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Low- and middle-income countries have tremendous potential for renewable energy production, including production of renewable carbon from locally prolific crops. In this work, bamboo endemic to West Africa (Bambusa vulgaris) was studied as a feedstock for the production of renewable sugars as the gateway to the local production of biofuels and bio-based chemical products. The effectiveness of delignification and amorphization pretreatments was evaluated, with the observation that quantitative (97 ± 4%) sugar yields could be obtained with a rapid initial hydrolysis rate (82 ± 4 mg g−1 h−1) but only when amorphization was performed following delignification. Experimental measurements and further characterization using 13C solid state nuclear magnetic resonance (NMR) helped establish the importance of amorphization and delignification and explained why the order of these treatments determined their effectiveness. The economics of the bamboo-based process were compared with those projected for corn stover, selected as a well-studied benchmark crop. Because of the higher bamboo growth rate compared with corn stover and the effectiveness of the pretreatment, the projected net present value (NPV) of the bamboo biorefinery was positive ($190 MM, U.S.), whereas the corn biorefinery projected to negative NPV (−$430 MM, U.S.). A socially sustainable framework for deployment of a bamboo biorefinery in a low- or middle-income economy was then proposed, guided by the principle of local ownership and stakeholder buy-in. The findings presented here motivate further investment in development of bamboo cultivation and conversion to sugars as a rapid route to decarbonization of low- and middle-income economies. [ABSTRACT FROM AUTHOR]

Simultaneous saccharification and fermentation (SSF) is effective for minimizing sugar inhibition during high solids fermentation of biomass solids to ethanol. However, fungal enzymes used during SSF are optimal between 50 and 60 °C, whereas most fermentative yeast, such as Saccharomyces cerevisiae, do not tolerate temperatures above 37 °C. Kluyveromyces marxianus variant CBS 6556 is a thermotolerant eukaryote that thrives at 43 °C, thus potentially serving as a promising new host for SSF operation in biorefineries. Here, we attempt to leverage the thermotolerance of the strain to demonstrate the application of CBS 6556 in a high solids (up to 20 wt% insoluble solid loading) SSF configuration to understand its capabilities and limitations as compared to a proven SSF strain, S. cerevisiae D5A. For this study, we first pretreated hardwood poplar chips using Co-Solvent Enhanced Lignocellulosic Fractionation (CELF) to remove lignin and hemicellulose and to produce cellulose-enriched pretreated solids for SSF. Our results demonstrate that although CBS 6556 could not directly outperform D5A, it demonstrated similar tolerance to high gravity sugar solutions, superior growth rates at higher temperatures and higher early stage ethanol productivity. We discovered that CBS 6556's membrane was particularly sensitive to higher ethanol concentrations causing it to suffer earlier fermentation arrest than D5A. Cross-examination of metabolite data between CBS 6556 and D5A and cell surface imaging suggests that the combined stresses of high ethanol concentrations and temperature to CBS 6556's cell membrane was a primary factor limiting its ethanol productivity. Hence, we believe K. marxianus to be an excellent host for future genetic engineering efforts to improve membrane robustness especially at high temperatures in order to achieve higher ethanol productivity and titers, serving as a viable alternative to D5A. [ABSTRACT FROM AUTHOR]

