Deep reaction network exploration of glucose pyrolysis.

Resolving the reaction networks associated with biomass pyrolysis is central to understanding product selectivity and aiding catalyst design to produce more valuable products. However, even the pyrolysis network of relatively simple [Formula: see text]-D-glucose remains unresolved due to its significant complexity in terms of the depth of the network and the number of major products. Here, a transition-state-guided reaction exploration has been performed that provides complete pathways to most significant experimental pyrolysis products of [Formula: see text]-D-glucose. The resulting reaction network involves over 31,000 reactions and transition states computed at the semiempirical quantum chemistry level and approximately 7,000 kinetically relevant reactions and transition states characterized with density function theory, comprising the largest reaction network reported for biomass pyrolysis. The exploration was conducted using graph-based rules to explore the reactivities of intermediates and an adaption of the Dijkstra algorithm to identify kinetically relevant intermediates. This simple exploration policy surprisingly (re)identified pathways to most major experimental pyrolysis products, many intermediates proposed by previous computational studies, and also identified new low-barrier reaction mechanisms that resolve outstanding discrepancies between reaction pathways and yields in isotope labeling experiments. This network also provides explanatory pathways for the high yield of hydroxymethylfurfural and the reaction pathway that contributes most to the formation of hydroxyacetaldehyde during glucose pyrolysis. Due to the limited domain knowledge required to generate this network, this approach should also be transferable to other complex reaction network prediction problems in biomass pyrolysis.

Natural photoredox catalysts promote light-driven lytic polysaccharide monooxygenase reactions and enzymatic turnover of biomass.

Lytic polysaccharide monooxygenases (LPMOs) catalyze oxidative cleavage of crystalline polysaccharides such as cellulose and chitin and are important for biomass conversion in the biosphere as well as in biorefineries. The target polysaccharides of LPMOs naturally occur in copolymeric structures such as plant cell walls and insect cuticles that are rich in phenolic compounds, which contribute rigidity and stiffness to these materials. Since these phenolics may be photoactive and since LPMO action depends on reducing equivalents, we hypothesized that LPMOs may enable light-driven biomass conversion. Here, we show that redox compounds naturally present in shed insect exoskeletons enable harvesting of light energy to drive LPMO reactions and thus biomass conversion. The primary underlying mechanism is that irradiation of exoskeletons with visible light leads to the generation of H2O2, which fuels LPMO peroxygenase reactions. Experiments with a cellulose model substrate show that the impact of light depends on both light and exoskeleton dosage and that light-driven LPMO activity is inhibited by a competing H2O2-consuming enzyme. Degradation experiments with the chitin-rich exoskeletons themselves show that solubilization of chitin by a chitin-active LPMO is promoted by light. The fact that LPMO reactions, and likely reactions catalyzed by other biomass-converting redox enzymes, are fueled by light-driven abiotic reactions in nature provides an enzyme-based explanation for the known impact of visible light on biomass conversion.

Engineering a coenzyme-independent dioxygenase for one-step production of vanillin from ferulic acid.

Vanillin is one of the world's most important flavor and fragrance compounds used in foods and cosmetics. In plants, vanillin is reportedly biosynthesized from ferulic acid via the hydratase/lyase-type enzyme VpVAN. However, in biotechnological and biocatalytic applications, the use of VpVAN limits the production of vanillin. Although microbial enzymes are helpful as substitutes for plant enzymes, synthesizing vanillin from ferulic acid in one step using microbial enzymes remains a challenge. Here, we developed a single enzyme that catalyzes vanillin production from ferulic acid in a coenzyme-independent manner via the rational design of a microbial dioxygenase in the carotenoid cleavage oxygenase family using computational simulations. This enzyme acquired catalytic activity toward ferulic acid by introducing mutations into the active center to increase its affinity for ferulic acid. We found that the single enzyme can catalyze not only the production of vanillin from ferulic acid but also the synthesis of other aldehydes from p-coumaric acid, sinapinic acid, and coniferyl alcohol. These results indicate that the approach used in this study can greatly expand the range of substrates available for the dioxygenase family of enzymes. The engineered enzyme enables efficient production of vanillin and other value-added aldehydes from renewable lignin-derived compounds. IMPORTANCE: The final step of vanillin biosynthesis in plants is reportedly catalyzed by the enzyme VpVAN. Prior to our study, VpVAN was the only reported enzyme that directly converts ferulic acid to vanillin. However, as many characteristics of VpVAN remain unknown, this enzyme is not yet suitable for biocatalytic applications. We show that an enzyme that converts ferulic acid to vanillin in one step could be constructed by modifying a microbial dioxygenase-type enzyme. The engineered enzyme is of biotechnological importance as a tool for the production of vanillin and related compounds via biocatalytic processes and metabolic engineering. The results of this study may also provide useful insights for understanding vanillin biosynthesis in plants.

