.7-, 2.0- and 1.9-fold increases in production with the substrates PASC, FP, and Avicel, respectively, compared to cellulase alone. Moreover, we examined the thermostability of BaLPMO10A. The mutants exhibited enhanced thermostability with an apparent melting temperature increase of up to 7.5 °C compared to the WT. The engineered BaLPMO10A with higher activity and thermal stability provides a better tool for cellulose depolymerization.

Elucidation of Structure and Physical Properties of Pyrolytic Sugar Oligomers Derived from Cellulose Depolymerization/Dehydration Reactions: A Density Functional Theory Study

Fast pyrolysis of lignocellulosic materials is a promising research area to produce renewable fuels and chemicals. Dehydration is known to be among the most important reaction families during cellulose pyrolysis; water is the most important product. Together with water, dehydration reactions also form a range of poorly known oligomer species of varying molecular sizes, often collected as part of the bio-oil water-soluble (WS) fraction. In this work, we used electronic structure calculations to evaluate the relative thermodynamic stabilities of several oligomer species from cellulose depolymerization intermediates undergoing three consecutive dehydration events. A library of the thermodynamically favored candidate molecular structures was compiled. Results revealed that most of the water molecules are eliminated from the non-reducing end, forming thermodynamically more stable conjugated compounds. This is consistent with results reported in literature where dehydration reactions occur preferably at the non-reducing ends of oligomers. The theoretical Fourier-Transform Infrared Spectroscopy and NMR spectra of these proposed sugar oligomers conform qualitatively to the experimental result of pyrolytic sugars. Understanding their chemical structure could help to develop rational strategies to mitigate coke formation as sugars are often blamed to cause coke formation during bio-oil refining. The estimated physical–chemical properties (boiling point, melting point, Gibbs free energy of formation, enthalpy of formation, and solubility parameters among others) are also fundamental to conducting first-principles engineering calculations to design and analyze new pyrolysis reactors and bio-oil up-grading units.

Mechanistic role of γ-valerolactone co-solvent to promote ethyl levulinate production from cellulose transformation in ethanol

Direct utilization of cellulosic material to produce specialty chemicals such as levulinate ester could greatly increase biorefinery profitability, but low-level efficiency due to its structural nature limits the strategy for industrial deployment. We report herein that adding γ-valerolactone (GVL) co-solvent during the acid-catalyzed conversion of cellulose in ethanol leads to a high reaction rate and improved catalytic activity towards ethyl levulinate (EL) production. With GVL as the co-solvent (the volume ratio of GVL to ethanol in 1:4), the yield of EL highly enhanced from 31% to 56% under mild operating conditions (170 °C for 2 h) over a low loading Al(OTf)3 of 0.005 mol/L. The mechanistic role of GVL co-solvent to accelerate EL formation from cellulose has been fully elucidated via the combination of experimental and theoretical approaches. It demonstrates that GVL intervention not only favored the dissolution and depolymerization of cellulose, but also enabled the formation of Al species with higher acidity and catalytic activity by modulating the solvation environment, both of which are in charge of promoting cellulose conversion to EL. The activation energy barriers for cellulose depolymerization and glucoside alcoholysis have decreased by 30.8 kJ/mol and 24.8 kJ/mol, respectively. The understanding of this solvation effect can be employed to optimize the rate and yield for production of the versatile bio-based ester compound straight from cellulose valorization.