Background: Conventional aqueous dilute sulfuric acid (DSA) pretreatment of lignocellulosic biomass facilitates hemicellulose solubilization and can improve subsequent enzymatic digestibility of cellulose to fermentable glucose. However, much of the lignin after DSA pretreatment either remains intact within the cell wall or readily redeposits back onto the biomass surface. This redeposited lignin has been shown to reduce enzyme activity and contribute to rapid enzyme deactivation, thus, necessitating significantly higher enzyme loadings than deemed economical for biofuel production from biomass. Results: In this study, we demonstrate how detrimental lignin redeposition on biomass surface after pretreatment can be prevented by employing Co-solvent Enhanced Lignocellulosic Fractionation (CELF) pretreatment that uses THF–water co-solvents with dilute sulfuric acid to solubilize lignin and overcome limitations of DSA pretreatment. We first find that enzymatic hydrolysis of CELF-pretreated switchgrass can sustain a high enzyme activity over incubation periods as long as 5 weeks with enzyme doses as low as 2 mg protein/g glucan to achieve 90% yield to glucose. A modified Ninhydrin-based protein assay revealed that the free-enzyme concentration in the hydrolysate liquor, related to enzyme activity, remained unchanged over long hydrolysis times. DSA-pretreated switchgrass, by contrast, had a 40% drop in free enzymes in solution during incubation, providing evidence of enzyme deactivation. Furthermore, measurements of enzyme adsorption per gram of lignin suggested that CELF prevented lignin redeposition onto the biomass surface, and the little lignin left in the solids was mostly integral to the original lignin–carbohydrate complex (LCC). Scanning electron micrographs and NMR characterization of lignin supported this observation. Conclusions: Enzymatic hydrolysis of solids from CELF pretreatment of switchgrass at low enzyme loadings was sustained for considerably longer times and reached higher conversions than for DSA solids. Analysis of solids following pretreatment and enzymatic hydrolysis showed that prolonged cellulase activity could be attributed to the limited lignin redeposition on the biomass surface making more enzymes available for hydrolysis of more accessible glucan. [ABSTRACT FROM AUTHOR]

A combination of thermochemical pretreatment and biological digestion technologies is usually required to overcome lignocellulosic recalcitrance and accomplish effective biomass deconstruction. This study is aimed at understanding switchgrass breakdown by hydrothermal, dilute acid, dilute alkali, and co-solvent enhanced lignocellulosic fractionation (CELF) pretreatments followed by application of traditional fungal enzymatic hydrolysis (EH) and Clostridium thermocellum consolidated bioprocessing (CBP) to the resulting solids. Unpretreated and pretreated switchgrass and their EH and CBP residues were characterized by a suite of analytical techniques to understand structural changes that occurred during deconstruction. CELF pretreated solids showed the highest accessibility and digestibility by both EH and CBP followed by dilute alkali and then dilute acid/hydrothermal pretreated solids. Lignin removal from biomass had a more positive impact on substrate accessibility and digestibility than did xylan removal, while xyloglucan removal by pretreatment appeared essential for cellulose digestion by fungal enzymes. The extent of CBP digestion of cellulose and non-cellulosic glycans was larger than that by EH. Unlike dilute alkali pretreatment, cellulose crystallinity increased for acid-based pretreatments in the following order: hydrothermal, dilute acid, and CELF. Acid-based pretreatments also substantially reduced cellulose degree of polymerization. All thermochemical and biological digestion approaches increased syringyl to guaiacyl lignin (S/G) ratio and reduced β-O-4 lignin interunit linkage and hydroxycinnamates content from levels in unpretreated switchgrass. The substantial increase in S/G ratio after hydrothermal and dilute alkali preatreatments suggested that high temperatures or alkali removed a large portion of G lignin from switchgrass. [ABSTRACT FROM AUTHOR]

A particularly promising approach to deconstructing and fractionating lignocellulosic biomass to produce green renewable fuels and high-value chemicals pretreats the biomass with organic solvents in aqueous solution. Here, neutron scattering and moleculardynamics simulations reveal the temperature-dependent morphological changes in poplar wood biomass during tetrahydrofuran (THF):water pretreatment and provide a mechanism by which the solvent components drive efficient biomass breakdown. Whereas lignin dissociates over a wide temperature range (>25 °C) cellulose disruption occurs only above 150 °C. Neutron scattering with contrast variation provides direct evidence for the formation of THF-rich nanoclusters (Rg ~ 0.5 nm) on the nonpolar cellulose surfaces and on hydrophobic lignin, and equivalent waterrich nanoclusters on polar cellulose surfaces. The disassembly of the amphiphilic biomass is thus enabled through the local demixing of highly functional cosolvents, THF and water, which preferentially solvate specific biomass surfaces so as to match the local solute polarity. A multiscale description of the efficiency of THF:water pretreatment is provided: matching polarity at the atomic scale prevents lignin aggregation and disrupts cellulose, leading to improvements in deconstruction at the macroscopic scale. [ABSTRACT FROM AUTHOR]

