Lignocellulose Deconstruction Research Articles

DES-driven sustainable dual valorization of lignocellulose into carbon dots and porous biochar for effective wastewater remediation

Deep eutectic solvents (DES) are renowned for their effectiveness in deconstructing lignocellulose and extracting lignin, yet the challenges lie in lignin condensation and the disposal of the DES remnants after pretreatment. To overcome these issues, this work proposed a holistic strategy utilizing deep eutectic solvent (DES)-driven lignocellulose deconstruction to upgrade lignocellulose into nitrogen-doped carbon dots (CDs) and iron-decorated porous carbons, serving as photocatalysts and adsorbents, respectively. These nitrogen-doped CDs via the choline chloride/FeCl3 DES pretreatment exhibited abundant nitrogen/oxygen functional groups, enhancing photocatalytic activities and facilitating effective charge separation and transfer. The photocatalytic efficiency of the CDs on dyes reached 97 % under acidic conditions primarily, and free radical quenching experiments indicated that singlet oxygen was the dominant oxidant species. Moreover, the adsorption capabilities of Fe-decorated porous carbons for Congo red reached 2432.3 mg·g−1, surpassing most existing carbon materials. The adsorption mechanism was due to a synergistic effect including physical adsorption, coordination, hydrogen bonding, electrostatic, and π-π interactions. This study proposed a synergetic conversion of DES and lignocellulose into functional carbon materials for wastewater remediation, which inspired the development of a green and cost-effective biorefinery.

Sustainable pretreatment method of lignocellulosic depolymerization for enhanced ruminant productivity using laccase protein immobilized agarose beads

Laccase, the selectively lignin degrader, vital to the initiation of lignocellulosic deconstruction was immobilized onto activated agarose beads to increase its reuse potential. Laccase cross-linked beads (~ 3.42 mm) recorded a specific activity of 23 Umg− 1, retaining about 80.43% enzyme activity after 45 days of storage. The immobilization yield and efficiency were 89% and 97% respectively. The equilibrium data fitted the Freundlich equation (R2 = 0.9987) demonstrating multilayer adsorption and the presence of Cu, Fe, and S in the elemental analysis of immobilized beads established effective binding between activated agarose beads and the laccase protein. Characterization studies of the immobilized laccase-treated crop residues revealed significant differences in the lignin polymer after each treatment cycle. An increase in digestibility of 26.21% and 7.62% was observed in paddy and finger millet-treated straws respectively, over the controls corroborating efficient lignin depolymerization. The propitious performance of laccase beads authenticated in the batch enzymatic reactor to treat crop residues paves headway as a sustainable green technology in the deconstruction of crop residues for use as ruminant feed, augmenting productivity.

Distribution of xylan linked glucuronic acid labelled by molecularly imprinted polymers on pulp fiber surface

Efficiently utilization of plant resources is heavily restricted by the resistance of lignocellulose in plant cells, which is related to the interlinkages of lignocellulose components. Hemicellulose in plant cell wall is bound to cellulose by hydrogen bond and linked with lignin in lignin-carbohydrate complex (LCC). In the xylan chain of hemicellulose, glucuronic acid (GA) is a typical side-group, which provides clues for us to label and locate hemicellulose. The way to label GA on the surface of pulp fibers obtained from pulping process is benefit to explore the deconstruction of lignocellulose. Herein, a new visualization method, fluorescence modified molecularly imprinted polymers (MIP) were applied to recognize and locate GA on the pulp fiber surface. The method combining fluorescence imaging and integrated 3D fiber structure verified the feasibility of the MIP for specific GA recognition. The results showed that xylan (represented by GA) was closely attached to lignin, distributed along the inner wall of pulp fiber cells, and gradually taken off from the inside edge of fiber cells with the deconstruction of lignocellulose. This research provided a basis to develop visualization bioimaging technology to identify biomass components.