Aspergillus fumigatus-induced biogenic silver nanoparticles' efficacy as antimicrobial and antibiofilm agents with potential anticancer activity: An in vitro investigation.

A worldwide hazard to human health is posed by the growth of pathogenic bacteria that have contaminated fresh, processed, cereal, and seed products in storage facilities. As the number of multidrug-resistant (MDR) pathogenic microorganisms rises, we must find safe, and effective antimicrobials. The use of green synthesis of nanoparticles to combat microbial pathogens has gained a rising interest. The current study showed that Aspergillus fumigatus was applied as a promising biomass for the green synthesis of biogenic silver nanoparticles (Ag NPs). The UV-visible spectra of biosynthesized Ag NPs appeared characteristic surface plasmon absorption at 475 nm, round-shaped with sizes ranging from 17.11 to 75.54 nm and an average size of 50.37 ± 2.3 nm. In vitro tests were conducted to evaluate the antibacterial, antioxidant, and anticancer effects of various treatment procedures for Ag NP applications. The synthesized Ag NPs was revealed antimicrobial activity against Aspergillus flauvas, A. niger, Bacillus cereus, Candida albicans, Esherichia coli, Pseudomonas aerugonosa, and Staphylococcus aureus under optimum conditions. The tested bacteria were sensitive to low Ag NPs concentrations (5, 10, 11, 8, 7, 10, and 7 mg/mL) which was observed for the mentioned-before tested microorganisms, respectively. The tested bacterial pathogens experienced their biofilm formation effectively suppressed by Ag NPs at sub-inhibitory doses. Antibacterial reaction mechanism of Ag NPs were tested using scanning electron microscopy (SEM) to verify their antibacterial efficacy towards S. aureus and P. aeruginosa. These findings clearly show how harmful Ag NPs are to pathogenic bacteria. The synthesized Ag NPs showed antitumor activity with IC50 at 5 µg/mL against human HepG-2 and MCF-7 cellular carcinoma cells, while 50 mg/mL was required to induce 70 % of normal Vero cell mortality. These findings imply that green synthetic Ag NPs can be used on cancer cell lines in vitro for anticancer effect beside their potential as a lethal factor against some tested pathogenic microbes.

Conversion of Sugars to Lactic Acid using homogeneous Niobium-substituted Polyoxometalate Catalysts.

The catalytic conversion of biomass into high-value chemicals is an increasing field of research. This study uniquely investigates the use of various Keggin-type heteropoly salts (HPS) for the chemical conversion of sugars into lactic acid under mild conditions of 160°C and 20 bar N2. In the first phase, Nb- and V-substituted HPSs were employed to synthesize lactic acid from dihydroxyacetone, an intermediate in the conversion of sugars to lactic acid. Results indicated that increasing the Nb content within the Keggin structure enhances the yield of lactic acid while reducing the formation of the byproduct acetaldehyde. A correlation was established between the redox activity of the HPS and the catalytic performance. The most active catalyst, Na5[PNb2Mo10O40], (NaNb2) achieved a lactic acid yield of 20.9% after 1 h of reaction. In the second phase of the study, NaNb2 was applied for the conversion of different sugars including glucose, fructose, mannose, sucrose, xylose, and cellobiose. It was demonstrated that the catalyst remains active for complex hexoses, achieving lactic acid yields of up to 12%. Post-mortem analysis using infrared (IR) and Raman spectroscopy, nuclear magnetic resonance (NMR), and inductively coupled plasma optical emission spectrometry (ICP-OES) confirmed the stability of NaNb2.

