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Current Opinion in Biotechnology Jun 2017The biochemical properties of lignin present major obstacles to deriving societally beneficial entities from lignocellulosic biomass, an abundant and renewable... (Review)
Review
The biochemical properties of lignin present major obstacles to deriving societally beneficial entities from lignocellulosic biomass, an abundant and renewable feedstock. Similar to other biopolymers such as polysaccharides, polypeptides, and ribonucleic acids, lignin polymers are derived from multiple types of monomeric units. However, lignin's renowned recalcitrance is largely attributable to its racemic nature and the variety of covalent inter-unit linkages through which its aromatic monomers are linked. Indeed, unlike other biopolymers whose monomers are consistently inter-linked by a single type of covalent bond, the monomeric units in lignin are linked via non-enzymatic, combinatorial radical coupling reactions that give rise to a variety of inter-unit covalent bonds in mildly branched racemic polymers. Yet, despite the chemical complexity and stability of lignin, significant strides have been made in recent years to identify routes through which valued commodities can be derived from it. This paper discusses emerging biological and biochemical means through which degradation of lignin to aromatic monomers can lead to the derivation of commercially valuable products.
Topics: Animal Feed; Biomass; Ether; Lignin; Polysaccharides
PubMed: 28346893
DOI: 10.1016/j.copbio.2017.02.015 -
Plant Physiology Mar 2022Lignin is a complex phenylpropanoid polymer deposited in the secondary cell walls of vascular plants. Unlike most gymnosperm and eudicot lignins that are generated via...
Lignin is a complex phenylpropanoid polymer deposited in the secondary cell walls of vascular plants. Unlike most gymnosperm and eudicot lignins that are generated via the polymerization of monolignols, grass lignins additionally incorporate the flavonoid tricin as a natural lignin monomer. The biosynthesis and functions of tricin-integrated lignin (tricin-lignin) in grass cell walls and its effects on the utility of grass biomass remain largely unknown. We herein report a comparative analysis of rice (Oryza sativa) mutants deficient in the early flavonoid biosynthetic genes encoding CHALCONE SYNTHASE (CHS), CHALCONE ISOMERASE (CHI), and CHI-LIKE (CHIL), with an emphasis on the analyses of disrupted tricin-lignin formation and the concurrent changes in lignin profiles and cell wall digestibility. All examined CHS-, CHI-, and CHIL-deficient rice mutants were largely depleted of extractable flavones, including tricin, and nearly devoid of tricin-lignin in the cell walls, supporting the crucial roles of CHS and CHI as committed enzymes and CHIL as a noncatalytic enhancer in the conserved biosynthetic pathway leading to flavone and tricin-lignin formation. In-depth cell wall structural analyses further indicated that lignin content and composition, including the monolignol-derived units, were differentially altered in the mutants. However, regardless of the extent of the lignin alterations, cell wall saccharification efficiencies of all tested rice mutants were similar to that of the wild-type controls. Together with earlier studies on other tricin-depleted grass mutant and transgenic plants, our results reflect the complexity in the metabolic consequences of tricin pathway perturbations and the relationships between lignin profiles and cell wall properties.
Topics: Acyltransferases; Flavonoids; Lignin; Oryza
PubMed: 34963002
DOI: 10.1093/plphys/kiab606 -
International Journal of Molecular... Apr 2022Oxidative depolymerization of lignin is a hot topic in the field of biomass valorization. The most recent and green procedures have been herein detailed. Photochemical... (Review)
Review
Oxidative depolymerization of lignin is a hot topic in the field of biomass valorization. The most recent and green procedures have been herein detailed. Photochemical and electrochemical approaches are reviewed highlighting the pros and cons of each method. Mechanochemistry activated strategies are able to combine oxidation and depolymerization in the deconstruction of lignin. Homogenous and heterogeneous catalytic systems are exemplified stressing the green aspects associated with both the procedures. Solvent-free approaches as well as those carried out in alternative media are listed. Finally, the few examples of selenium catalyzed lignin valorization reported so far are cited.
Topics: Biomass; Catalysis; Lignin; Oxidation-Reduction; Oxidative Stress
PubMed: 35457195
DOI: 10.3390/ijms23084378 -
Plant Physiology Jan 2022Recent studies demonstrate that several polyphenolic compounds produced from beyond the canonical monolignol biosynthetic pathways can behave as lignin monomers,...