Fungal systems for lignocellulose deconstruction: From enzymatic mechanisms to hydrolysis optimization

AbstractLignocellulosic biomass is an abundant renewable feedstock, but its complex structure of lignocellulose poses barriers to its enzymatic hydrolysis and fermentation. Fungi possess diverse lignocellulolytic enzyme systems that synergistically deconstruct lignocellulose into soluble sugars for fermentation. This review elucidates recent advances in understanding the molecular mechanisms underpinning fungal degradation of lignocellulose. We analyze major enzyme classes tailored by fungi to depolymerize cellulose, hemicellulose, and lignin. Highlighted are the concerted actions and intimate partnerships between these biomass‐degrading enzymes. Current challenges impeding large‐scale implementation of enzymatic hydrolysis are discussed, along with emerging biotechnological opportunities. Advanced pretreatments, high‐throughput enzyme engineering platforms, and machine learning or artificial intelligence‐guided lignocellulolytic enzyme cocktail optimization represent promising ways to improve hydrolytic efficiencies. Elucidating the coordinated interplay and regulation of fungal lignocellulolytic machinery can facilitate optimization of fungal biotechnology platforms. Harnessing the efficiency of fungal biomass deconstruction promises to enhance the development of biorefinery processes for sustainable bioenergy.

Sugar Transport in Thermophiles: Bridging Lignocellulose Deconstruction and Bioconversion.

Biomass degrading thermophiles play an indispensable role in building lignocellulose-based supply chains. They operate at high temperatures to improve process efficiencies and minimize mesophilic contamination, can overcome lignocellulose recalcitrance through their native carbohydrate-active enzyme (CAZyme) inventory, and can utilize a wide range of sugar substrates. However, sugar transport in thermophiles is poorly understood and investigated, as compared to enzymatic lignocellulose deconstruction and metabolic conversion of sugars to value-added chemicals. Here, we review the general modes of sugar transport in thermophilic bacteria and archaea, covering the structural, molecular, and biophysical basis of their high-affinity sugar uptake. We also review how thermophilic sugar transporters are identified and characterized, including recent genetic studies on their function. With this understanding of sugar transport, we discuss strategies for how sugar transport can be engineered in thermophiles, with the potential to enhance the conversion of lignocellulosic biomass into renewable products.

Horizontal metaproteomics and CAZymes analysis oflignocellulolytic microbial consortia selectively enriched from cow rumen and termitegut

Selectively enriched microbial consortia are potentially useful for theconversion of lignocellulose (LC) into biofuels and commodity chemicals. Consortiaare also of interest to elucidate the roles of individual microorganisms and thedynamics of enzymes involved in LC deconstruction. Using metaproteomics, 16 S rRNAgene amplicon sequencing and multivariate discriminant analysis, we revealed thetemporal dynamics of microbial species and their proteins during anaerobicconversion of LC by microbial consortia derived from cow rumen (RWS) and termite gut(TWS) microbiomes. Bacteroidetes (Bacteroidota), Firmicutes (Bacillota) andProteobacteria (Pseudomonadota) phyla were dominant, irrespective the inoculumorigin, displaying functional complementarities. We identified a large variety ofcarbohydrate-active enzymes, distributed in 94 CAZy families, involved in biomassdeconstruction. Additionally, proteins involved in short chain fatty acidsbiosynthesis were detected. Multivariate analysis clearly differentiates RWS and TWSmetaproteomes, with differences originating in the initial inoculates. Furthersupervised discriminant analysis of the temporal succession of CAZymes revealed thatboth consortia consume easily accessible oligosaccharides during the early stage ofincubation, degrading more complex hemicellulose and cellulose fractions at laterstages, an action that pursues throughout the incubation period. Our results providenew insights regarding the functional roles and complementarities existing inlignocellulolytic consortia and highlight their potential for biorefineryapplications.

Exploring the cellulolytic and hemicellulolytic activities of manganese peroxidase for lignocellulose deconstruction

