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Biochemicals are widely used in the medicine and food industries and are more efficient and safer than synthetic chemicals. The amphipathic surfactants can interact with the microorganisms and embed the extracellular metabolites, which induce microbial metabolites secretion and biosynthesis, performing an attractive prospect of promoting the biochemical production. However, the commonness and differences of surfactant-mediated bio-manufacture in various fields are largely unexplored. Accordingly, this review comprehensively summarized the properties of surfactants, different application scenarios of surfactant-meditated bio-manufacture, and the mechanism of surfactants increasing metabolites production. Various biochemical productions such as pigments, amino acids, and alcohols could be enhanced using the cloud point and the micelles of surfactants. Besides, the amphiphilicity of surfactants also promoted the utilization of fermentation substrates, especially lignocellulose and waste sludge, by microorganisms, indirectly increasing the metabolites production. The increase in target metabolites production was attributed to the surfactants changing the permeability and composition of the cell membrane, hence improving the secretion ability of microorganisms. Moreover, surfactants could regulate the energy metabolism, the redox state and metabolic flow in microorganisms, which induced target metabolites synthesis. This review aimed to broaden the application fields of surfactants and provide novel insights into the production of microbial biochemicals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Biohydrogen (Bio-H 2 ) is widely recognized as a sustainable and environmentally friendly energy source, devoid of any detrimental impact on the environment. Lignocellulosic biomass (LB) is a readily accessible and plentiful source material that can be effectively employed as a cost-effective and sustainable substrate for Bio-H 2 production. Despite the numerous challenges, the ongoing progress in LB pretreatment technology, microbial fermentation, and the integration of molecular biology techniques have the potential to enhance Bio-H 2 productivity and yield. Consequently, this technology exhibits efficiency and the capacity to meet the future energy demands associated with the valorization of recalcitrant biomass. To date, several pretreatment approaches have been investigated in order to improve the digestibility of feedstock. Nevertheless, there has been a lack of comprehensive systematic studies examining the effectiveness of pretreatment methods in enhancing Bio-H 2 production through dark fermentation. Additionally, there is a dearth of economic feasibility evaluations pertaining to this area of research. Thus, this review has conducted comparative studies on the technological and economic viability of current pretreatment methods. It has also examined the potential of these pretreatments in terms of carbon neutrality and circular economy principles. This review paves the way for a new opportunity to enhance Bio-H 2 production with technological approaches., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Inc.)

Durian peel, an abundant waste in Malaysia could be a potential substrate for fermentable sugar recovery for value-added biochemical production. Common pretreatment such as acid or alkaline pretreatment resulted in the need for extensive solid washing which generated wastewater. Herein, this study aims to introduce sonication on top of chemical pretreatment to destruct lignin and reduce the chemical usage during the durian peel pretreatment process. In this study, the morphology and the chemical composition of the pretreated durian peels were studied. The sugar yield produced from the chemical pretreatment and the combined ultrasound and chemical pretreatment were compared. The morphology and chemical structure of durian peels were investigated by Scanning Electron Microscope (SEM), Fourier Transform Infrared (FTIR) analysis and X-ray diffraction (XRD). The SEM images showed that the structural change became more significant when sonication was introduced. Second, XRD profile indicated a relatively higher crystallinity index and FTIR spectra displayed a lower intensity of lignin and hemicellulose for ultrasound plus alkaline (UB) pretreatment as compared to acid, alkaline and ultrasound plus acid (UA) pretreatment. UB and UA pretreatment portrayed higher yield (376.60 ± 12.14 and 237.38 ± 3.96 mg reducing sugar/g dry biomass, respectively) than their controls without the application of ultrasound. Therefore, it could be concluded that ultrasound was able to intensify the fermentable sugar recovery from durian peel by inducing physical and chemical effect of cavitation to alter the morphology of durian peel. Fermentation of UB treated durian peel resulted in 2.68 mol hydrogen/mol consumed sugar and 131.56 mL/L medium /h of hydrogen productivity. This study is important because it will shed light on a way to handle durian waste disposal problems and generate fermentable sugars for the production of high value-added products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

In their pristine state, starch and lignin are abundant and inexpensive natural polymers frequently considered green alternatives to oil-based and synthetic polymers. Despite their availability and owing to their physicochemical properties; starch and lignin are not often utilized in their pristine forms for high-performance applications. Generally, chemical and physical modifications transform them into starch- and lignin-based materials with broadened properties and functionality. In the last decade, the combination of starch and lignin for producing reinforced materials has gained significant attention. The reinforcing of starch matrices with lignin has received primary focus because of the enhanced water sensitivity, UV protection, and mechanical and thermal resistance that lignin introduces to starch-based materials. This review paper aims to assess starch-lignin materials' production and characterization technologies, highlighting their physicochemical properties, outcomes, challenges, and opportunities. First, this paper describes the current status, sources, and chemical modifications of lignin and starch. Next, the discussion is oriented toward starch-lignin materials and their production approaches, such as blends, composites, plasticized/crosslinked films, and coupled polymers. Special attention is given to the characterization methods of starch-lignin materials, focusing on their advantages, disadvantages, and expected outcomes. Finally, the challenges, opportunities, and future perspectives in developing starch-lignin materials, such as adhesives, coatings, films, and controlled delivery systems, are discussed., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Urbanization has driven the demand for fossil fuels, however, the overly exploited resource has caused severe damage on environmental pollution. Biorefining using abundant lignocellulosic biomass is an emerging strategy to replace traditional fossil fuels. Value-added lignin biomass reduces the waste pollution in the environment and provides a green path of conversion to obtain renewable resources. The technology is designed to produce biofuels, biomaterials and value-added products from lignocellulosic biomass. In the biorefinery process, the pretreatment step is required to reduce the recalcitrant structure of lignocellulose biomass and improve the enzymatic digestion. There is still a gap in the full and deep understanding of the biorefinery process including the pretreatment process, thus it is necessary to provide optimized and adapted biorefinery solutions to cope with the conversion process in different biorefineries to further provide efficiency in industrial applications. Current research progress on value-added applications of lignocellulosic biomass still stagnates at the biofuel phase, and there is a lack of comprehensive discussion of emerging potential applications. This review article explores the advantages, disadvantages and properties of pretreatment methods including physical, chemical, physico-chemical and biological pretreatment methods. Value-added bioproducts produced from lignocellulosic biomass were comprehensively evaluated in terms of encompassing biochemical products , cosmetics, pharmaceuticals, potent functional materials from cellulose and lignin, waste management alternatives, multifunctional carbon materials and eco-friendly products. This review article critically identifies research-related to sustainability of lignocellulosic biomass to promote the development of green chemistry and to facilitate the refinement of high-value, environmentally-friendly materials. In addition, to align commercialized practice of lignocellulosic biomass application towards the 21st century, this paper provides a comprehensive analysis of lignocellulosic biomass biorefining and the utilization of biorefinery green technologies is further analyzed as being considered sustainable, including having potential benefits in terms of environmental, economic and social impacts. This facilitates sustainability options for biorefinery processes by providing policy makers with intuitive evaluation and guidance., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Searching for renewable alternatives for fossil carbon resources to produce chemicals, fuels and materials is essential for the development of a sustainable society. Lignin, a major component of lignocellulosic biomass, is an abundant renewable source of aromatics and is currently underutilized as it is often burned as an undesired side stream in the production of paper and bioethanol. This lignin harbors great potential as source of high value aromatic chemicals and materials. Biorefinery schemes focused on lignin are currently under development with aim of acquiring added value from lignin. However, the performance of these novel lignin-focused biorefineries is closely linked with the quality of extracted lignin in terms of the level of degradation and modification. Thus, the reactivity including the degradation pathways of the native lignin contained in the plant material needs to be understood in detail to potentially achieve higher value from lignin. Undegraded native-like lignin with an as close as possible structure to native lignin contained in the lignocellulosic plant material serves as a promising model lignin to support detailed studies on the structure and reactivity of native lignin, yielding key understanding for the development of lignin-focused biorefineries. The aim of this review is to highlight the different methods to attain "native-like" lignins that can be valuable for such studies. This is done by giving a basic introduction on what is known about the native lignin structure and the techniques and methods used to analyze it followed by an overview of the fractionation and isolation methods to isolate native-like lignin. Finally, a perspective on the isolation and use of native-like lignin is provided, showing the great potential that this type of lignin brings for understanding the effect of different biomass treatments on the native lignin structure., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Dye-decolorizing Peroxidases (DyPs) are heme-containing enzymes in fungi and bacteria that catalyze the reduction of hydrogen peroxide to water with concomitant oxidation of various substrates, including anthraquinone dyes, lignin-related phenolic and non-phenolic compounds, and metal ions. Investigation of DyPs has shed new light on peroxidases, one of the most extensively studied families of oxidoreductases; still, details of their microbial physiological role and catalytic mechanisms remain to be fully disclosed. They display a distinctive ferredoxin-like fold encompassing anti-parallel β-sheets and α-helices, and long conserved loops surround the heme pocket with a role in catalysis and stability. A tunnel routes H 2 O 2 to the heme pocket, whereas binding sites for the reducing substrates are in cavities near the heme or close to distal aromatic residues at the surface. Variations in reactions, the role of catalytic residues, and mechanisms were observed among different classes of DyP. They were hypothetically related to the presence or absence of distal H 2 O molecules in the heme pocket. The engineering of DyPs for improved properties directed their biotechnological applications, primarily centered on treating textile effluents and degradation of other hazardous pollutants, to fields such as biosensors and valorization of lignin, the most abundant renewable aromatic polymer. In this review, we track recent research contributions that furthered our understanding of the activity, stability, and structural properties of DyPs and their biotechnological applications. Overall, the study of DyP-type peroxidases has significant implications for environmental sustainability and the development of new bio-based products and materials with improved end-of-life options via biodegradation and chemical recyclability, fostering the transition to a sustainable bio-based industry in the circular economy realm., Competing Interests: Declaration of Competing Interest None., (Copyright © 2023 The Author(s). Published by Elsevier Inc. All rights reserved.)