Waste Valorization in a Sustainable Bio-Based Economy: The Road to Carbon Neutrality.

The development of sustainable chemistry underlying the quest to minimize and/or valorize waste in the carbon-neutral manufacture of chemicals is followed over the last four to five decades. Both chemo- and biocatalysis have played an indispensable role in this odyssey. in particular developments in protein engineering, metagenomics and bioinformatics over the preceding three decades have played a crucial supporting role in facilitating the widespread application of both whole cell and cell-free biocatalysis. The pressing need, driven by climate change mitigation, for a drastic reduction in greenhouse gas (GHG) emissions, has precipitated an energy transition based on decarbonization of energy and defossilization of organic chemicals production. The latter involves waste biomass and/or waste CO2 as the feedstock and green electricity generated using solar, wind, hydroelectric or nuclear energy. The use of waste polysaccharides as feedstocks will underpin a renaissance in carbohydrate chemistry with pentoses and hexoses as base chemicals and bio-based solvents and polymers as environmentally friendly downstream products. The widespread availability of inexpensive electricity and solar energy has led to increasing attention for electro(bio)catalysis and photo(bio)catalysis which in turn is leading to myriad innovations in these fields.

Efficient hydrodeoxygenation of lignin-derived phenolic compounds over bifunctional catalyst comprising H4PMo11VO40 coupled with Ni/C.

In the catalytic transformation of bio-oil into liquid fuels having alkanes via hydrodeoxygenation (HDO), the acid and metal sites in the catalyst are pivotal for promoting the HDO of lignin-derived phenolic compounds. This study introduces a novel bifunctional catalyst comprising phosphomolybdenum-vanadium heteropolyacids (H4PMo11VO40) coupled with Ni/C. The HDO reaction of the model compound guaiacol was carried out under reaction conditions of 230 °C, revealing the superior performance of H4PMo11VO40 with Ni/C catalysts compared to the conventional acids, even at low dosage. The Keggin structure of H4PMo11VO40 provided a solid catalyst with strong acidic and redox properties, alongside advantages such as ease of synthesis, cost-effectiveness, and tunable acid and redox properties at the molecular level. Characterization of Ni/C and the prepared acid demonstrated favorable pore structure with a mesopore volume of 0.281 cm3/g and an average pore size of 3.404 nm, facilitating uniform distribution and catalytic activity of Ni-metal. Incorporating acid enhances the acidic sites, fostering synergistic interactions between metal and acidic sites within the catalyst, thereby significantly enhancing HDO performance. Guaiacol conversion at 230 °C reached 100%, with a cyclohexane selectivity of 89.3%. This study presents a promising pathway for converting lignin-derived phenolic compounds.

Organic waste-to-bioplastics: Conversion with eco-friendly technologies and approaches for sustainable environment.

Petrochemical-based synthetic plastics poses a threat to humans, wildlife, marine life and the environment. Given the magnitude of eventual depletion of petrochemical sources and global environmental pollution caused by the manufacturing of synthetic plastics such as polyethylene (PET) and polypropylene (PP), it is essential to develop and adopt biopolymers as an environment friendly and cost-effective alternative to synthetic plastics. Research into bioplastics has been gaining traction as a way to create a more sustainable and eco-friendlier environment with a reduced environmental impact. Biodegradable bioplastics can have the same characteristics as traditional plastics while also offering additional benefits due to their low carbon footprint. Therefore, using organic waste from biological origin for bioplastic production not only reduces our reliance on edible feedstock but can also effectively assist with solid waste management. This review aims at providing an in-depth overview on recent developments in bioplastic-producing microorganisms, production procedures from various organic wastes using either pure or mixed microbial cultures (MMCs), microalgae, and chemical extraction methods. Low production yield and production costs are still the major bottlenecks to their deployment at industrial and commercial scale. However, their production and commercialization pose a significant challenge despite such potential. The major constraints are their production in small quantity, poor mechanical strength, lack of facilities and costly feed for industrial-scale production. This review further explores several methods for producing bioplastics with the aim of encouraging researchers and investors to explore ways to utilize these renewable resources in order to commercialize degradable bioplastics. Challenges, future prospects and Life cycle assessment of bioplastics are also highlighted. Utilizing a variety of bioplastics obtained from renewable and cost-effective sources (e.g., organic waste, agro-industrial waste, or microalgae) and determining the pertinent end-of-life option (e.g., composting or anaerobic digestion) may lead towards the right direction that assures the sustainable production of bioplastics.