Lignin valorization has risen as a promising pathway to supplant the use of petrochemicals for chemical commodities and fuels. However, the challenges of separating and breaking down lignin from lignocellulosic biomass are the primary barriers to success. Integrated biorefinery systems that incorporate both homo‐ and heterogeneous catalysis for the upgrading of lignin intermediates have emerged as a viable solution. Homogeneous catalysis can perform selected chemistries, such as the hydrolysis and dehydration of ester or ether bonds, that are more suitable for the pretreatment and fractionation of biomass. Heterogeneous catalysis, however, offers a tunable platform for the conversion of extracted lignin into chemicals, fuels, and materials. Tremendous effort has been invested in elucidating the necessary factors for the valorization of lignin by using heterogeneous catalysts, with efforts to explore more robust methods to drive down costs. Current progress in lignin conversion has fostered numerous advances, but understanding the key catalyst design principles is important for advancing the field. This Minireview aims to provide a summary on the fundamental design principles for the selective conversion of lignin by using heterogeneous catalysts, including the pairing of catalyst metals, supports, and solvents. The review puts a particular focus on the use of bimetallic catalysts on porous supports as a strategy for the selective conversion of lignin. Finally, future research on the valorization of lignin is proposed on the basis of recent progress. [ABSTRACT FROM AUTHOR]

Xylan is an important polysaccharide found in the hemicellulose fraction of lignocellulosic biomass that can be hydrolysed to xylose and further dehydrated to the furfural, an important renewable platform fuel precursor. Here, pairing molecular simulation and experimental evidence, we reveal how the unique temperature-dependent phase behaviour of water–tetrahydrofuran (THF) co-solvent can delay xylan solubilization to synergistically improve catalytic co-processing of biomass to furfural and 5-HMF. Our results indicate, based on polymer correlations between polymer conformational behaviour and solvent quality, that both co-solvent and aqueous environments serve as ‘good’ solvents for xylan. Interestingly, the simulations also revealed that unlike other cell-wall components (i.e., lignin and cellulose), the make-up of the solvation shell of xylan in THF–water is dependent on the temperature-phase behaviour. At temperatures between 333 K and 418 K, THF and water become immiscible, and THF is evacuated from the solvation shell of xylan, while above and below this temperature range, THF and water are both present in the polysaccharide's solvation shell. This suggested that the solubilization of xylan in THF–water may be similar to aqueous-only solutions at temperatures between 333 K and 418 K and different outside this range. Experimental reactions on beachwood xylan corroborate this hypothesis by demonstrating 2-fold reduction of xylan solubilization in THF–water within a miscible temperature regime (445 K) and unchanged solubilization within an immiscible regime (400 K). Translating this phase-dependent behaviour to processing of maple wood chips, we demonstrate how the weaker xylan solvation in THF–water under miscible conditions can delay furfural production from xylan, allowing 5-HMF production from cellulose to “catch-up” such that their high yield production from biomass can be synergized in a single pot reaction. [ABSTRACT FROM AUTHOR]