Lignin is the most affluent natural aromatic biopolymer on the earth, which is the promising renewable source for valuable products to promote the sustainability of biorefinery. Flavonoids are a class of plant polyphenolic secondary metabolites containing the benzene ring structure with various biological activities, which are largely applied in health food, pharmaceutical, and medical fields. Due to the aromatic similarity, microbial conversion of lignin derived aromatics to flavonoids could facilitate flavonoid biosynthesis and promote the lignin valorization. This review thereby prospects a novel valorization route of lignin to high-value natural products and demonstrates the potential advantages of microbial bioconversion of lignin to flavonoids. The biodegradation of lignin polymers is summarized to identify aromatic monomers as momentous precursors for flavonoid synthesis. The biosynthesis pathways of flavonoids in both plants and strains are introduced and compared. After that, the key branch points and important intermediates are clearly discussed in the biosynthesis pathways of flavonoids. Moreover, the most significant enzyme reactions including Claisen condensation, cyclization and hydroxylation are demonstrated in the biosynthesis pathways of flavonoids. Finally, current challenges and potential future strategies are also discussed for transforming lignin into various flavonoids. The holistic microbial conversion routes of lignin to flavonoids could make a sustainable production of flavonoids and improve the feasibility of lignin valorization., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing interests., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Enzymatic hydrolysis is a critical process for the cellulase-mediated lignocellulosic biorefinery to produce sugar syrups that can be converted into a whole range of biofuels and biochemicals. Such a process operating at high-solid loadings (i.e., scarcely any free water or roughly ≥ 15% solids, w/w) is considered more economically feasible, as it can generate a high sugar concentration at low operation and capital costs. However, this approach remains restricted and incurs "high-solid effects", ultimately causing the lower hydrolysis yields with increasing solid loadings. The lack of available water leads to a highly viscous system with impaired mixing that exhibits strong transfer resistance and reaction limitation imposed on enzyme action. Evidently, high-solid enzymatic hydrolysis involves multi-scale mass transfer and multi-phase enzyme reaction, and thus requires a synergistic perspective of transfer and biotransformation to assess the interactions among water, biomass components, and cellulase enzymes. Porous particle characteristics of biomass and its interface properties determine the water form and distribution state surrounding the particles, which are summarized in this review aiming to identify the water-driven multi-scale/multi-phase bioprocesses. Further aided by the cognition of rheological behavior of biomass slurry, solute transfer theories, and enzyme kinetics, the coupling effects of flow-transfer-reaction are revealed under high-solid conditions. Based on the above basic features, this review lucidly explains the causes of high-solid hydrolysis hindrances, highlights the mismatched issues between transfer and reaction, and more importantly, presents the advanced strategies for transfer and reaction enhancements from the viewpoint of process optimization, reactor design, as well as enzyme/auxiliary additive customization., Competing Interests: Declaration of Competing Interest None., (Copyright © 2022. Published by Elsevier Inc.)