Biomass-derived carbon dots as emerging visual platforms for fluorescent sensing.

Biomass-derived carbon dots (CDs) are non-toxic and fluorescently stable, making them suitable for extensive application in fluorescence sensing. The use of cheap and renewable materials not only improves the utilization rate of waste resources, but it is also drawing increasing attention to and interest in the production of biomass-derived CDs. Visual fluorescence detection based on CDs is the focus of current research. This method offers high sensitivity and accuracy and can be used for rapid and accurate determination under complex conditions. This paper describes the biomass precursors of CDs, including plants, animal remains and microorganisms. The factors affecting the use of CDs as fluorescent probes are also discussed, and a brief overview of enhancements made to the preparation process of CDs is provided. In addition, the application prospects and challenges related to biomass-derived CDs are demonstrated.

Lignocellulolytic Potential of Microbial Consortia Isolated from a Local Biogas Plant: The Case of Thermostable Xylanases Secreted by Mesophilic Bacteria.

Lignocellulose biomasses (LCB), including spent mushroom substrate (SMS), pose environmental challenges if not properly managed. At the same time, these renewable resources hold immense potential for biofuel and chemicals production. With the mushroom market growth expected to amplify SMS quantities, repurposing or disposal strategies are critical. This study explores the use of SMS for cultivating microbial communities to produce carbohydrate-active enzymes (CAZymes). Addressing a research gap in using anaerobic digesters for enriching microbiomes feeding on SMS, this study investigates microbial diversity and secreted CAZymes under varied temperatures (37 °C, 50 °C, and 70 °C) and substrates (SMS as well as pure carboxymethylcellulose, and xylan). Enriched microbiomes demonstrated temperature-dependent preferences for cellulose, hemicellulose, and lignin degradation, supported by thermal and elemental analyses. Enzyme assays confirmed lignocellulolytic enzyme secretion correlating with substrate degradation trends. Notably, thermogravimetric analysis (TGA), coupled with differential scanning calorimetry (TGA-DSC), emerged as a rapid approach for saccharification potential determination of LCB. Microbiomes isolated at mesophilic temperature secreted thermophilic hemicellulases exhibiting robust stability and superior enzymatic activity compared to commercial enzymes, aligning with biorefinery conditions. PCR-DGGE and metagenomic analyses showcased dynamic shifts in microbiome composition and functional potential based on environmental conditions, impacting CAZyme abundance and diversity. The meta-functional analysis emphasised the role of CAZymes in biomass transformation, indicating microbial strategies for lignocellulose degradation. Temperature and substrate specificity influenced the degradative potential, highlighting the complexity of environmental-microbial interactions. This study demonstrates a temperature-driven microbial selection for lignocellulose degradation, unveiling thermophilic xylanases with industrial promise. Insights gained contribute to optimizing enzyme production and formulating efficient biomass conversion strategies. Understanding microbial consortia responses to temperature and substrate variations elucidates bioconversion dynamics, emphasizing tailored strategies for harnessing their biotechnological potential.

Renewable Energy Potential: Second-Generation Biomass as Feedstock for Bioethanol Production.

Biofuels are clean and renewable energy resources gaining increased attention as a potential replacement for non-renewable petroleum-based fuels. They are derived from biomass that could either be animal-based or belong to any of the three generations of plant biomass (agricultural crops, lignocellulosic materials, or algae). Over 130 studies including experimental research, case studies, literature reviews, and website publications related to bioethanol production were evaluated; different methods and techniques have been tested by scientists and researchers in this field, and the most optimal conditions have been adopted for the generation of biofuels from biomass. This has ultimately led to a subsequent scale-up of procedures and the establishment of pilot, demo, and large-scale plants/biorefineries in some regions of the world. Nevertheless, there are still challenges associated with the production of bioethanol from lignocellulosic biomass, such as recalcitrance of the cell wall, multiple pretreatment steps, prolonged hydrolysis time, degradation product formation, cost, etc., which have impeded the implementation of its large-scale production, which needs to be addressed. This review gives an overview of biomass and bioenergy, the structure and composition of lignocellulosic biomass, biofuel classification, bioethanol as an energy source, bioethanol production processes, different pretreatment and hydrolysis techniques, inhibitory product formation, fermentation strategies/process, the microorganisms used for fermentation, distillation, legislation in support of advanced biofuel, and industrial projects on advanced bioethanol. The ultimate objective is still to find the best conditions and technology possible to sustainably and inexpensively produce a high bioethanol yield.