It has been previously shown that cellulose-lignin droplets’ strong interactions, resulting from lignin coalescence and redisposition on cellulose surface during thermochemical pretreatments, increase cellulose recalcitrance to biological conversion, especially at commercially viable low enzyme loadings. However, information on the impact of cellulose–hemicellulose interactions on cellulose recalcitrance following relevant pretreatment conditions are scarce. Here, to investigate the effects of plausible hemicellulose precipitation and re-association with cellulose on cellulose conversion, different pretreatments were applied to pure Avicel® PH101 cellulose alone and Avicel mixed with model hemicellulose compounds followed by enzymatic hydrolysis of resulting solids at both low and high enzyme loadings. Solids produced by pretreatment of Avicel mixed with hemicelluloses (AMH) were found to contain about 2 to 14.6% of exogenous, precipitated hemicelluloses and showed a remarkably much lower digestibility (up to 60%) than their respective controls. However, the exogenous hemicellulosic residues that associated with Avicel following high temperature pretreatments resulted in greater losses in cellulose conversion than those formed at low temperatures, suggesting that temperature plays a strong role in the strength of cellulose–hemicellulose association. Molecular dynamics simulations of hemicellulosic xylan and cellulose were found to further support this temperature effect as the xylan–cellulose interactions were found to substantially increase at elevated temperatures. Furthermore, exogenous, precipitated hemicelluloses in pretreated AMH solids resulted in a larger drop in cellulose conversion than the delignified lignocellulosic biomass containing comparably much higher natural hemicellulose amounts. Increased cellulase loadings or supplementation of cellulase with xylanases enhanced cellulose conversion for most pretreated AMH solids; however, this approach was less effective for solids containing mannan polysaccharides, suggesting stronger association of cellulose with (hetero) mannans or lack of enzymes in the mixture required to hydrolyze such polysaccharides. [ABSTRACT FROM AUTHOR]

Background: Consolidated bioprocessing (CBP) by anaerobes, such as Clostridium thermocellum, which combine enzyme production, hydrolysis, and fermentation are promising alternatives to historical economic challenges of using fungal enzymes for biological conversion of lignocellulosic biomass. However, limited research has integrated CBP with real pretreated biomass, and understanding how pretreatment impacts subsequent deconstruction by CBP vs. fungal enzymes can provide valuable insights into CBP and suggest other novel biomass deconstruction strategies. This study focused on determining the effect of pretreatment by dilute sulfuric acid alone (DA) and with tetrahydrofuran (THF) addition via co-solvent-enhanced lignocellulosic fractionation (CELF) on deconstruction of corn stover and Populus with much different recalcitrance by C. thermocellum vs. fungal enzymes and changes in pretreated biomass related to these differences. Results: Coupling CELF fractionation of corn stover and Populus with subsequent CBP by the anaerobe C. thermocellum completely solubilized polysaccharides left in the pretreated solids within only 48 h without adding enzymes. These results were better than those from the conventional DA followed by either CBP or fungal enzymes or CELF followed by fungal enzyme hydrolysis, especially at viable enzyme loadings. Enzyme adsorption on CELF-pretreated corn stover and CELF-pretreated Populus solids were virtually equal, while DA improved the enzyme accessibility for corn stover more than Populus. Confocal scanning light microscopy (CSLM), transmission electron microscopy (TEM), and NMR characterization of solids from both pretreatments revealed differences in cell wall structure and lignin composition, location, coalescence, and migration-enhanced digestibility of CELF-pretreated solids. Conclusions: Adding THF to DA pretreatment (CELF) greatly enhanced deconstruction of corn stover and Populus by fungal enzymes and C. thermocellum CBP, and the CELF-CBP tandem was agnostic to feedstock recalcitrance. Composition measurements, material balances, cellulase adsorption, and CSLM and TEM imaging revealed adding THF enhanced the enzyme accessibility, cell wall fractures, and cellular dislocation and cell wall delamination. Overall, enhanced deconstruction of CELF solids by enzymes and particularly by C. thermocellum could be related to lignin removal and alteration, thereby pointing to these factors being key contributors to biomass recalcitrance as a barrier to low-cost biological conversion to sustainable fuels. [ABSTRACT FROM AUTHOR]