Lignocellulosic biorefinery based on sugar-platform has been considered as an efficient strategy to replace fossil fuel-based refinery. In the bioconversion process, pretreatment is an essential step to firstly open up lignocellulose cell wall structure and enhance the accessibility of carbohydrates to hydrolytic enzymes. However, various lignin and/or carbohydrates degradation products (e.g. phenolics, 5-hydroxymethylfurfural, furfural) are also generated during pretreatment, which severely inhibit the following enzymatic hydrolysis and the downstream fermentation process. Among them, the lignin derived phenolics have been considered as the most inhibitory compounds and their inhibitory effects are highly dependent on the source of biomass and the type of pretreatment strategy. Although liquid-solid separation and subsequent washing can remove the lignin derived phenolics and other inhibitors, this is undesirable in the realistic industrial application where the whole slurry of pretreated biomass needs to be directly used in the hydrolysis process. This review summarizes the phenolics formation mechanism for various commonly applied pretreatment methods and discusses the key factors that affect the inhibitory effect of phenolics on cellulose hydrolysis. In addition, the recent achievements on the rational design of inhibition mitigation strategies to boost cellulose hydrolysis for sugar-platform biorefinery are also introduced. This review also provides guidance for rationally designing detoxification strategies to facilitate whole slurry hydrolysis which helps to realize the industrialization of lignocellulose biorefinery., Competing Interests: Declaration of Competing Interest Authors declare no conflict of interest., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Lignin represents the most abundant renewable aromatics in nature, which has complicated and heterogeneous structure. The rapid development of biotransformation technology has brought new opportunities to achieve the complete lignin valorization. Especially, Rhodococcus sp. possesses excellent capabilities to metabolize aromatic hydrocarbons degraded from lignin. Furthermore, it can convert these toxic compounds into high value added bioproducts, such as microbial lipids, polyhydroxyalkanoate and carotenoid et al. Accordingly, this review will discuss the potentials of Rhodococcus sp. as a cell factory for lignin biotransformation, including phenol tolerance, lignin depolymerization and lignin-derived aromatic hydrocarbon metabolism. The detailed metabolic mechanism for lignin biotransformation and bioproducts spectrum of Rhodococcus sp. will be comprehensively discussed. The available molecular tools for the conversion of lignin by Rhodococcus sp. will be reviewed, and the possible direction for lignin biotransformation in the future will also be proposed., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Aromatic compounds are ubiquitous in nature; they are the building blocks of abundant lignin, and constitute a substantial proportion of synthetic chemicals and organic pollutants. Uptake and degradation of aromatic compounds by bacteria have relevance in bioremediation, bio-based plastic recycling, and microbial conversion of lignocellulosic biomass into high-value commodity chemicals. While remarkable progress has been achieved in understanding aromatic metabolism in biodegraders, the membrane transporter systems responsible for uptake and efflux of aromatic compounds and their degradation products are still poorly understood. Membrane transporters are responsible for the initial recognition, uptake, and efflux of aromatic compounds; thus, in addition to controlling influx and efflux, the transporter system also forms part of stress tolerance mechanisms through excreting toxic metabolites. This review discusses significant advancements in our understanding of the nature and identity of the bacterial membrane transporter systems for aromatics, the molecular and structural basis of substrate recognition, mechanisms of translocation, functional regulation, and biotechnological applications. Most of these developments were enabled through the availability of crystal structures, advancements in computational biophysics, genome sequencing, omics studies, bioinformatics, and synthetic biology. We provide a comprehensive overview of recently reported knowledge on aromatic transporter systems in bacteria, point gaps in our understanding of the underlying translocation mechanisms, highlight existing limitations in harnessing transporter systems in synthetic biology applications, and suggest future research directions., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Lignin is a promising renewable biopolymer being investigated worldwide as an environmentally benign substitute of fossil-based aromatic compounds, e.g. for the use as an excipient with antioxidant and antimicrobial properties in drug delivery or even as active compound. For its successful implementation into process streams, a quick, easy, and reliable method is needed for its molecular weight determination. Here we present a method using 1 H spectra of benchtop as well as conventional NMR systems in combination with multivariate data analysis, to determine lignin's molecular weight (M w and M n ) and polydispersity index (PDI). A set of 36 organosolv lignin samples (from Miscanthus x giganteus, Paulownia tomentosa and Silphium perfoliatum) was used for the calibration and cross validation, and 17 samples were used as external validation set. Validation errors between 5.6% and 12.9% were achieved for all parameters on all NMR devices (43, 60, 500 and 600 MHz). Surprisingly, no significant difference in the performance of the benchtop and high-field devices was found. This facilitates the application of this method for determining lignin's molecular weight in an industrial environment because of the low maintenance expenditure, small footprint, ruggedness, and low cost of permanent magnet benchtop NMR systems., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Development and deployment of commercial biorefineries based on conversion of lignocellulosic biomass into biofuels and bioproducts faces many challenges that must be addressed before they are commercially viable. One of the biggest challenges faced is the efficient and scalable valorization of lignin, one of the three major components of the plant cell wall. Lignin is the most abundant aromatic biopolymer on earth, and its presence hinders the extraction of cellulose and hemicellulose that is essential to biochemical conversion of lignocellulose to fuels and chemicals. There has been a significant amount of work over the past 20 years that has sought to develop innovative processes designed to extract and recycle lignin into valuable compounds and help reduce the overall costs of the biorefinery process. Due to the complex matrix of lignin, which is essential for plant survival, the development of a reliable and efficient lignin conversion technology has been difficult to achieve. One approach that has received significant interest relies on the use of enzymes, notably laccases, a class of multi‑copper green oxidative enzymes that catalyze bond breaking in lignin to produce smaller oligomers. In this review, we first assess the different innovations of lignin valorization using laccases within the context of a biorefinery process, and then assess the latest economical advances that these innovations offered. Finally, we review laccase characterization and optimization, as well as the prospects and bottlenecks of this class of enzymes within the industrial and biorefining sectors., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Bioconversion of renewable lignocellulosics to produce liquid fuels and chemicals is one of the most effective ways to solve the problem of fossil resource shortage, energy security, and environmental challenges. Among the many biorefinery pathways, hydrolysis of lignocellulosics to fermentable monosaccharides by cellulase is arguably the most critical step of lignocellulose bioconversion. In the process of enzymatic hydrolysis, the direct physical contact between enzymes and cellulose is an essential prerequisite for the hydrolysis to occur. However, lignin is considered one of the most recalcitrant factors hindering the accessibility of cellulose by binding to cellulase unproductively, which reduces the saccharification rate and yield of sugars. This results in high costs for the saccharification of carbohydrates. The various interactions between enzymes and lignin have been explored from different perspectives in literature, and a basic lignin inhibition mechanism has been proposed. However, the exact interaction between lignin and enzyme as well as the recently reported promotion of some types of lignin on enzymatic hydrolysis is still unclear at the molecular level. Multiple analytical techniques have been developed, and fully unlocking the secret of lignin-enzyme interactions would require a continuous improvement of the currently available analytical techniques. This review summarizes the current commonly used advanced research analytical techniques for investigating the interaction between lignin and enzyme, including quartz crystal microbalance with dissipation (QCM-D), surface plasmon resonance (SPR), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), nuclear magnetic resonance (NMR) spectroscopy, fluorescence spectroscopy (FLS), and molecular dynamics (MD) simulations. Interdisciplinary integration of these analytical methods is pursued to provide new insight into the interactions between lignin and enzymes. This review will serve as a resource for future research seeking to develop new methodologies for a better understanding of the basic mechanism of lignin-enzyme binding during the critical hydrolysis process., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Lipids are a biorefinery platform to prepare fuel, food and health products. They are traditionally obtained from plants, but those of microbial origin allow for a better use of land and C resources, among other benefits. Several (thermo)chemical and biochemical strategies are used for the conversion of C contained in lignocellulosic biomass into lipids. In particular, pyrolysis can process virtually any biomass and is easy to scale up. Products offer cost-effective, renewable C in the form of readily fermentable molecules and other upgradable intermediates. Although the production of microbial lipids has been studied for 30 years, their incorporation into biorefineries was only described a few years ago. As pyrolysis becomes a profitable technology to depolymerize lignocellulosic biomass into assimilable C, the number of investigations on it raises significantly. This article describes the challenges and opportunities resulting from the combination of lignocellulosic biomass pyrolysis and lipid biosynthesis with oleaginous microorganisms. First, this work presents the basics of the individual processes, and then it shows state-of-the-art processes for the preparation of microbial lipids from biomass pyrolysis products. Advanced knowledge on separation techniques, structure analysis, and fermentability is detailed for each biomass pyrolysis fraction. Finally, the microbial fatty acid platform comprising biofuel, human food and animal feed products, and others, is presented. Literature shows that the microbial lipid production from anhydrosugars, like levoglucosan, and short-chain organic acids, like acetic acid, is straightforward. Indeed, processes achieving nearly theoretical yields form the latter have been described. Some authors have shown that lipid biosynthesis from different lignin sources is biochemically feasible. However, it still imposes major challenges regarding strain performance. No report on the fermentation of pyrolytic lignin is yet available. Research on the microbial uptake of pyrolytic humins remains vacant. Microorganisms that make use of methane show promising results at the proof-of-concept level. Overall, despite some issues need to be tackled, it is now possible to conceive new versatile biorefinery models by combining lignocellulosic biomass pyrolysis products and robust oleaginous microbial cell factories., (Copyright © 2021 Elsevier Inc. All rights reserved.)

It is well-known that ultrasound has been studied for its cavitation, mechanical and thermal effects. As a pretreatment technology, ultrasonic alkali treatment has attracted much attention in the field of biomass biochemical transformation. In this study, the structural and dynamic changes of wood cell walls during ultrasound-water, alkali, and ultrasound-alkali treatments were investigated by stereoscopic microscopy, confocal Raman microscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction. The results indicated that the ultrasound-water, alkali, and ultrasound-alkali treatments had the effect of removing extractives from conduits. The uniform self-shrinking samples with shrinkage conduits were obtained by the alkali and ultrasound-alkali treatments. All of the treatments affected the relative content, structure and distribution of the chemical components in the wood cell walls. Compared with water-immersion samples, the relative content of hemicellulose of the treated samples reduced from 32.31% to 7.02% for ultrasound-8% NaOH treated samples. For the signal intensity of lignin, ultrasound-water treated and ultrasound-alkali treated samples displayed a more significant reductions than the alkali treated samples in the cell wall region. The crystal zone and amorphous zone of cellulose coexisted before and after the treatment, for all of the treated samples, and particularly for the ultrasound-assisted treated samples, the crystallinity increased from 38.15% for water-immersion samples to 57.42% for ultrasound-8% NaOH treated samples., (Copyright © 2021. Published by Elsevier B.V.)