Binary Iron-Manganese Cocatalyst for Simultaneous Activation of C-C and C-O Bonds to Maximally Utilize Lignin for Syngas Generation over InGaN.

Solar-powered lignin reforming offers a carbon-neutral route for syngas production. This study explores a dual non-precious iron-manganese cocatalyst to simultaneously activate both C-C and C-O bonds for maximizing the utilization of various substituents of native lignin to yield syngas. By assembling with InGaN nanowires on a Si wafer, the as-designed dual FeMn cocatalyst affords a measurable syngas evolution rate of 42.4 mol·gcat-1·h-1 from native lignin in distilled water with a high selectivity of 93% and tunable H2/CO ratios under concentrated light, leading to a considerable light-to-fuel efficiency of 11.8%. The high FeMn atom efficiency arising from the 1-dimensional nanostructure of InGaN enables the achievement of a high turnover frequency (TOF) of 220896 mol syngas per mol FeMn per hour. By correlating exploration experiments, the critical role of the dual FeMn cocatalyst in the evolving mechanism of lignin and water toward syngas is disclosed at the atomic level. It is discovered that the synergetic iron-manganese cocatalyst supported by InGaN nanowires enables simultaneous activation of C-C and C-O bonds with comparable minimized dissociation energies. This work demonstrates a new and earth-abundant bifunctional cocatalyst for utilizing various substituents of lignin to produce syngas powered by sunlight beyond fossil fuels.

Visible Light-Switchable Lattice Oxygen Sites for Selective C-H and C(O)-C Bond Electrooxidation.

Lattice-oxygen is highly oxidizable, ideal for electrocatalytic C-H oxidation but insufficient alone for C(O)-C bond cleavage due to the non-removable nature of lattice sites. Here, we present a visible light-assisted electrochemical method of in-situ formulating removable lattice-oxygen sites in a nickel-oxyhydroxide (ESE-NiOOH) electrocatalyst. This catalyst efficiently converts aromatic alcohols and carbonyls with C(O)-C fragments from lignin and plastics into benzoic acids (BAs) with high yields (83-99%). Without light irradiation, ESE-NiOOH's intrinsic lattice-oxygen is non-removable and inert for C(O)-C bond cleavage. In-situ characterizations show light-induced lattice-oxygen removal and regeneration via OH- refilling. Theoretical calculations identify the nucleophilic oxygen attack on ketone-derived carbanion as a rate-determining step, which can be remarkably facilitated by removable lattice-oxygen to activate α-C-H bonds. As a proof-of-concept, an "electrochemical funnel" strategy is developed for high-efficiency upgrading aromatic mixtures with C(O)-C moieties into BA with up to 94% yield. This in-situ removal-regeneration approach for lattice sites opens an avenue for the tailored design of interfacial electrocatalysts to selectively upcycle waste carbon sources into valuable products.

In situ H2 O2 Generation by Choline Oxidase and Its Application in Amino Polysaccharide Degradation by Coupling to Lytic Polysaccharide Monooxygenase.

Chitin, the most abundant amino polysaccharide in Nature, has many applications in different fields. However, processing of this recalcitrant biopolymer in an environmentally friendly manner remains a major challenge. In this context, lytic polysaccharide monooxygenases (LPMOs) are of interest, as they can act on the most recalcitrant parts of chitin and related insoluble biopolymers such as cellulose. Efficient LPMO catalysis can be achieved by feeding reactions with H2 O2 , but careful control of H2 O2 is required to avoid autocatalytic enzyme inactivation. Herein, we present a coupled enzyme system in which a choline oxidase from Arthrobacter globiformis is employed for controlled in situ generation of H2 O2 that fuels LPMO-catalyzed oxidative degradation of chitin. We show that the rate, stability and extent of the LPMO reaction can be manipulated by varying the amount of choline oxidase and/or its substrate, choline chloride, and that efficient peroxygenase reactions may be achieved using sub-µM concentrations of the H2 O2 -generating enzyme. This coupled system requires only sub-stoichiometric amounts of the reductant that is needed to keep the LPMO in its active, reduced state. It is conceivable that this enzyme system may be used for bioprocessing of chitin in choline-based natural deep eutectic solvents.