Recent studies demonstrate that several polyphenolic compounds produced from beyond the canonical monolignol biosynthetic pathways can behave as lignin monomers, participating in radical coupling reactions and being incorporated into lignin polymers. Here, we show various classes of flavonoids, the chalconoid naringenin chalcone, the flavanones naringenin and dihydrotricin, and the flavone tricin, incorporated into the lignin polymer of papyrus (Cyperus papyrus L.) rind. These flavonoids were released from the rind lignin by Derivatization Followed by Reductive Cleavage (DFRC), a chemical degradative method that cleaves the β-ether linkages, indicating that at least a fraction of each was integrated into the lignin as β-ether-linked structures. Due to the particular structure of tricin and dihydrotricin, whose C-3' and C-5' positions at their B-rings are occupied by methoxy groups, these compounds can only be incorporated into the lignin through 4'-O-β bonds. However, naringenin chalcone and naringenin have no substituents at these positions and can therefore form additional carbon-carbon linkages, including 3'- or 5'-β linkages that form phenylcoumaran structures not susceptible to cleavage by DFRC. Furthermore, Nuclear Magnetic Resonance analysis indicated that naringenin chalcone can also form additional linkages through its conjugated double bond. The discovery expands the range of flavonoids incorporated into natural lignins, further broadens the traditional definition of lignin, and enhances the premise that any phenolic compound present at the cell wall during lignification could be oxidized and potentially integrated into the lignin structure, depending only on its chemical compatibility. This study indicates that papyrus lignin has a unique structure, as it is the only lignin known to date that integrates such a diversity of phenolic compounds from different classes of flavonoids. This discovery will open up new ways to engineer and design lignins with specific properties and for enhanced value.
Topics: Binding Sites; Biosynthetic Pathways; Cyperus; Egypt; Flavonoids; Lignin; Molecular Structure
PubMed: 34662399
DOI: 10.1093/plphys/kiab469 -
Current Opinion in Biotechnology Feb 2016Lignin is a complex polyphenolic constituent of plant secondary cell walls. Inspired largely by the recalcitrance of lignin to biomass processing, plant engineering... (Review)
Review
Lignin is a complex polyphenolic constituent of plant secondary cell walls. Inspired largely by the recalcitrance of lignin to biomass processing, plant engineering efforts have routinely sought to alter lignin quantity, composition, and structure by exploiting the inherent plasticity of lignin biosynthesis. More recently, researchers are attempting to strategically design plants for increased degradability by incorporating monomers that lead to a lower degree of polymerisation, reduced hydrophobicity, fewer bonds to other cell wall constituents, or novel chemically labile linkages in the polymer backbone. In addition, the incorporation of value-added structures could help valorise lignin. Designer lignins may satisfy the biological requirement for lignification in plants while improving the overall efficiency of biomass utilisation.
Topics: Animals; Carbohydrate Metabolism; Carbohydrates; Cell Wall; Hydrophobic and Hydrophilic Interactions; Lignin; Plants
PubMed: 26775114
DOI: 10.1016/j.copbio.2015.10.009 -
Advanced Science (Weinheim,... Dec 2022Recent studies have found that green hydrogen production and biomass utilization technologies can be combined to efficiently produce both hydrogen and value-added...
Recent studies have found that green hydrogen production and biomass utilization technologies can be combined to efficiently produce both hydrogen and value-added chemicals using biomass as an electron and proton source. However, the majority of them have been limited to proof-of-concept demonstrations based on batch systems. Here the authors report the design of modular flow systems for the continuous depolymerization and valorization of lignin and low-voltage hydrogen production. A redox-active phosphomolybdic acid is used as a catalyst to depolymerize lignin with the production of aromatic compounds and extraction of electrons for hydrogen production. Individual processes for lignin depolymerization, byproduct separation, and hydrogen production with catalyst reactivation are modularized and integrated to perform the entire process in the serial flow. Consequently, this work enabled a one-flow process from biomass conversion to hydrogen gas generation under a cyclic loop. In addition, the unique advantages of the fluidic system (i.e., effective mass and heat transfer) substantially improved the yield and efficiency, leading to hydrogen production at a higher current density (20.5 mA cm ) at a lower voltage (1.5 V) without oxygen evolution. This sustainable eco-chemical platform envisages scalable co-production of valuable chemicals and green hydrogen for industrial purposes in an energy-saving and safe manner.
Topics: Lignin; Catalysis; Oxidation-Reduction; Hydrogen
PubMed: 36285674
DOI: 10.1002/advs.202204170 -
Molecules (Basel, Switzerland) Apr 2018Currently, lignin is mainly produced in pulping processes, but it is considered as an under-utilized chemical since it is being mainly used as a fuel source. Lignin... (Review)
Review
Currently, lignin is mainly produced in pulping processes, but it is considered as an under-utilized chemical since it is being mainly used as a fuel source. Lignin contains many hydroxyl groups that can participate in chemical reactions to produce value-added products. Flocculants, adsorbents, and dispersants have a wide range of applications in industry, but they are mainly oil-based chemicals and expensive. This paper reviews the pathways to produce water soluble lignin-based flocculants, adsorbents, and dispersants. It provides information on the recent progress in the possible use of these lignin-based flocculants, adsorbents, and dispersants. It also critically discusses the advantages and disadvantages of various approaches to produce such products. The challenges present in the production of lignin-based flocculants, adsorbents, and dispersants and possible scenarios to overcome these challenges for commercial use of these products in industry are discussed.