One way of satisfying increased market demand and simultaneously achieving a reduced environmental load in the industrial paper production is the use of fibrous agricultural residues. The aims of this study were i) to investigate the effect of alkaline - hydrodynamic cavitation (HC) pre-treatments on the delignification of Miscanthus × giganteus stalks (MGS) and ii) establishing the suitability of MGS as feedstock and their exploitation in pulp and paper manufacturing. It was demonstrated that the proposed treatment is an efficient delignification method for the non-wood fiber sources, such as miscanthus. A significant outcome of this work was the observation that HC treatment preserved the fibres lengths and surface quality of raw MGS, but at the same time increased the amount of kinked and curled fibers present in cavitated miscanthus fibers. The average miscanthus fiber length was found to be relatively short at 0.45 (±0.28) mm, while the slenderness ratio, the flexibility coefficient and Runkel ratio values were calculated to be 28.13, 38.16 and 1.62, respectively. The estimated physical properties of MGS pulp hand-sheets were 24.88 (±3.09) N m g -1 as the tensile index, 0.92 (±0.06) kPa m 2 g -1 as the burst index and 4.0 (±0.37) mN m 2 g -1 as the tear index. Overall the current work demonstrated effective use of hydrodynamic cavitation for improving the processing in pulp and paper manufacturing., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

Mild and effective pretreatments are essential to deconstruct lignocellulosic biomass so as to reuse cellulose content for value-added products. In this study, sequential multimode-ultrasound and microwave with natural ternary deep eutectic solvent (NATDES) pretreatments were used to deconstruct corn straw and optimized factors such as NATDES, ultrasonic, and microwave parameters. Results indicated that the ultrasound-NATDES or microwave-NATDES pretreatment could remove 37.86% and 52.36% lignin, respectively. When using sequential multimode-ultrasound and microwave assisted NATDES pretreatment, the delignification efficiency increased to 61.50%, and the cellulose content increased from 34.70% to 76.08%. In addition, the delignification of sequential multimode-ultrasound and microwave assisted NATDES pretreatment (under the mild conditions of microwave heating at 60 °C and 60 min) increased to 57.39%, and the cellulose content increased to 59.98%, too. This highlighted the effect of the combined ultrasound and microwave technology. Finally, the microstructural changes of mercury intrusion porosimeters, scanning electron microscopy, thermogravimetric, X-ray diffraction and Fourier transform mid-infrared spectroscopy were conducted to confirm the effectiveness of this method to deconstruct corn straw. A mechanism of the deconstruction of corn straw biomass in NATDES with the assistance of the sequential multimode-ultrasound and microwave heating was proposed. This research could open a window for future use of biomass energy by deconstructing lignocellulosic biomasses using environmentally friendly pretreatment methods., (Copyright © 2020 The Author(s). Published by Elsevier B.V. All rights reserved.)

Aluminum oxide (Al 2 O 3 ) nanoparticles (NPs) are among the nanoparticles most used industrially, but their impacts on living organisms are widely unknown. We evaluated the effects of 50-1000 mg L -1 Al 2 O 3 NPs on the growth, metabolism of lignin and its monomeric composition in soybean plants. Al 2 O 3 NPs did not affect the length of roots and stems. However, at the microscopic level, Al 2 O 3 NPs altered the root surface inducing the formation of cracks near to root apexes and damage to the root cap. The results suggest that Al 2 O 3 NPs were internalized and accumulated into the cytosol and cell wall of roots, probably interacting with organelles such as mitochondria. At the metabolic level, Al 2 O 3 NPs increased soluble and cell wall-bound peroxidase activities in roots and stems but reduced phenylalanine ammonia-lyase activity in stems. Increased lignin contents were also detected in roots and stems. The Al 2 O 3 NPs increased the p-hydroxyphenyl monomer levels in stems but reduced them in roots. The total phenolic content increased in roots and stems; cell wall-esterified p-coumaric and ferulic acids increased in roots, while the content of p-coumaric acid decreased in stems. In roots, the content of ionic aluminum (Al +3 ) was extremely low, corresponding to 0.0000252% of the aluminum applied in the nanoparticulate form. This finding suggests that all adverse effects observed were due to the Al 2 O 3 NPs only. Altogether, these findings suggest that the structure and properties of the soybean cell wall were altered by the Al 2 O 3 NPs, probably to reduce its uptake and phytotoxicity., (Copyright © 2020 Elsevier Masson SAS. All rights reserved.)

Garlic (Allium sativum L.) is an economically important vegetable crop which is used worldwide for culinary and medicinal purposes. Soil salinity constrains the yield components of garlic. Understanding the responsive mechanism of garlic to salinity is crucial to improve its tolerance. To address this problem, two garlic cultivars differing in salt tolerance were used to investigate the long-term adaptive responses to salt stress at phenotype and transcriptome levels. Phenotypic analysis showed four-week salt stress significantly decreased the yield components of salt-sensitive cultivar. Transcriptomes of garlics were de novo assembled and mined for transcriptional activities regulated by salt stress. The results showed that photosynthesis, energy allocation, and secondary metabolism were commonly enriched in both sensitive and tolerant genotypes. Moreover, distinct responsive patterns were also observed between the two genotypes. Compared with the salt-tolerant genotype, most transcripts encoding enzymes in the phenylpropanoid biosynthesis pathway were coordinately down regulated in the salt-sensitive genotype, resulting in alternation of the content and composition of lignin. Meanwhile, transcripts encoding the enzymes in the brassinosteroid (BR) biosynthesis pathway were also systematically down regulated in the salt-sensitive genotypes. Taken together, these results suggested that BR-mediated lignin accumulation possibly plays an important role in garlic adaption to salt stress. These findings expand the understanding of responsive mechanism of garlic to salt stress., (Copyright © 2020 Elsevier Masson SAS. All rights reserved.)

Silicon (Si) is the second most abundant element on earth crust, consisting primarily of silicate minerals. Si is found in the tissues of almost all terrestrial plants and is mostly deposited in specialized cells or cell walls as amorphous silica. Numerous discoveries have shown that in addition to non-covalent interactions through amorphous silica, Si can form covalent bonds with plant cell wall components such as hemicelluloses, pectin and lignin. The covalent bonds may be formed via Si-O-C linkages between monosilicic acid (H 4 SiO 4 ) and cis-diols of cell wall polysaccharides or lignin. The covalently bound organosilicon, independent of amorphous inorganic silica, may play a crucial role in plant cell wall structure and remodeling and thus plant growth and its resistance against biotic and abiotic stresses. This review discusses the existing research on the discovery of plant silicon-cell wall complexes and proposes a model of their covalent bond formation and biofunction., (Copyright © 2020 Elsevier Masson SAS. All rights reserved.)