BackgroundA cost-effective pretreatment and saccharification process is a necessary prerequisite for utilizing lignocellulosic biomass (LCB) in biofuel and biomaterials production. Utilizing a multifunctional enzyme with both pretreatment and saccharification functions in a single step for simultaneous biological pretreatment and saccharification process (SPS) will be a green method of low cost and high efficiency. Manganese peroxidase (MnP, EC 1.11.1.13), a well-known lignin-degrading peroxidase, is generally preferred for the biological pretreatment of biomass. However, exploring the role and performance of MnP in LCB conversion will promote the application of MnP for lignocellulose-based biorefineries.ResultsIn this study, we explored the ability of an MnP from Moniliophthora roreri, MrMnP, in LCB degradation. With Mn2+ and H2O2, MrMnP decomposed 5.0 g/L carboxymethyl cellulose to 0.14 mM of reducing sugar with a conversion yield of 5.0 mg/g, including 40 μM cellobiose, 70 μM cellotriose, 20 μM cellotetraose, and 10 μM cellohexaose, and degraded 1.0 g/L mannohexaose to 0.33 μM mannose, 4.08 μM mannotriose, and 4.35 μM mannopentaose. Meanwhile, MrMnP decomposed 5.0 g/L lichenan to 0.85 mM of reducing sugar with a conversion yield of 30.6 mg/g, including 10 μM cellotriose, 20 μM cellotetraose, and 80 μM cellohexose independently of Mn2+ and H2O2. Moreover, the versatility of MrMnP in LCB deconstruction was further verified by decomposing locust bean gum and wheat bran into reducing sugars with a conversion yield of 54.4 mg/g and 29.5 mg/g, respectively, including oligosaccharides such as di- and tri-saccharides. The catalytic mechanism underlying MrMnP degraded lignocellulose was proposed as that with H2O2, MrMnP oxidizes Mn2+ to Mn3+. Subsequently, it forms a complex with malonate, facilitating the degradation of CMC and mannohexaose into reducing sugars. Without H2O2, MrMnP directly oxidizes malonate to hydroperoxyl acetic acid radical to form compound I, which then attacks the glucosidic bond of lichenan.ConclusionThis study identified a new function of MrMnP in the hydrolysis of cellulose and hemicellulose, suggesting that MrMnP exhibits its versatility in the pretreatment and saccharification of LCB. The results will lead to an in-depth understanding of biocatalytic saccharification and contribute to forming new enzymatic systems for using lignocellulose resources to produce sustainable and economically viable products and the long-term development of biorefinery, thereby increasing the productivity of LCB as a green resource.

Elucidating multi-scale deconstruction of bamboo crystalline cellulose by novel acetylcholine chloride based deep eutectic solvents for enhanced enzymatic hydrolysis

Exploration and application of novel and sustainable deep eutectic solvents (DESs) on lignocellulose pretreatment are promising approaches to efficient bioconversion. However, comprehensive understanding on efficient DESs selection and inner mechanisms of lignocellulose deconstruction are still limited. Herein, bio-based acetylcholine chloride (AChCl) was firstly utilized as hydrogen bond acceptor in cooperation with lactic acid, urea and glycerol respectively for microwave-assisted pretreatment on moso bamboo in short time. High enzymatic conversion yield of bamboo cellulose (∼85%) was achieved by lactic acid-AChCl DES due to its lower pH value and viscosity, followed by glycerol-AChCl and urea-AChCl DES. In addition to the features of proposed DESs, changed chemical and physical properties of highly recalcitrant bamboo biomass after pretreatments were systematically determined. Besides of great amount of lignin (∼90%)/ xylan (100%) removal, micro- to nano-scale variations of cellulose structures including more dissociated microfibrils, lowered crystallinity, and enlarged crystallite sizes all played key roles in promoting bioconversion yields. Moreover, the multi-factors contributing to improved hydrolysis performance were integrated to evaluate the effects of novel DESs pretreatments on lignocellulose deconstruction, which may provide new strategies on bioconversion enhancement and process optimization.

Papermaking wastewater treatment coupled to 2,3-butanediol production by engineered psychrotrophic Raoultella terrigena

The simultaneous bioremediation and bioconversion of papermaking wastewater by psychrotrophic microorganisms holds great promise for developing sustainable environments and economies in cold regions. Here, the psychrotrophic bacterium Raoultella terrigena HC6 presented high endoglucanase (26.3 U/mL), xylosidase (732 U/mL), and laccase (8.07 U/mL) activities for lignocellulose deconstruction at 15 °C. mRNA monitoring and phenotypic variation analyses confirmed that cold-inducible cold shock protein A (CspA) facilitated the expression of the cel208, xynB68, and lac432 genes to increase the enzyme activities in strain HC6. Furthermore, the cspA gene-overexpressing mutant (strain HC6-cspA) was deployed in actual papermaking wastewater and achieved 44.3%, 34.1%, 18.4%, 80.2% and 100% removal rates for cellulose, hemicellulose, lignin, COD, and NO3--N at 15 °C. Simultaneously, 2,3-butanediol (2,3-BD) was produced from the effluent with a titer of 2.98 g/L and productivity of 0.154 g/L/h. This study reveals an association between the cold regulon and lignocellulolytic enzymes and provides a promising candidate for simultaneous papermaking wastewater treatment and 2,3-BD production.