Sustainable production of biofuels from the algae-derived biomass.

The worldwide fossil fuel reserves are rapidly and continually being depleted as a result of the rapid increase in global population and rising energy sector needs. Fossil fuels should not be used carelessly since they produce greenhouse gases, air pollution, and global warming, which leads to ecological imbalance and health risks. The study aims to discuss the alternative renewable energy source that is necessary to meet the needs of the global energy industry in the future. Both microalgae and macroalgae have great potential for several industrial applications. Algae-based biofuels can surmount the inadequacies presented by conventional fuels, thereby reducing the 'food versus fuel' debate. Cultivation of algae can be performed in all three systems; closed, open, and hybrid frameworks from which algal biomass is harvested, treated and converted into the desired biofuels. Among these, closed photobioreactors are considered the most efficient system for the cultivation of algae. Different types of closed systems can be employed for the cultivation of algae such as stirred tank photobioreactor, flat panel photobioreactor, vertical column photobioreactor, bubble column photobioreactor, and horizontal tubular photobioreactor. The type of cultivation system along with various factors, such as light, temperature, nutrients, carbon dioxide, and pH affect the yield of algal biomass and hence the biofuel production. Algae-based biofuels present numerous benefits in terms of economic growth. Developing a biofuel industry based on algal cultivation can provide us with a lot of socio-economic advantages contributing to a publicly maintainable result. This article outlines the third-generation biofuels, how they are cultivated in different systems, different influencing factors, and the technologies for the conversion of biomass. The benefits provided by these new generation biofuels are also discussed. The development of algae-based biofuel would not only change environmental pollution control but also benefit producers' economic and social advancement.

Ni-Based Hydrotalcite (HT)-Derived Cu Catalysts for Catalytic Conversion of Bioethanol to Butanol.

Catalytic conversion of biomass-derived ethanol into n-butanol through Guerbet coupling reaction has become one of the key reactions in biomass valorization, thus attracting significant attention recently. Herein, a series of supported Cu catalysts derived from Ni-based hydrotalcite (HT) were prepared and performed in the continuous catalytic conversion of ethanol into butanol. Among the prepared catalysts, Cu/NiAlOx shows the best performance in terms of butanol selectivity and catalyst stability, with a sustained ethanol conversion of ~35% and butanol selectivity of 25% in a time-on-stream (TOS) of 110 h at 280 °C. While for the Cu/NiFeOx and Cu/NiCoOx, obvious catalyst deactivation and/or low butanol selectivity were obtained. Extensive characterization studies of the fresh and spent catalysts, i.e., X-ray diffraction (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Hydrogen temperature-programmed reduction (H2-TPR), reveal that the catalysts' deactivation is mainly caused by the support deconstruction during catalysis, which is highly dependent on the reducibility. Additionally, an appropriate acid-base property is pivotal for enhancing the product selectivity, which is beneficial for the key process of aldol-condensation to produce butanol.

Efficient Secretory Production of Lytic Polysaccharide Monooxygenase BaLPMO10 and Its Application in Plant Biomass Conversion.