Cellulose nanofiber (CNF) hydrogels with low lignin (8%) (LL-CNF) and high lignin (18%) (HL-CNF) content were produced at nominal powers of 240, 720 and 1200 W using high-intensity ultrasound technology (HIUS). Freeze-dried CNF hydrogels were evaluated as scaffolds for gingival fibroblast cells proliferation aiming biomedical applications. HIUS processing improved the dispersibility of the CNF and increased the water retention value by more than 5 times. The LL-CNF had a maximum fibrillation yield of 46 wt.%, whereas the HL-CNF had a maximum fibrillation yield of 40 wt.% at nominal power of ≥720 W. Regardless of the lignin content, the CNF hydrogels exhibited a typical elastic gel-like behavior with the highest elasticity of 263 Pa. After freeze-drying, the CNF aerogels had porosity ≥ 96.8%, and swelling capacity up to 42.1 g PBS/g aerogel. Moreover, the cell proliferation assay showed no differences in proliferation among the LL-CNF and HL-CNF scaffolds up to 11 days. Therefore, CNF scaffolds prepared with lignin content up to 18% present promising application in the biomedical field., (Copyright © 2019. Published by Elsevier B.V.)

Delignification of sawdust was studied using ultrasound assisted alkali peroxide approach using longitudinal horn for the first time and the efficacy compared with more commonly used configurations of ultrasonic reactors. Comparison with the conventional approach based on stirring has also been presented to establish the process intensification benefits. Effect of different operating parameters such as sodium carbonate concentration (0.1, 0.15, 0.2, 0.25 M), hydrogen peroxide concentration (0.2, 0.4, 0.6, 0.8, 1 M) and biomass loading (2, 4, 6, 8, 10 wt%), on the efficacy of lignin extraction has been investigated for different ultrasonic reactors. The optimum conditions for probe type ultrasonic horn were established as 150 W, 50% duty cycle and 80% amplitude with optimum process conditions as Na 2 CO 3 concentration as 0.2 M, H 2 O 2 concentration as 1 M, biomass loading of 10 wt% and operating time of 70 min. Longitudinal horn resulted in best efficacy (both in terms of yield and energy requirements) followed by ultrasonic horn and ultrasonic bath whereas the conventional approach was least effective. The obtained lignin was also analyzed using different characterization techniques. The presence of peaks at wavelength range of 875-817, 1123-1110, and at 1599 cm -1 for the extracted sample confirmed the presence of lignin. Increase in the crystallinity index of the processed sample (maximum for longitudinal horn) also confirmed the lignin removal as lignin is amorphous in nature. Overall it has been concluded that ultrasound can be effectively used for delignification with longitudinal horn as best configuration., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In Gordts et al. (2015), we have shown that lignosulfonic acid, a commercially available lignin derivative, possesses broad antiviral activity against human immunodeficiency virus (HIV) and Herpes simplex virus (HSV) by preventing viral entry into susceptible target cells. Because of the interesting safety profile as potential microbicide, we now determined the antiviral activity of a series of lignosulfonates in order to understand better which molecular features can contribute to their antiviral activity. Here, 24 structurally different lignosulfonates were evaluated for their capacity to inhibit HIV and HSV transmission and replication in various cellular assays. These derivatives differ in origin (hardwood or softwood), counter-ion used during sulphite processing (Na + , Ca 2+ , or NH 4 + ), sulphur content, carboxylic acid percentage, and molecular weight fraction, which allowed to determine structure-activity relationships. We demonstrate that the broad antiviral activity of lignosulfonates is mainly dependent on their molecular weight and that their mechanism of action is based on interactions with the viral envelope glycoproteins. This makes the lignosulfonates a potential low-cost microbicide that protects women from sexual HIV and HSV transmission and thus prevents life-long infection., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Humic substances readily identifiable in the environment are involved in several biotic and abiotic reactions affecting carbon turnover, soil fertility, plant nutrition and stimulation, xenobiotic transformation and microbial respiration. Inspired by natural roles of humic substances, several applications of these substances, including crop stimulants, redox mediators, anti-oxidants, human medicines, environmental remediation and fish feeding, have been developed. The annual market for humic substances has grown rapidly for these reasons and due to eco-conscious features, but there is a limited supply of natural coal-related resources such as lignite and leonardite from which humic substances are extracted in bulk. The structural similarity between humic substances and lignin suggests that lignocellulosic refinery resulting in lignin residues as a by-product could be a potential candidate for a bulk source of humic-like substances, but structural differences between the two polymeric materials indicate that additional transformation procedures allowing lignin architecture to fully mimic commercial humic substances are required. In this review, we introduce the emerging concept of artificial humification of lignin-related materials as a promising strategy for lignin valorization. First, the core structural features of humic substances and the relationship between these features and the physicochemical properties, natural functions and versatile applications of the substances are described. In particular, the mechanism by which humic substances stimulate the growth of plants and hence can improve crop productivity is highlighted. Second, top-down and bottom-up transformation pathways for scalable humification of small lignin-derived phenols, technical lignins and lignin-containing plant residues are described in detail. Finally, future directions are suggested for research and development of artificial lignin humification to achieve alternative ways of producing customized analogues of humic substances., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The updated definition of prebiotic expands the range of potential applications in which emerging xylooligosaccharides (XOS) can be used. It has been demonstrated that XOS exhibit prebiotic effects at lower amounts compared to others, making them competitively priced prebiotics. As a result, the industry is focused on developing alternative approaches to improve processes efficiency that can meet the increasing demand while reducing costs. Recent advances have been made towards greener and more efficient processes, by applying process integration strategies to produce XOS from costless lignocellulosic residues and using genetic engineering to create microorganisms that convert these residues to XOS. In addition, collecting more in vivo data on their performance will be key to achieve regulatory claims, greatly increasing XOS commercial value., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Lignin is one of the most abundant renewable resources on earth and is readily produced as a sidestream during biomass fractioning. So far, these large quantities of lignin have been severely underutilized, thereby wasting this valuable renewable. Recent technological advances in lignin recovery, breakdown, and conversion have now started forming the first sustainable value chains to take advantage of lignin. Microbial cell factories, inspired by nature's miscellaneous set of lignin-degrading microbes, are at the heart of these novel processes. Recent success stories in which the enzymes and pathways of these microbes were harnessed for biobased production from lignin hold great promise for a sustainable upgrading of this renewable polymer into value-added compounds., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

This study demonstrated the effect of two-pot sequential pretreatment, comprising of ultrasound assisted deep eutectic solvent (DES) with the aim to investigate the effects of ultrasound amplitude and duration in enhancing delignification. Oil palm fronds (OPF) were ultrasonicated in a water medium, followed by a pretreatment using DES (choline chloride:urea). Fourier transform infra-red spectroscopy, X-ray diffraction, field emission scanning electron microscope, Brunauer-Emmet-Teller and solubilised lignin concentration were conducted to confirm the effectiveness of ultrasound assisted DES on the pretreatment of OPF. The recommended ultrasound conditions were determined to be 70% amplitude and duration of 30 min, where the sequential DES pretreatment was able to reduce lignin content of OPF to 14.01%, while improving xylose recovery by 58%., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The present study evaluated the role of nitric oxide (NO) in mediating adventitious root (AR) growth, lignification and related enzymatic changes in the hypocotyls of Vigna radiata. To meet the objectives, the changes in AR growth, lignin content, and the activities of enzymes-peroxidases, polyphenol oxidases, and phenylalanine ammonia lyases- with NO donor and its scavenger were monitored. Hypocotyls were cultivated in aqueous solution supplemented with different concentrations of SNP (sodium nitroprusside, NO donor compound) and its scavenging compound (2,4-carboxyphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; cPTIO). Specifically, at low concentrations, SNP induced AR growth, increased the total lignin content and altered the activities of related oxidoreductases- peroxidases, polyphenol oxidases and phenylalanine ammonia lyases- which are involved in lignin biosynthesis pathway. At higher concentrations, a decline in AR growth and lignification was noticed. We analysed the function of NO in AR formation by depleting the endogenous NO using scavenging compound cPTIO. Hypocotyls grown in a medium supplemented with scavenger cPTIO exhibited significant decline in AR growth and the activities of lignin synthesizing enzymes. Application of NO scavenger showed that stimulatory properties on root lignification may be owing to NO itself. In addition, changes in AR growth were significantly correlated with these modified biochemical activities. Our analysis revealed that NO supplementation induces prominent alterations in lignin level during AR formation and this might be due to an alteration in the activity of lignin biosynthetic enzymes, which further affected the polymerization of monolignols and AR growth., (Copyright © 2019 Elsevier Masson SAS. All rights reserved.)