Lignin deconstruction by anaerobic fungi

Lignocellulose forms plant cell walls, and its three constituent polymers, cellulose, hemicellulose and lignin, represent the largest renewable organic carbon pool in the terrestrial biosphere. Insights into biological lignocellulose deconstruction inform understandings of global carbon sequestration dynamics and provide inspiration for biotechnologies seeking to address the current climate crisis by producing renewable chemicals from plant biomass. Organisms in diverse environments disassemble lignocellulose, and carbohydrate degradation processes are well defined, but biological lignin deconstruction is described only in aerobic systems. It is currently unclear whether anaerobic lignin deconstruction is impossible because of biochemical constraints or, alternatively, has not yet been measured. We applied whole cell-wall nuclear magnetic resonance, gel-permeation chromatography and transcriptome sequencing to interrogate the apparent paradox that anaerobic fungi (Neocallimastigomycetes), well-documented lignocellulose degradation specialists, are unable to modify lignin. We find that Neocallimastigomycetes anaerobically break chemical bonds in grass and hardwood lignins, and we further associate upregulated gene products with the observed lignocellulose deconstruction. These findings alter perceptions of lignin deconstruction by anaerobes and provide opportunities to advance decarbonization biotechnologies that depend on depolymerizing lignocellulose.

Molecular simulations inform biomass dissolution in ionic liquids in pursuit of benign solvent-system design

A tiered computational framework developed to discover safer and selective ionic liquids for lignocellulosic biomass deconstruction.

Insight into CAZymes of Alicyclobacillus mali FL18: Characterization of a New Multifunctional GH9 Enzyme.

In the bio-based era, cellulolytic and hemicellulolytic enzymes are biocatalysts used in many industrial processes, playing a key role in the conversion of recalcitrant lignocellulosic waste biomasses. In this context, many thermophilic microorganisms are considered as convenient sources of carbohydrate-active enzymes (CAZymes). In this work, a functional genomic annotation of Alicyclobacillus mali FL18, a recently discovered thermo-acidophilic microorganism, showed a wide reservoir of putative CAZymes. Among them, a novel enzyme belonging to the family 9 of glycosyl hydrolases (GHs), named AmCel9, was identified; in-depth in silico analyses highlighted that AmCel9 shares general features with other GH9 members. The synthetic gene was expressed in Escherichia coli and the recombinant protein was purified and characterized. The monomeric enzyme has an optimal catalytic activity at pH 6.0 and has comparable activity at temperatures ranging from 40 °C to 70 °C. It also has a broad substrate specificity, a typical behavior of multifunctional cellulases; the best activity is displayed on β-1,4 linked glucans. Very interestingly, AmCel9 also hydrolyses filter paper and microcrystalline cellulose. This work gives new insights into the properties of a new thermophilic multifunctional GH9 enzyme, that looks a promising biocatalyst for the deconstruction of lignocellulose.

Biochemical and Regulatory Analyses of Xylanolytic Regulons in Caldicellulosiruptor bescii Reveal Genus-Wide Features of Hemicellulose Utilization.