Simultaneous saccharification and fermentation (SSF) of solid biomass can reduce the complexity and improve the economics of lignocellulosic ethanol production by consolidating process steps and reducing end-product inhibition of enzymes compared with separate hydrolysis and fermentation (SHF). However, a longstanding limitation of SSF has been too low ethanol yields at the high-solids loading of biomass needed during fermentation to realize sufficiently high ethanol titers favorable for more economical ethanol recovery. Here, we illustrate how competing factors that limit ethanol yields during high-solids fermentations are overcome by integrating newly developed cosolvent-enhanced lignocellulosic fractionation (CELF) pretreatment with SSF. First, fed-batch glucose fermentations by Saccharomyces cerevisiae D5A revealed that this strain, which has been favored for SSF, can produce ethanol at titers of up to 86 g.L-1. Then, optimizing SSF of CELF-pretreated corn stover achieved unprecedented ethanol titers of 79.2, 81.3 and 85.6 g.L-1 in batch shake flask, corresponding to ethanol yields of 90.5%, 86.1% and 80.8% at solids loadings of 20.0 wt %, 21.5 wt % and 23.0 wt %, respectively. Ethanol yields remained at over 90% despite reducing enzyme loading to only 10 mg protein.g glucan-1 [∼6.5 filter paper units (FPU)], revealing that the enduring factors limiting further ethanol production were reduced cell viability and glucose uptake by D5A and not loss of enzyme activity or mixing issues, thereby demonstrating an SSF-based process that was limited by a strain's metabolic capabilities and tolerance to ethanol. [ABSTRACT FROM AUTHOR]

A major challenge to economically produce ethanol from lignocellulosic biomass is to achieve industrially relevant ethanol titers (＞50 g L−1) to control operating and capital costs for downstream ethanol operations while maintaining high ethanol yields. However, due to reduced fermentation effectiveness at high biomass solids loadings, excessive amounts of enzymes are typically required to obtain reasonable ethanol titers, thereby trading off reduced operating and capital costs with high enzyme costs. In this study, we applied our newly developed Co-Solvent Enhanced Lignocellulosic Fractionation (CELF) pretreatment to produce highly digestible glucan-rich solids from corn stover. Simultaneous saccharification and fermentation (SSF) was then applied to pretreated solids from CELF at 15.5 wt% solids loadings (corresponding to 11 wt% glucan loadings) in modified shake flasks to achieve an ethanol titer of 58.8 g L−1 at 89.2% yield with an enzyme loading of 15 mg-protein per g-glucan-in-raw-corn-stover (-RCS) in only 5 days. By comparison, SSF of corn stover solids from dilute acid pretreatment at 18.3 wt% solids loading (or 10 wt% glucan loading) only achieved an ethanol titer and a yield of 47.8 g L−1 and 73.0%, respectively, despite needing longer fermentation times (∼20 days) and an additional 18 h of prehydrolysis at 50 °C. Remarkably, although longer fermentation times were required at more economical enzyme loadings of 5 and 2 mg-protein per g-glucan-in-RCS, high solids SSF of CELF pretreated corn stover realized final ethanol titers consistently above 50 g L−1 and yields over 80%. [ABSTRACT FROM AUTHOR]

The deconstruction of cellulose is an essential step in the production of ethanol from lignocellulosic biomass. However, the presence of lignin hinders this process. Recently, a novel cosolvent based biomass pretreatment method called CELF (Cosolvent Enhanced Lignocellulosic Fractionation) which employs tetrahydrofuran (THF) in a single phase mixture with water, was found to be highly effective at solubilizing and extracting lignin from lignocellulosic biomass and achieving high yields of fermentable sugars. Here, using all-atom molecular-dynamics simulation, we find that THF preferentially solvates lignin, and in doing so, shifts the equilibrium configurational distribution of the biopolymer from a crumpled globule to coil, independent of temperature. Whereas pure water is a bad solvent for lignin, the THF : water cosolvent acts as a “theta” solvent, in which solvent : lignin and lignin : lignin interactions are approximately equivalent in strength. Under these conditions, polymers do not aggregate, thus providing a mechanism for the observed lignin solubilization that facilitates unfettered access of celluloytic enzymes to cellulose. [ABSTRACT FROM AUTHOR]