Filamentous fungi, as the main producers of lignocellulolytic enzymes in industry, need to be engineered to improve the economy of large-scale lignocellulose conversion. Investigation of the cellular processes involved in lignocellulolytic enzyme production, as well as optimization of enzyme mixtures for higher hydrolysis efficiency, have provided effective targets for the engineering of lignocellulolytic fungi. Recently, the development of efficient genetic manipulation systems in several lignocellulolytic fungi opens up the possibility of systems engineering of these strains. Here, we review the recent progresses made in the engineering of lignocellulolytic fungi and highlight the research gaps in this area., (Copyright © 2018 Elsevier Inc. All rights reserved.)

As a significant platform chemical, 2, 3-butanediol (2, 3-BD) has found wide applications in industry. The success of microbial 2, 3-BD production was limited by the use of pathogenic microorganisms and low titer in engineered hosts. The utilization of cheaply available feedstock such as lignocellulose was another major challenge to achieve economic production of 2, 3-BD. To address those issues, engineering strategies including both genetic modifications and process optimization have been employed. In this review, we summarized the state-of-the-art progress in the biotechnological production of 2, 3-BD. Metabolic engineering and process engineering strategies were discussed., (Copyright © 2018. Published by Elsevier Inc.)

Lignocellulosic biomass is a sustainable feedstock for fuel ethanol production, but it is characterized by low mass and energy densities, and distributed production with relatively small scales is more suitable for cellulosic ethanol, which can better balance cost for the feedstock logistics. Lignocellulosic biomass is recalcitrant to degradation, and pretreatment is needed, but more efficient pretreatment technologies should be developed based on an in-depth understanding of its biosynthesis and regulation for engineering plant cell walls with less recalcitrance. Simultaneous saccharification and co-fermentation has been developed for cellulosic ethanol production, but the concept has been mistakenly defined, since the saccharification and co-fermentation are by no means simultaneous. Lignin is unreactive, which not only occupies reactor spaces during the enzymatic hydrolysis of the cellulose component and ethanol fermentation thereafter, but also requires extra mixing, making high solid loading difficult for lignocellulosic biomass and ethanol titers substantially compromised, which consequently increases energy consumption for ethanol distillation and stillage discharge, presenting another challenge for cellulosic ethanol production. Pentose sugars released from the hydrolysis of hemicelluloses are not fermentable with Saccharomyces cerevisiae used for ethanol production from sugar- and starch-based feedstocks, and engineering the brewing yeast and other ethanologenic species such as Zymomonas mobilis with pentose metabolism has been performed within the past decades. However strategies for the simultaneous co-fermentation of pentose and hexose sugars that have been pursued overwhelmingly for strain development might be modified for robust ethanol production. Finally, unit integration and system optimization are needed to maximize economic and environmental benefits for cellulosic ethanol production. In this article, we critically reviewed updated progress, and highlighted challenges and strategies for solutions., (Copyright © 2019 Elsevier Inc. All rights reserved.)

In this work, potassium iodide (KI) and graphene oxide (GO) were utilized to promote the selectivity of photocatalytic process for alkali lignin oxidation over ZnO. Different concertation of GO was added during the microwave synthesis procedure of ZnO, and the characterization results revealed that graphene can shift the conduction band to more reducing potential, resulting to higher production of superoxide anion radicals (O 2 - ) compared to OH. Response Surface Methodology revealed the most suitable interaction among loading of GO, KI and irradiation time on lignin and total phenolic compound (TPC) degradation. Specifically, the optimal conditions (i.e. maximum lignin (52%) and minimum TPC (55%) degradation) were at [KI] = 0.64 mM; GO content into ZnO 1.2 mg/mL; 240 min of irradiation time. The results showed that higher addition of graphene into structure of ZnO could preserve more phenolics from degradation due to less production of OH. Furthermore, the addition of KI at optimized conditions could enhance the selectivity of degradation of lignin and phenolics via producing I radicals and quenching the excess amount of generated OH, respectively. The lower generation of OH at optimized conditions was quantitatively confirmed by a photoluminescence simplified technique. In addition, the effect of the photocatalytic process on substrate's anaerobic degradability was examined in order to evaluate the suitability of the pretreated solution for energy recovery. Indeed, besides the higher TPC concentration, the biogas production of treated straw at optimized conditions was increased by 35% compared to the untreated sample., (Copyright © 2018. Published by Elsevier Ltd.)

Conversion of lignocellulosic biomass to fuels and chemicals has attracted immense research and development around the world. Lowering recalcitrance of biomass in a cost-effective manner is a challenge to commercialize biomass-based technologies. Deep eutectic solvents (DESs) are new 'green' solvents that have a high potential for biomass processing because of their low cost, low toxicity, biodegradability, easy recycling and reuse. This article discusses the properties of DESs and recent advances in their application for lignocellulosic biomass processing. The effectiveness of DESs in hydrolyzing lignin-carbohydrate complexes, removing lignin/hemicellulose from biomass as well as their effect on biomass deconstruction, crystallinity and enzymatic digestibility have been discussed. Moreover, this review presents recent findings on the compatibility of natural DESs with enzymes and microorganisms., (Copyright © 2018. Published by Elsevier Inc.)