Caldicellulosiruptor species scavenge carbohydrates from runoff containing plant biomass that enters hot springs and from grasses that grow in more moderate parts of thermal features. While only a few Caldicellulosiruptor species can degrade cellulose, all known species are hemicellulolytic. The most well-characterized species, Caldicellulosiruptor bescii, decentralizes its hemicellulase inventory across five different genomic loci and two isolated genes. Transcriptomic analyses, comparative genomics, and enzymatic characterization were utilized to assign functional roles and determine the relative importance of its six putative endoxylanases (five glycoside hydrolase family 10 [GH10] enzymes and one GH11 enzyme) and two putative exoxylanases (one GH39 and one GH3) in C. bescii. Two genus-wide conserved xylanases, C. bescii XynA (GH10) and C. bescii Xyl3A (GH3), had the highest levels of sugar release on oat spelt xylan, were in the top 10% of all genes transcribed by C. bescii, and were highly induced on xylan compared to cellulose. This indicates that a minimal set of enzymes are used to drive xylan degradation in the genus Caldicellulosiruptor, complemented by hemicellulolytic inventories that are tuned to specific forms of hemicellulose in available plant biomasses. To this point, synergism studies revealed that the pairing of specific GH family proteins (GH3, -11, and -39) with C. bescii GH10 proteins released more sugar in vitro than mixtures containing five different GH10 proteins. Overall, this work demonstrates the essential requirements for Caldicellulosiruptor to degrade various forms of xylan and the differences in species genomic inventories that are tuned for survival in unique biotopes with variable lignocellulosic substrates. IMPORTANCE Microbial deconstruction of lignocellulose for the production of biofuels and chemicals requires the hydrolysis of heterogeneous hemicelluloses to access the microcrystalline cellulose portion. This work extends previous in vivo and in vitro efforts to characterize hemicellulose utilization by integrating genomic reconstruction, transcriptomic data, operon structures, and biochemical characteristics of key enzymes to understand the deployment and functionality of hemicellulases by the extreme thermophile Caldicellulosiruptor bescii. Furthermore, comparative genomics of the genus revealed both conserved and divergent mechanisms for hemicellulose utilization across the 15 sequenced species, thereby paving the way to connecting functional enzyme characterization with metabolic engineering efforts to enhance lignocellulose conversion.

A new l-cysteine-assisted glycerol organosolv pretreatment for improved enzymatic hydrolysis of corn stover

Deconstruction of lignocellulose via efficient pretreatment is crucial for producing fermentable sugars. In this study, effects of glycerol organosolv pretreatment (GOP) on main chemical composition of corn stover were investigated. Results indicate that the residual corn stover after 80 wt% glycerol pretreatment (at 220 °C for 0.5 h) yielded 75.97 % glucose and 78.21 % xylose after enzymatic hydrolysis, which were enhanced by 3.39- and 6.08-fold compared to the untreated corn stover. Subsequently, an l-cysteine-assisted GOP was proposed with higher yields of glucose (86.20 %) and xylose (91.13 %). When pretreating corn stover with 80 wt% glycerol containing 0.07 wt% l-cysteine at 220 °C for 0.5 h, higher fermentable sugars of 26.08 g were produced from 100 g feedstock after enzymolysis. Intrinsic mechanisms of the proposed pretreatment for enhancing enzymatic digestibility were elucidated by physiochemical characterization technologies and techno-economic analysis was also studied. This study provides guidance for fermentable sugars production from renewable lignocellulose.

A processive GH9 family endoglucanase of Bacillus licheniformis and the role of its carbohydrate-binding domain.

One of the critical steps in lignocellulosic deconstruction is the hydrolysis of crystalline cellulose by cellulases. Endoglucanases initially facilitate the breakdown of cellulose in lignocellulosic biomass and are further aided by other cellulases to produce fermentable sugars. Furthermore, if the endoglucanase is processive, it can adsorb to the smooth surface of crystalline cellulose and release soluble sugars during repeated cycles of catalysis before dissociating. Most glycoside hydrolase family 9 (GH9) endoglucanases have catalytic domains linked to a CBM (carbohydrate-binding module) (mostly CBM3) and present the second-largest cellulase family after GH5. GH9 endoglucanases are relatively less characterized. Bacillus licheniformis is a mesophilic soil bacterium containing many glycoside hydrolase (GH) enzymes. We identified an endoglucanase gene, gh9A, encoding the GH9 family enzyme H1AD14 in B. licheniformis and cloned and overexpressed H1AD14 in Escherichia coli. The purified H1AD14 exhibited very high enzymatic activity on endoglucanase substrates, such as β-glucan, lichenan, Avicel, CMC-Na (sodium carboxymethyl cellulose) and PASC (phosphoric acid swollen cellulose), across a wide pH range. The enzyme is tolerant to 2 M sodium chloride and retains 74% specific activity on CMC after 10 days, the highest amongst the reported GH9 endoglucanases. The full-length H1AD14 is a processive endoglucanase and efficiently saccharified sugarcane bagasse. The deletion of the CBM reduces the catalytic activity and processivity. The results add to the sparse knowledge of GH9 endoglucanases and offer the possibility of characterizing and engineering additional enzymes from B. licheniformis toward developing a cellulase cocktail for improved biomass deconstruction. KEY POINTS: • H1AD14 is a highly active and processive GH9 endoglucanase from B. licheniformis. • H1AD14 is thermostable and has a very long half-life. • H1AD14 showed higher saccharification efficiency than commercial endoglucanase.