We introduce a new pretreatment called co-solvent-enhanced lignocellulosic fractionation (CELF) to reduce enzyme costs dramatically for high sugar yields from hemicellulose and cellulose, which is essential for the low-cost conversion of biomass to fuels. CELF employs THF miscible with aqueous dilute acid to obtain up to 95 % theoretical yield of glucose, xylose, and arabinose from corn stover even if coupled with enzymatic hydrolysis at only 2 mgenzyme gglucan−1. The unusually high saccharification with such low enzyme loadings can be attributed to a very high lignin removal, which is supported by compositional analysis, fractal kinetic modeling, and SEM imaging. Subsequently, nearly pure lignin product can be precipitated by the evaporation of volatile THF for recovery and recycling. Simultaneous saccharification and fermentation of CELF-pretreated solids with low enzyme loadings and Saccharomyces cerevisiae produced twice as much ethanol as that from dilute-acid-pretreated solids if both were optimized for corn stover. [ABSTRACT FROM AUTHOR]

Metal halides are selective catalysts suitable for production of the fuel precursors furfural and 5-HMF from sugars derived from lignocellulosic biomass. However, they do not perform nearly as well when applied to biomass even in combination with immiscible extracting solvents or expensive ionic co-solvents. Here, we couple metal halides with a highly tunable co-solvent system employing renewable tetrahydrofuran (THF) to significantly enhance co-production of furfural and 5-HMF from biomass in a single phase reaction strategy capable of integrating biomass deconstruction with catalytic dehydration of sugars. Screening of several promising metal halide species at 170 °C in pH-controlled reactions with sugar solutions and larger 1 L reactions with maple wood and corn stover revealed how the interplay between relative Brønsted and Lewis acidities was responsible for enhancing catalytic performance in THF co-solvent. Combining FeCl3 with THF co-solvent was particularly effective, achieving one of the highest reported simultaneous yields of furfural (95%) and 5-HMF (51%) directly from biomass with minimal levulinic acid formation (6%). Furthermore, over 90% of the lignin from biomass was extracted by THF and recovered as a fine lignin powder. Tuning the volume ratio of THF to water from 4 : 1 to 1 : 1 preserved 10% to 31% of the reacted biomass as a glucan-rich solid suitable for further catalytic reaction, enzymatic digestion, or possible pulp and paper production. [ABSTRACT FROM AUTHOR]

Furfural is a natural precursor to furan-based chemicals and has the potential to become a major renewable platform chemical for the production of biochemicals and biofuels. However, current industrial furfural production relies on relatively old and inefficient strategies that have hindered its capacity, and low production yields have strongly diminished its competitiveness with petroleum-based alternatives in the global market. This mini-review provides a critical analysis of past and current progress to enhance furfural production from lignocellulosic biomass. First, important chemical and fuel products derived from the catalytic conversion of furfural are outlined. We then discuss the importance of developing integrated production strategies to co-produce furfural with other valuable chemicals. Furfural formation and loss chemistries are explored to understand effective methods to improve furfural yields from pentosans. Finally, selected relevant commercial and academic technologies that promise to improve lignocellulosic furfural production are discussed. © 2013 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

A novel single phase co-solvent system using tetrahydrofuran (THF) promotes hydrolysis of maple wood to sugars, sugar dehydration, and lignin extraction simultaneously and achieves higher overall yields of the fuel precursors furfural, 5-hydroxymethylfurfural (HMF), and levulinic acid (LA) than previously reported from biomass. In a one-pot reaction, we obtained yields of 86% furfural, 21% HMF, and 40% LA in the liquid phase and over 90% extraction of lignin as a solid powder. The co-solvent reaction also produced a glucan-rich residue that is highly digestible by enzymes for biological conversion to ethanol or further thermochemical reaction to additional HMF and levulinic acid. These findings enable an integrated conversion platform in which THF is both a co-solvent and final co-product to enhance production of fuel precursors for catalytic upgrading to renewable liquid hydrocarbons fuels. [ABSTRACT FROM AUTHOR]