Osteoclasts are multinucleated cells that originate from hemopoietic stem cells. Targeting over activated osteoclasts is thought to be an effective therapeutic approach to osteoporosis. In a previous study, we reported that Tatarinan O, a lignin-like compound, suppressed RANKL-induced osteoclastogenesis. In this study, we further examined the effects on osteoclast formation of three lignin-like compounds including Tatarinan N (TN), Tatarinan U (TU) and Tatarinan V (TV), all containing a common structure of asarone. We found that only TN suppressed RANKL-induced osteoclast differentiation, bone resorption pit formation and F-acting ring formation. TU and TV did not influence RANKL-induced osteoclastogenesis. We also found that TN dose-dependently inhibited the expression of osteoclastogenesis-associated genes, including TRAP, cathepsin K and MMP-9. Furthermore, we found that TN down-regulated the key transcription factor NFATc1 and c-Fos by preventing the activation of NF-κB and phosphorylation of MAPKs including ERK1/2 and p38 but not JNK. TN attenuated calcineurin expression via suppression of the Btk-PLCγ2 cascade and reduction of intracellular Ca 2+ , modulating NFATc1 activation. Taking together, our results indicated that TN might have therapeutic potential for osteoporosis., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The purpose of this paper was to investigate the effect of ultrasound-ionic liquid (IL) pretreatment on the enzymatic and acid hydrolysis of the sugarcane bagasse and wheat straw. The lignocellulosic biomass was dissociated in ILs ([Bmim]Cl and [Bmim]AOC) aided by ultrasound waves. Sonication was performed at different frequencies (20, 28, 35, 40, and 50kHz), a power of 100W, a time of 30min and a temperature of 80°C. The changes in the structure and crystallinity of the cellulose were studied by Fourier transform infrared (FT-IR), X-ray diffraction (XRD) and thermal gravimetric analysis (TGA). The amounts of the total reducing sugars, glucose, cellobiose, xylose and arabinose in the hydrolysates were determined. The results of FT-IR, XRD and TGA revealed that the structure of cellulose of both biomass samples remained intact after the pretreatment, but the crystallinity decreased. The enzymatic and acid hydrolysis of the biomass samples pretreated with the ultrasound-IL result in higher yields of the reducing sugars compared with the IL-pretreated sample. Enzymatic hydrolysis of bagasse and wheat straw pretreated with [Bmim]Cl-ultrasound resulted in maximal yields of glucose at 20kHz (40.32% and 53.17%) and acid hydrolysis resulted in maximal yields of glucose at 40kHz (33.32% and 48.07%). Enzymatic hydrolysis of bagasse and wheat straw pretreated with [Bmim]OAc-ultrasound show maximal yields of glucose at 28kHz and acid hydrolysis at 50kHz. Combination of ultrasound with [Bmim]OAc is more effective than [Bmim]Cl in terms of the yields of reducing sugar., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Motivated by industrial demands and ongoing scientific discoveries continuous efforts are made to identify and create improved biocatalysts dedicated to plant biomass conversion. α-1,2 and α-1,3 arabinofuranosyl specific α-l-arabinofuranosidases (EC 3.2.1.55) are debranching enzymes catalyzing hydrolytic release of α-l-arabinofuranosyl residues, which decorate xylan or arabinan backbones in lignocellulosic and pectin constituents of plant cell walls. The CAZy database classifies α-l-arabinofuranosidases in Glycoside Hydrolase (GH) families GH2, GH3, GH43, GH51, GH54 and GH62. Only GH62 contains exclusively α-l-arabinofuranosidases and these are of fungal and bacterial origin. Twenty-two GH62 enzymes out of 223 entries in the CAZy database have been characterized and very recently new knowledge was acquired with regard to crystal structures, substrate specificities, and phylogenetics, which overall provides novel insights into structure/function relationships of GH62. Overall GH62 α-l-arabinofuranosidases are believed to play important roles in nature by acting in synergy with several cell wall degrading enzymes and members of GH62 represent promising candidates for biotechnological improvements of biofuel production and in various biorefinery applications., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Fungi produce heme-containing peroxidases and peroxygenases, flavin-containing oxidases and dehydrogenases, and different copper-containing oxidoreductases involved in the biodegradation of lignin and other recalcitrant compounds. Heme peroxidases comprise the classical ligninolytic peroxidases and the new dye-decolorizing peroxidases, while heme peroxygenases belong to a still largely unexplored superfamily of heme-thiolate proteins. Nevertheless, basidiomycete unspecific peroxygenases have the highest biotechnological interest due to their ability to catalyze a variety of regio- and stereo-selective monooxygenation reactions with H 2 O 2 as the source of oxygen and final electron acceptor. Flavo-oxidases are involved in both lignin and cellulose decay generating H 2 O 2 that activates peroxidases and generates hydroxyl radical. The group of copper oxidoreductases also includes other H 2 O 2 generating enzymes - copper-radical oxidases - together with classical laccases that are the oxidoreductases with the largest number of reported applications to date. However, the recently described lytic polysaccharide monooxygenases have attracted the highest attention among copper oxidoreductases, since they are capable of oxidatively breaking down crystalline cellulose, the disintegration of which is still a major bottleneck in lignocellulose biorefineries, along with lignin degradation. Interestingly, some flavin-containing dehydrogenases also play a key role in cellulose breakdown by directly/indirectly "fueling" electrons for polysaccharide monooxygenase activation. Many of the above oxidoreductases have been engineered, combining rational and computational design with directed evolution, to attain the selectivity, catalytic efficiency and stability properties required for their industrial utilization. Indeed, using ad hoc software and current computational capabilities, it is now possible to predict substrate access to the active site in biophysical simulations, and electron transfer efficiency in biochemical simulations, reducing in orders of magnitude the time of experimental work in oxidoreductase screening and engineering. What has been set out above is illustrated by a series of remarkable oxyfunctionalization and oxidation reactions developed in the frame of an intersectorial and multidisciplinary European RTD project. The optimized reactions include enzymatic synthesis of 1-naphthol, 25-hydroxyvitamin D 3 , drug metabolites, furandicarboxylic acid, indigo and other dyes, and conductive polyaniline, terminal oxygenation of alkanes, biomass delignification and lignin oxidation, among others. These successful case stories demonstrate the unexploited potential of oxidoreductases in medium and large-scale biotransformations., (Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.)