Topics: Adsorption; Biomass; Flocculation; Lignin; Solubility
PubMed: 29642602
DOI: 10.3390/molecules23040868 -
Biomacromolecules Jun 2023The lignin-carbohydrate complexes (LCCs) typically present in the liquors produced in the pre-hydrolysis of biomass cause severe difficulties in downstream...
The lignin-carbohydrate complexes (LCCs) typically present in the liquors produced in the pre-hydrolysis of biomass cause severe difficulties in downstream fractionation. To address this issue, a series of LCC samples were accessed from solutions obtained from the pre-hydrolysis of extractive-free pine wood meal (H-LCC) and compared with LCC obtained from the corresponding residues (B-LCC). Chromatographic and spectroscopic techniques revealed that 8.2% of the lignins were degraded at 160 °C, resulting from the breakage of β-O-4' linkages during pre-hydrolysis. Meanwhile, (reactive) hemicelluloses were mainly removed from the fibers' cell walls. Some hemicelluloses in the pre-hydrolysis liquor, such as glucomannans, were associated with degraded lignin fragments via ether and ester bonds. However, the newly formed LCCs were pH-labile and underwent rapid hydrolysis. Overall, we reveal details about LCC formation and degradation during pre-hydrolysis at given temperatures, critically important in efforts to improve biomass processing and valorization.
Topics: Lignin; Hydrolysis; Magnetic Resonance Spectroscopy; Carbohydrates; Wood
PubMed: 37264927
DOI: 10.1021/acs.biomac.3c00053 -
Applied Microbiology and Biotechnology Sep 2018Commercial mushrooms are produced on lignocellulose such as straw, saw dust, and wood chips. As such, mushroom-forming fungi convert low-quality waste streams into... (Review)
Review
Commercial mushrooms are produced on lignocellulose such as straw, saw dust, and wood chips. As such, mushroom-forming fungi convert low-quality waste streams into high-quality food. Spent mushroom substrate (SMS) is usually considered a waste product. This review discusses the applications of SMS to promote the transition to a circular economy. SMS can be used as compost, as a substrate for other mushroom-forming fungi, as animal feed, to promote health of animals, and to produce packaging and construction materials, biofuels, and enzymes. This range of applications can make agricultural production more sustainable and efficient, especially if the CO emission and heat from mushroom cultivation can be used to promote plant growth in greenhouses.
Topics: Agaricales; Agriculture; Culture Media; Lignin; Waste Products
PubMed: 30027491
DOI: 10.1007/s00253-018-9226-8 -
Plant Physiology Jan 2023Bioengineering approaches to modify lignin content and structure in plant cell walls have shown promise for facilitating biochemical conversions of lignocellulosic...
Bioengineering approaches to modify lignin content and structure in plant cell walls have shown promise for facilitating biochemical conversions of lignocellulosic biomass into valuable chemicals. Despite numerous research efforts, however, the effect of altered lignin chemistry on the supramolecular assembly of lignocellulose and consequently its deconstruction in lignin-modified transgenic and mutant plants is not fully understood. In this study, we aimed to close this gap by analyzing lignin-modified rice (Oryza sativa L.) mutants deficient in 5-HYDROXYCONIFERALDEHYDE O-METHYLTRANSFERASE (CAldOMT) and CINNAMYL ALCOHOL DEHYDROGENASE (CAD). A set of rice mutants harboring knockout mutations in either or both OsCAldOMT1 and OsCAD2 was generated in part by genome editing and subjected to comparative cell wall chemical and supramolecular structure analyses. In line with the proposed functions of CAldOMT and CAD in grass lignin biosynthesis, OsCAldOMT1-deficient mutant lines produced altered lignins depleted of syringyl and tricin units and incorporating noncanonical 5-hydroxyguaiacyl units, whereas OsCAD2-deficient mutant lines produced lignins incorporating noncanonical hydroxycinnamaldehyde-derived units. All tested OsCAldOMT1- and OsCAD2-deficient mutants, especially OsCAldOMT1-deficient lines, displayed enhanced cell wall saccharification efficiency. Solid-state nuclear magnetic resonance (NMR) and X-ray diffraction analyses of rice cell walls revealed that both OsCAldOMT1- and OsCAD2 deficiencies contributed to the disruptions of the cellulose crystalline network. Further, OsCAldOMT1 deficiency contributed to the increase of the cellulose molecular mobility more prominently than OsCAD2 deficiency, resulting in apparently more loosened lignocellulose molecular assembly. Such alterations in cell wall chemical and supramolecular structures may in part account for the variations of saccharification performance of the OsCAldOMT1- and OsCAD2-deficient rice mutants.
Topics: Lignin; Oryza; Plant Proteins; Mutation; Cell Wall
PubMed: 36124989
DOI: 10.1093/plphys/kiac432