Cover Feature: Heterogeneous Catalyst Design Principles for the Conversion of Lignin into High-Value Commodity Fuels and Chemicals (ChemSusChem 8/2020) Keywords: biomass; heterogeneous catalysts; lignin valorization; renewable resources; supported catalysts EN biomass heterogeneous catalysts lignin valorization renewable resources supported catalysts 1920 1920 1 04/22/20 20200421 NES 200421 B The Cover Feature b shows the organic depiction of heterogeneous catalysts as the building blocks for metaphysical corn. Biomass, heterogeneous catalysts, lignin valorization, renewable resources, supported catalysts. [Extracted from the article]

Background: In this work, three pretreatments under investigation at the DOE Bioenergy Research Centers (BRCs) were subjected to a side-by-side comparison to assess their performance on model bioenergy hardwoods (a eucalyptus and a hybrid poplar). These include co-solvent-enhanced lignocellulosic fractionation (CELF), pretreatment with an ionic liquid using potentially biomass-derived components (cholinium lysinate or [Ch][Lys]), and two-stage Cu-catalyzed alkaline hydrogen peroxide pretreatment (Cu-AHP). For each of the feedstocks, the pretreatments were assessed for their impact on lignin and xylan solubilization and enzymatic hydrolysis yields as a function of enzyme loading. Lignins recovered from the pretreatments were characterized for polysaccharide content, molar mass distributions, β-aryl ether content, and response to depolymerization by thioacidolysis. Results: All three pretreatments resulted in significant solubilization of lignin and xylan, with the CELF pretreatment solubilizing the majority of both biopolymer categories. Enzymatic hydrolysis yields were shown to exhibit a strong, positive correlation with the lignin solubilized for the low enzyme loadings. The pretreatment-derived solubles in the [Ch][Lys]-pretreated biomass were presumed to contribute to inhibition of enzymatic hydrolysis in the eucalyptus as a substantial fraction of the pretreatment liquor was carried forward into hydrolysis for this pretreatment. The pretreatment-solubilized lignins exhibited significant differences in polysaccharide content, molar mass distributions, aromatic monomer yield by thioacidolysis, and β-aryl ether content. Key trends include a substantially higher polysaccharide content in the lignins recovered from the [Ch][Lys] pretreatment and high β-aryl ether contents and aromatic monomer yields from the Cu-AHP pretreatment. For all lignins, the 13C NMR-determined β-aryl ether content was shown to be correlated with the monomer yield with a second-order functionality. Conclusions: Overall, it was demonstrated that the three pretreatments highlighted in this study demonstrated uniquely different functionalities in reducing biomass recalcitrance and achieving higher enzymatic hydrolysis yields for the hybrid poplar while yielding a lignin-rich stream that may be suitable for valorization. Furthermore, modification of lignin during pretreatment, particularly cleavage of β-aryl ether bonds, is shown to be detrimental to subsequent depolymerization. [ABSTRACT FROM AUTHOR]

Background: Pretreatment is effective in reducing the natural recalcitrance of plant biomass so polysaccharides in cell walls can be accessed for conversion to sugars. Furthermore, lignocellulosic biomass must typically be reduced in size to increase the pretreatment effectiveness and realize high sugar yields. However, biomass size reduction is a very energy-intensive operation and contributes significantly to the overall capital cost. Results: In this study, the effect of particle size reduction and biomass presoaking on the deconstruction of Alamo switchgrass was examined prior to pretreatment by dilute sulfuric acid (DSA) and Co-solvent Enhanced Lignocellulosic Fractionation (CELF) at pretreatment conditions optimized for maximum sugar release by each pretreatment coupled with subsequent enzymatic hydrolysis. Sugar yields by enzymatic hydrolysis were measured over a range of enzyme loadings. In general, DSA successfully solubilized hemicellulose, while CELF removed nearly 80% of Klason lignin from switchgrass in addition to the majority of hemicellulose. Presoaking and particle size reduction did not have a significant impact on biomass compositions after pretreatment for both DSA and CELF. However, presoaking for 4 h slightly increased sugar yields by enzymatic hydrolysis of DSA-pretreated switchgrass compared to unsoaked samples, whereas sugar yields from enzymatic hydrolysis of CELF solids continued to increase substantially for up to 18 h of presoaking time. Of particular importance, DSA required particle size reduction by knife milling to < 2 mm in order to achieve adequate sugar yields by subsequent enzymatic hydrolysis. CELF solids, on the other hand, realized nearly identical sugar yields from unmilled and milled switchgrass even at very low enzyme loadings. Conclusions: CELF was capable of achieving nearly theoretical sugar yields from enzymatic hydrolysis of pretreated switchgrass solids without size reduction, unlike DSA. These results indicate that CELF may be able to eliminate particle size reduction prior to pretreatment and thereby reduce overall costs of biological processing of biomass to fuels. In addition, presoaking proved much more effective for CELF than for DSA, particularly at low enzyme loadings. [ABSTRACT FROM AUTHOR]