The adverse environmental impacts of the fossil fuel and the concerns of energy security necessitate the development of alternative clean energy sources from renewable feedstocks. Lignocellulosic biomass is a 2nd generation feedstock used in the production of biofuels and bio-based products that are conventionally derived from fossil resources. The biochemical conversion, which entails biomass pretreatment, enzymatic hydrolysis and fermentation, is one major platform used to transform lignocelluloses into biofuels. However, lignin presents many challenges to enzymatic hydrolysis leading to the need of high enzyme dose, low hydrolysis yield, low level of recyclability, high cost of enzymatic hydrolysis (because of the high cost of enzymes), and so on. Therefore, enzymatic hydrolysis, which is not cost effective, becomes one of major cost contributors. To mitigate the negative effects of lignin, extensive research has been conducted to explore the fundamental mechanisms of lignin-enzyme interactions to develop technologies to overcome the negative effects of lignin on enzymatic hydrolysis. Non-productive adsorption, which is characterized by hydrophobic, electrostatic and/or hydrogen bonding interactions, is widely known as the primary mechanism governing lignin-enzyme interactions. In addition, lignin-enzyme interaction is also influenced by steric hindrance (i.e., the physical blocking of enzyme access to carbohydrates by lignin). However, the mechanisms underlying the lignin-enzyme interactions remain unclear. This article aims to present a comprehensive review on the lignin-enzyme interactions (i.e. the mechanism, governing driving forces, modeling, and technologies for mitigating the negative effect of lignin). The current challenges inherent in this process and possible avenues of research in cellulosic biorefinery conclude this article., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Currently, nanosystems have been developed and applied as promising vehicles for different biomedical applications. We have developed three lignin nanoparticles (LNPs): pure lignin nanoparticles (pLNPs), iron(III)-complexed lignin nanoparticles (Fe-LNPs), and Fe 3 O 4 -infused lignin nanoparticles (Fe 3 O 4 -LNPs) with round shape, narrow size distribution, reduced polydispersity and good stability at pH 7.4. The LNPs showed low cytotoxicity in all the tested cell lines and hemolytic rates below 12% after 12 h of incubation. Additionally, they induced hydrogen peroxide production in a small extent and time-dependent manner, and the interaction with the cells increased over time, exhibiting a dose-dependent cell uptake. Concerning the drug loading, pLNPs showed the capacity to efficiently load poorly water-soluble drugs and other cytotoxic agents, e.g. sorafenib and benzazulene (BZL), and improve their release profiles at pH 5.5 and 7.4 in a sustained manner. Furthermore, the BZL-pLNPs presented an enhanced antiproliferation effect in different cells compared to the pure BZL and showed a maximal inhibitory concentration ranging from 0.64 to 12.4 μM after 24 h incubation. Overall, LNPs are promising candidates for drug delivery applications, and the superparamagnetic behavior of Fe 3 O 4 -LNPs makes them promising for cancer therapy and diagnosis, such as magnetic targeting and magnetic resonance imaging., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Lignin, a major constituent of plant cell-wall and by-product of paper based industries is traditionally used for low value applications (heat or electricity generation), but its potential in high value utilization has also been widely reported. In this work, we synthesized lignin colloidal particles using ultrasonic spray-freezing route without any chemical functionalization of material, and stabilized it by electrostatic route. As per our knowledge, this technique is the first reported method which yields hollow/solid lignin colloids having good particle size control without any chemical functionalization of material. Dioxane soluble fraction of Alkali lignin (d-lignin) was used without any further chemical functionalization. d-lignin dissolved in DMSO was sprayed upon liquid nitrogen cooled copper plate using an ultrasonic nebulizer. The resulting frozen droplets were collected and found to possess hollow and solid morphology. Particles thus obtained were characterized for their size distribution and morphology, and compared to theoretically anticipated values. Size tunability of particles in relation to concentration of sprayed lignin solution was also studied. In addition to that, six layers of lignin colloids were deposited on quartz slide with the aid of negligible UV absorbing polyelectrolyte aqueous solution PDADMAC [Poly (diallyldimethylammonium chloride)]. Gradation in UV absorbing ability of lignin with increase in number of layers could be clearly observed. Hollow and solid lignin colloids, apart from their application in sunscreen cosmetics owing to their UV absorbing ability, show potential applications in drug delivery also., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Highly stable and dispersible nanocrystalline cellulose (NCC) was successfully isolated from oil palm empty fruit bunch microcrystalline cellulose (OPEFB-MCC), with yields of 93% via a sono-assisted TEMPO-oxidation and a subsequent sonication process. The sono-assisted treatment has a remarkable effect, resulting in an increase of more than 100% in the carboxylate content and a significant increase of approximately 39% in yield compared with the non-assisted process. TEM images reveal the OPEFB-NCC to have rod-like crystalline morphology with an average length and width of 122 and 6nm, respectively. FTIR and solid-state 13 C-NMR analyses suggest that oxidation of cellulose chain hydroxyl groups occurs at C6. XRD analysis shows that OPEFB-NCC consists primarily of a crystalline cellulose I structure. Both XRD and 13 C-NMR indicate that the OPEFB-NCC has a lower crystallinity than the OPEFB-MCC starting material. Thermogravimetric analysis illustrates that OPEFB-NCC is less thermally stable than OPEFB-MCC but has a char content of 46% compared with 7% for the latter, which signifies that the carboxylate functionality acts as a flame retardant., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Recent studies have revealed that lignin-like polymerized polyphenols can activate innate immune systems. In this study, we aimed to evaluate whether these polymerized polyphenols could activate leukocytes from different murine strains. Splenocytes from 12 mouse strains were investigated. Our results revealed species differences in reactivity to phenolic polymers on interferon-γ (IFN-γ) release. Mice that possessed the H2(a) or H2(k) haplotype antigens were the highly responsive strains. To clarify these different points in soluble factors, multiplex cytokine profiling analysis was carried out and we identified interleukin (IL)-2 as a key molecule for IFN-γ induction by polymerized polyphenols. Furthermore, inhibition of IL-2 and IL-2Rα by neutralizing antibodies significantly decreased cytokine production in the highly responsive mice strains. Our results indicate that species difference in reactivity to phenolic polymers is mediated by adequate release of IL-2 and its receptor, IL-2Rα., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The degradation of plant biomass is a major challenge towards the production of bio-based compounds and materials. As key lignocellulolytic enzyme producers, filamentous fungi represent a promising reservoir to tackle this challenge. Among them, the coprophilous ascomycete Podospora anserina has been used as a model organism to study various biological mechanisms because its genetics are well understood and controlled. In 2008, the sequencing of its genome revealed a great diversity of enzymes targeting plant carbohydrates and lignin. Since then, a large array of lignocellulose-acting enzymes has been characterized and genetic analyses have enabled the understanding of P. anserina metabolism and development on plant biomass. Overall, these research efforts shed light on P. anserina strategy to unlock recalcitrant lignocellulose deconstruction., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Ultrasound (US) can be used to disrupt microcrystalline cellulose to give nanofibers via ultrasonic cavitation. Sodium percarbonate (SP), consisting of sodium carbonate and hydrogen peroxide, generates highly reactive radicals, which cause oxidative delignification. Here, we describe a novel pretreatment technique using a combination of US and SP (US-SP) for the efficient saccharification of cellulose and hemicellulose in lignocellulosic corn stover. Although US-SP pretreatment was conducted under mild condition (i.e., at room temperature and atmospheric pressure), the pretreatment greatly increased lignin removal and cellulose digestibility. We also determined the optimum US-SP treatment conditions, such as ultrasonic power output, pretreatment time, pretreatment temperature, and SP concentration for an efficient cellulose saccharification. Moreover, xylose could be effectively recovered from US-SP pretreated biomass without the formation of microbial inhibitor furfural., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Thermochemical-biological hybrid processing uses thermochemical decomposition of lignocellulosic biomass to produce a variety of intermediate compounds that can be converted into fuels and chemicals through microbial fermentation. It represents a unique opportunity for biomass conversion as it mitigates some of the deficiencies of conventional biochemical (pretreatment-hydrolysis-fermentation) and thermochemical (pyrolysis or gasification) processing. Thermochemical-biological hybrid processing includes two pathways: (i) pyrolysis/pyrolytic substrate fermentation, and (ii) gasification/syngas fermentation. This paper provides a comprehensive review of these two hybrid processing pathways, including the characteristics of fermentative substrates produced in the thermochemical stage and microbial utilization of these compounds in the fermentation stage. The current challenges of these two biomass conversion pathways include toxicity of the crude pyrolytic substrates, the inhibition of raw syngas contaminants, and the mass-transfer limitations in syngas fermentation. Possible approaches for mitigating substrate toxicities are discussed. The review also provides a summary of the current efforts to commercialize hybrid processing., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Agricultural and forest residues obtained after harvesting are promising renewable sources, suitable as a source of pulp for cellulose nanocrystal manufacturing. Cavitation-assisted softening of the lignin-carbohydrate matrix offers sample opportunity for cellulose fibril liberation and degradation of amorphous cellulose. The present work addresses cavitation assisted cellulose fibril and crystal liberation and film forming properties of the supernatant phase of treated agricultural and forest residues. The effectiveness of this method has been evaluated according to crystallinity indices and hydrogen bond energies, as measured by FT-IR analysis. It has been observed that the use of cavitation increased the crystallinity and caused partial removal and degradation of the lignin matrix. Overall, it appears that considerable improvement of crystallinity can be obtained from agricultural and forest residues through the use of cavitation., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Lignin, the main natural aromatic polymer was always aroused researchers interest. Currently around 90% of this biomaterial is burned for energy. It has a very complex and complicated structure which depends on the separation method and plant species, what determine difficulties to use as a raw material widely. This research presents a physical method to modify lignin by ultrasonic irradiation in order to obtain nanoparticles. The nanoparticles synthesized were dimensionally and morphologically characterized. At the same time the preoccupations were to determine the structural and compositional changes that occurred after sonication. To achieve this, two types of commercial lignins (wheat straw and Sarkanda grass) were used and the modifications were analyzed by FTIR-spectroscopy, GPC-chromatography, (31)P-NMR-spectroscopy and HSQC0. The results confirm that the compositional and structural changes of nanoparticles obtained are not significantly modified at the intensity applied but depend on the nature of lignin., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Modification of lignin is recognized as an important aspect of the successful refining of lignocellulosic biomass, and enzyme-assisted processing and upcycling of lignin is receiving significant attention in the literature. Laccases (EC 1.10.3.2) are taking the centerstage of this attention, since these enzymes may help degrading lignin, using oxygen as the oxidant. Laccases can catalyze polymerization of lignin, but the question is whether and how laccases can directly catalyze modification of lignin via catalytic bond cleavage. Via a thorough review of the available literature and detailed illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin model compounds; ii) For laccases to catalyze inter-unit bond cleavage in lignin substrates, the presence of a mediator system is required. Clearly, the higher the redox potential of the laccase enzyme, the broader the range of substrates, including o- and p-diphenols, aminophenols, methoxy-substituted phenols, benzenethiols, polyphenols, and polyamines, which may be oxidized. In addition, the currently available analytical methods that can be used to detect enzyme catalyzed changes in lignin are summarized, and an improved nomenclature for unequivocal interpretation of the action of laccases on lignin is proposed., (Copyright © 2015 Elsevier Inc. All rights reserved.)