Enzyme Discovery in Anaerobic Fungi (Neocallimastigomycetes) Enables Lignocellulosic Biorefinery Innovation.

Lignocellulosic biorefineries require innovative solutions to realize their full potential, and the discovery of novel lignocellulose-active enzymes could improve biorefinery deconstruction processes. Enzymatic deconstruction of plant cell walls is challenging, as noncarbohydrate linkages in hemicellulosic sidechains and lignin protect labile carbohydrates from hydrolysis. Highly specialized microbes that degrade plant biomass are attractive sources of enzymes for improving lignocellulose deconstruction, and the anaerobic gut fungi (Neocallimastigomycetes) stand out as having great potential for harboring novel lignocellulose-active enzymes. We discuss the known aspects of Neocallimastigomycetes lignocellulose deconstruction, including their extensive carbohydrate-active enzyme content, proficiency at deconstructing complex lignocellulose, unique physiology, synergistic enzyme complexes, and sizeable uncharacterized gene content. Progress describing Neocallimastigomycetes and their enzymes has been rapid in recent years, and it will only continue to expand. In particular, direct manipulation of anaerobic fungal genomes, effective heterologous expression of anaerobic fungal enzymes, and the ability to directly relate chemical changes in lignocellulose to fungal gene regulation will accelerate the discovery and subsequent deployment of Neocallimastigomycetes lignocellulose-active enzymes.

Metaproteomics reveals enzymatic strategies deployed by anaerobic microbiomes to maintain lignocellulose deconstruction at high solids

Economically viable production of cellulosic biofuels requires operation at high solids loadings—on the order of 15 wt%. To this end we characterize Nature’s ability to deconstruct and utilize mid-season switchgrass at increasing solid loadings using an anaerobic methanogenic microbiome. This community exhibits undiminished fractional carbohydrate solubilization at loadings ranging from 30 g/L to 150 g/L. Metaproteomic interrogation reveals marked increases in the abundance of specific carbohydrate-active enzyme classes. Significant enrichment of auxiliary activity family 6 enzymes at higher solids suggests a role for Fenton chemistry. Stress-response proteins accompanying these reactions are similarly upregulated at higher solids, as are β-glucosidases, xylosidases, carbohydrate-debranching, and pectin-acting enzymes—all of which indicate that removal of deconstruction inhibitors is important for observed undiminished solubilization. Our work provides insights into the mechanisms by which natural microbiomes effectively deconstruct and utilize lignocellulose at high solids loadings, informing the future development of defined cultures for efficient bioconversion.

Structural basis of lignocellulose deconstruction by the wood-feeding anobiid beetle Nicobium hirtum

The details of the lignocellulose deconstruction processes in the digestive systems of wood-feeding insects remain elusive. This study aimed to examine the biochemical conversion of lignocellulose in the digestive system of a wood-feeding anobiid beetle, Nicobium hirtum, one of the most important pests of wooden products in Japan. To this end, N. hirtum larvae were fed with Japanese red pine (softwood) and Japanese beech (hardwood) sapwood diets, as well as an artificial diet containing Shorea wood (hardwood) sapwood sawdust. The structural differences between the original and digested (feces) lignocellulose samples were examined using wet-chemical and two-dimensional (2D) nuclear magnetic resonance (NMR) methods. Cellulose and hemicelluloses, especially mannan in the softwood diet, were preferentially degraded over lignin in the larval digestive system. As a result, lignin was enriched in the digested lignocellulose residues. Lignin compositional analyses based on thioacidolysis and 2D NMR determined that the proportions of oxidized lignin aromatic units were notably increased after digestion. Further, the 2D NMR analyses revealed the accumulation of aldehyde and hydroxypropiovanillone/syringone end-unit structures in lignin, indicating that oxidative and/or reductive modifications of lignin polymers occur in the larval digestive system. Such structural alterations of lignin may facilitate the dissociation of the lignin barrier, thereby liberating polysaccharides for subsequent enzymatic conversion for assimilation and energy.