Following publication of the original article [1], the authors reported that the omission of author name. [ABSTRACT FROM AUTHOR]

Background: The recalcitrance of cellulosic biomass is widely recognized as a key barrier to cost-effective biological processing to fuels and chemicals, but the relative impacts of physical, chemical and genetic interventions to improve biomass processing singly and in combination have yet to be evaluated systematically. Solubilization of plant cell walls can be enhanced by non-biological augmentation including physical cotreatment and thermochemical pretreatment, the choice of biocatalyst, the choice of plant feedstock, genetic engineering of plants, and choosing feedstocks that are less recalcitrant natural variants. A two-tiered combinatoric investigation of lignocellulosic biomass deconstruction was undertaken with three biocatalysts (Clostridium thermocellum, Caldicellulosiruptor bescii, Novozymes Cellic® Ctec2 and Htec2), three transgenic switchgrass plant lines (COMT, MYB4, GAUT4) and their respective nontransgenic controls, two Populus natural variants, and augmentation of biological attack using either mechanical cotreatment or cosolvent-enhanced lignocellulosic fractionation (CELF) pretreatment. Results: In the absence of augmentation and under the conditions tested, increased total carbohydrate solubilization (TCS) was observed for 8 of the 9 combinations of switchgrass modifications and biocatalysts tested, and statistically significant for five of the combinations. Our results indicate that recalcitrance is not a trait determined by the feedstock only, but instead is coequally determined by the choice of biocatalyst. TCS with C. thermocellum was significantly higher than with the other two biocatalysts. Both CELF pretreatment and cotreatment via continuous ball milling enabled TCS in excess of 90%. Conclusion: Based on our results as well as literature studies, it appears that some form of non-biological augmentation will likely be necessary for the foreseeable future to achieve high TCS for most cellulosic feedstocks. However, our results show that this need not necessarily involve thermochemical processing, and need not necessarily occur prior to biological conversion. Under the conditions tested, the relative magnitude of TCS increase was augmentation > biocatalyst choice > plant choice > plant modification > plant natural variants. In the presence of augmentation, plant modification, plant natural variation, and plant choice exhibited a small, statistically non-significant impact on TCS. [ABSTRACT FROM AUTHOR]

The Inside Cover depicts a novel cellulosic biomass pretreatmENt called co ‐ solvENt ‐ ENhanced lignocellulosic fractionation (CELF) that uses THF to greatly ENhance sugar and ethanol yields from dilute acid pretreatmENt of corn stover. CELF removed and recovered hemicellulose sugars and most of the lignin to produce highly digestible cellulose that was hydrolyzed to glucose using 90   % less ENzymes than dilute ‐ acid pretreatmENt. Sugar yields from hemicellulose and cellulose were over 95   % of theoretical, and over 90   % ethanol yields were obtained by simultaneous saccharification and fermENtation (SSF). More details can be found in the Full Paper by NguyEN et al. (DOI: 10.1002/cssc.201403045). [ABSTRACT FROM AUTHOR]