Lytic polysaccharide monooxygenases (LPMOs) can oxidatively break the glycosidic bonds of crystalline cellulose, providing more actionable sites for cellulase to facilitate the conversion of cellulose to cello-oligosaccharides, cellobiose and glucose. In this work, a bioinformatics analysis of BaLPMO10 revealed that it is a hydrophobic, stable and secreted protein. By optimizing the fermentation conditions, the highest protein secretion level was found at a IPTG concentration of 0.5 mM and 20 h of fermentation at 37 °C, with a yield of 20 mg/L and purity > 95%. The effect of metal ions on the enzyme activity of BaLPMO10 was measured, and it was found that 10 mM Ca2+ and Na+ increased the enzyme activity by 47.8% and 98.0%, respectively. However, DTT, EDTA and five organic reagents inhibited the enzyme activity of BaLPMO10. Finally, BaLPMO10 was applied in biomass conversion. The degradation of corn stover pretreated with different steam explosions was performed. BaLPMO10 and cellulase had the best synergistic degradation effect on corn stover pretreated at 200 °C for 12 min, improving reducing sugars by 9.2% compared to cellulase alone. BaLPMO10 was found to be the most efficient for ethylenediamine-pretreated Caragana korshinskii by degrading three different biomasses, increasing the content of reducing sugars by 40.5% compared to cellulase alone following co-degradation with cellulase for 48 h. The results of scanning electron microscopy revealed that BaLPMO10 disrupted the structure of Caragana korshinskii, making its surface coarse and poriferous, which increased the accessibility of other enzymes and thus promoted the process of conversion. These findings provide guidance for improving the efficiency of enzymatic digestion of lignocellulosic biomass.

Niobium: The Focus on Catalytic Application in the Conversion of Biomass and Biomass Derivatives.

The world scenario regarding consumption and demand for products based on fossil fuels has demonstrated the imperative need to develop new technologies capable of using renewable resources. In this context, the use of biomass to obtain chemical intermediates and fuels has emerged as an important area of research in recent years, since it is a renewable source of carbon in great abundance. It has the benefit of not contributing to the additional emission of greenhouse gases since the CO2 released during the energy conversion process is consumed by it through photosynthesis. In the presented review, the authors provide an update of the literature in the field of biomass transformation with the use of niobium-containing catalysts, emphasizing the versatility of niobium compounds for the conversion of different types of biomass.

Enzymatic Cocktail Formulation for Xylan Hydrolysis into Xylose and Xylooligosaccharides.

In the context of a biorefinery, lignocellulosic materials represent an important source of raw material for the bioconversion of cellulose, hemicellulose, and lignin into value-added products, such as xylose for fermentation, oligosaccharides, and bioplastics for packaging. Among the most abundant lignocellulosic materials in Brazil, sugarcane bagasse biomass stands out, as it is rich in cellulose and hemicellulose. In this context, through an experimental design, this study developed a robust enzyme cocktail containing xylanases and accessory enzymes to complete the hydrolysis of xylan from sugarcane bagasse, obtaining a low xylose yield and concentration (9% and 1.8 g/L, respectively, observed in experiment number 16 from the complete hydrolysis of a xylan assay), a fermentable sugar that is important in the production of second-generation ethanol, and a high xylooligosaccharides (XOS) yield and concentration (93.1% and 19.6 g/L, respectively, obtained from a xylooligosaccharides production assay); in general, xylan has prebiotic activities that favor an improvement in intestinal functions, with immunological and antimicrobial actions and other benefits to human health. In addition to completely hydrolyzing the sugarcane bagasse xylan, this enzymatic cocktail has great potential to be applied in other sources of lignocellulosic biomass for the conversion of xylan into xylose and XOS due to its enzymes content, involving both main chain and pendant groups hydrolysis of hemicelluloses.

Identification of Active Sites Formed on Cobalt Oxyhydroxide in Glucose Electrooxidation.

Transition-metal-based oxyhydroxides are efficient catalysts in biomass electrooxidation towards fossil-fuel-free production of valuable chemicals. However, identification of active sites remains elusive. Herein, using cobalt oxyhydroxide (CoOOH) as the archetype and the electrocatalyzed glucose oxidation reaction (GOR) as the model reaction, we track dynamic transformation of the electronic and atomic structure of the catalyst using a suite of operando and ex situ techniques. We reveal that two types of reducible Co3+ -oxo species are afforded for the GOR, including adsorbed hydroxyl on Co3+ ion (µ1 -OH-Co3+ ) and di-Co3+ -bridged lattice oxygen (µ2 -O-Co3+ ). Moreover, theoretical calculations unveil that µ1 -OH-Co3+ is responsible for oxygenation, while µ2 -O-Co3+ mainly contributes to dehydrogenation, both as key oxidative steps in glucose-to-formate transformation. This work provides a framework for mechanistic understanding of the complex near-surface chemistry of metal oxyhydroxides in biomass electrorefining.