Self-generated peroxyacetic acid in phosphoric acid plus hydrogen peroxide pretreatment mediated lignocellulose deconstruction and delignification

BackgroundPeroxyacetic acid involved chemical pretreatment is effective in lignocellulose deconstruction and oxidation. However, these peroxyacetic acid are usually artificially added. Our previous work has shown that the newly developed PHP pretreatment (phosphoric acid plus hydrogen peroxide) is promising in lignocellulose biomass fractionation through an aggressive oxidation process, while the information about the synergistic effect between H3PO4 and H2O2 is quite lack, especially whether some strong oxidant intermediates is existed. In this work, we reported the PHP pretreatment system could self-generate peroxyacetic acid oxidant, which mediated the overall lignocellulose deconstruction, and hemicellulose/lignin degradation.ResultsThe PHP pretreatment profile on wheat straw and corn stalk were investigated. The pathways/mechanisms of peroxyacetic acid mediated-PHP pretreatment were elucidated through tracing the structural changes of each component. Results showed that hemicellulose was almost completely solubilized and removed, corresponding to about 87.0% cellulose recovery with high digestibility. Rather high degrees of delignification of 83.5% and 90.0% were achieved for wheat straw and corn stalk, respectively, with the aid of peroxyacetic acid oxidation. A clearly positive correlation was found between the concentration of peroxyacetic acid and the extent of lignocellulose deconstruction. Peroxyacetic acid was mainly self-generated through H2O2 oxidation of acetic acid that was produced from hemicellulose deacetylation and lignin degradation. The self-generated peroxyacetic acid then further contributed to lignocellulose deconstruction and delignification.ConclusionsThe synergistic effect of H3PO4 and H2O2 in the PHP solvent system could efficiently deconstruct wheat straw and corn stalk lignocellulose through an oxidation-mediated process. The main function of H3PO4 was to deconstruct biomass recalcitrance and degrade hemicellulose through acid hydrolysis, while the function of H2O2 was to facilitate the formation of peroxyacetic acid. Peroxyacetic acid with stronger oxidation ability was generated through the reaction between H2O2 and acetic acid, which was released from xylan and lignin oxidation/degradation. This work elucidated the generation and function of peroxyacetic acid in the PHP pretreatment system, and also provide useful information to tailor peroxide-involved pretreatment routes, especially at acidic conditions.Graphical abstract

Multi-stage pre-treatment of lignocellulosic biomass for multi-product biorefinery: A review

With increasing population worldwide and the consumption of greenhouse gases (GHGs) emitting limited fossil fuel resources, the indispensable need of seeking sustainable energy sources and conversion methods have been realized that can offer possible alternative ways to substantially minimize biomass wastes and even pre-treatments assisted biorefinery systems to convert those wastes into biofuels and other bioproducts. Considerable attention, therefore, has been given to the generation of biofuels from lignocellulosic biomass including the agricultural wastes. Biochemical and biological methods for converting lignocellulosic biomass to biofuels are challenging because of their unreactive nature, and pre-treatments are the key for their successful and efficient conversions. This review explored, compared, and highlighted the significance of multi-stage pre-treatment over the single-step biorefinery systems for biofuels production from different sources. The multi-stage methods have exhibited to demand less energy consumption and reaction time, to enhance productivity of lignocellulose deconstruction. However, optimized and engineered multi-stage pre-treatment methods for multi-product biorefinery from specific feedstocks have not been fully investigated yet. The authors present the future research direction for potential industrial application of multi-stage pre-treatments with key technical considerations as well.