An “ideal lignin” facilitates full biomass utilization

The structural homogeneity and acid stability of linear C-lignins allow their deconstruction to useful monomers in high yield. Lignin, a major component of lignocellulosic biomass, is crucial to plant growth and development but is a major impediment to efficient biomass utilization in various processes. Valorizing lignin is increasingly realized as being essential. However, rapid condensation of lignin during acidic extraction leads to the formation of recalcitrant condensed units that, along with similar units and structural heterogeneity in native lignin, drastically limits product yield and selectivity. Catechyl lignin (C-lignin), which is essentially a benzodioxane homopolymer without condensed units, might represent an ideal lignin for valorization, as it circumvents these issues. We discovered that C-lignin is highly acid-resistant. Hydrogenolysis of C-lignin resulted in the cleavage of all benzodioxane structures to produce catechyl-type monomers in near-quantitative yield with a selectivity of 90% to a single monomer.

[1]  J. Ralph,et al.  An uncondensed lignin depolymerized in the solid state and isolated from lignocellulosic biomass: a mechanistic study , 2018 .

[2]  F. Liu,et al.  Toward engineering E. coli with an autoregulatory system for lignin valorization , 2018, Proceedings of the National Academy of Sciences.

[3]  S. V. D. Bosch,et al.  Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading. , 2018, Chemical Society reviews.

[4]  J. Luterbacher,et al.  Protection Group Effects During α,γ-Diol Lignin Stabilization Promote High-Selectivity Monomer Production. , 2018, Angewandte Chemie.

[5]  Katalin Barta,et al.  Bright Side of Lignin Depolymerization: Toward New Platform Chemicals , 2018, Chemical reviews.

[6]  J. Ralph,et al.  Characterization and Elimination of Undesirable Protein Residues in Plant Cell Wall Materials for Enhancing Lignin Analysis by Solution-State Nuclear Magnetic Resonance Spectroscopy. , 2017, Biomacromolecules.

[7]  R. Sun,et al.  Catalytic Hydrogenolysis of Lignins into Phenolic Compounds over Carbon Nanotube Supported Molybdenum Oxide , 2017 .

[8]  L. Daemen,et al.  Selective production of arenes via direct lignin upgrading over a niobium-based catalyst , 2017, Nature Communications.

[9]  Jianmin Lu,et al.  Promoting Lignin Depolymerization and Restraining the Condensation via an Oxidation-Hydrogenation Strategy , 2017 .

[10]  Wei‐Yin Sun,et al.  A redox-neutral catechol synthesis , 2017, Nature Communications.

[11]  Ydna M. Questell-Santiago,et al.  Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization , 2016, Science.

[12]  Ning Li,et al.  A facile and fast method for quantitating lignin in lignocellulosic biomass using acidic lithium bromide trihydrate (ALBTH) , 2016 .

[13]  Zhimin Xue,et al.  Biomass-Derived γ-Valerolactone-Based Solvent Systems for Highly Efficient Dissolution of Various Lignins: Dissolution Behavior and Mechanism Study , 2016 .

[14]  John Ralph,et al.  Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis , 2016, Angewandte Chemie.

[15]  M. Crowley,et al.  Radical Nature of C-Lignin , 2016 .

[16]  T. Yokoyama,et al.  NMR Assignment for Diaryl Ether Structures (4-O-5 Structures) in Pine Wood Lignin. , 2016, Biomacromolecules.

[17]  W. Boerjan,et al.  Designer lignins: harnessing the plasticity of lignification. , 2016, Current opinion in biotechnology.

[18]  Matthew J. Eckelman,et al.  Life Cycle Assessment of Catechols from Lignin Depolymerization , 2016 .

[19]  S. V. D. Bosch,et al.  Influence of bio-based solvents on the catalytic reductive fractionation of birch wood , 2015 .

[20]  T. Cantat,et al.  Convergent reductive depolymerization of wood lignin to isolated phenol derivatives by metal-free catalytic hydrosilylation , 2015 .

[21]  N. Westwood,et al.  Aromatic monomers by in situ conversion of reactive intermediates in the acid-catalyzed depolymerization of lignin. , 2015, Journal of the American Chemical Society.

[22]  Bert F. Sels,et al.  Reductive lignocellulose fractionation into soluble lignin-derived phenolic monomers and dimers and processable carbohydrate pulps , 2015 .

[23]  N. Westwood,et al.  Isolation of functionalized phenolic monomers through selective oxidation and C-O bond cleavage of the β-O-4 linkages in lignin. , 2015, Angewandte Chemie.

[24]  T. Yokoyama.  Revisiting the Mechanism of β-O-4 Bond Cleavage During Acidolysis of Lignin. Part 6: A Review , 2015 .

[25]  J. Coon,et al.  Formic-acid-induced depolymerization of oxidized lignin to aromatics , 2014, Nature.

[26]  R. Dixon,et al.  Coexistence but Independent Biosynthesis of Catechyl and Guaiacyl/Syringyl Lignin Polymers in Seed Coats[W][OPEN] , 2013, Plant Cell.

[27]  F. Busqué,et al.  Catechol‐Based Biomimetic Functional Materials , 2013, Advanced materials.

[28]  R. Rinaldi,et al.  Solvent effects on the hydrogenolysis of diphenyl ether with Raney nickel and their implications for the conversion of lignin. , 2012, ChemSusChem.

[29]  R. Dixon,et al.  A polymer of caffeyl alcohol in plant seeds , 2012, Proceedings of the National Academy of Sciences.

[30]  T. Foust,et al.  Computational Study of Bond Dissociation Enthalpies for a Large Range of Native and Modified Lignins , 2011 .

[31]  J. Ralph,et al.  CCoAOMT suppression modifies lignin composition in Pinus radiata. , 2011, The Plant journal : for cell and molecular biology.

[32]  T. Reiner,et al.  Towards quantitative catalytic lignin depolymerization. , 2011, Chemistry.

[33]  J. Ralph,et al.  Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d(6)/pyridine-d(5). , 2010, Organic & biomolecular chemistry.

[34]  K. Holtman,et al.  Quantitative 13C NMR Characterization of Milled Wood Lignins Isolated by Different Milling Techniques , 2006 .

[35]  V. Tarabanko,et al.  New Mechanism for the Catalytic Oxidation of Lignin to Vanillin , 2004 .

[36]  D. Argyropoulos,et al.  Quantitative (13)C NMR analysis of lignins with internal standards. , 2001, Journal of agricultural and food chemistry.

[37]  C. Chapple,et al.  Modified lignin in tobacco and poplar plants over-expressing the Arabidopsis gene encoding ferulate 5-hydroxylase. , 2000, The Plant journal : for cell and molecular biology.

[38]  D. E. Willis,et al.  Calculation of Flame Ionization Detector Relative Response Factors Using the Effective Carbon Number Concept , 1985 .

[39]  W. J. Dyer,et al.  A rapid method of total lipid extraction and purification. , 1959, Canadian journal of biochemistry and physiology.

[40]  Evan S. Beach,et al.  Depolymerization of organosolv lignin to aromatic compounds over Cu-doped porous metal oxides , 2014 .

[41]  R. Dixon,et al.  Novel seed coat lignins in the Cactaceae: structure, distribution and implications for the evolution of lignin diversity. , 2013, The Plant journal : for cell and molecular biology.

[42]  Amie D. Sluiter,et al.  Determination of Structural Carbohydrates and Lignin in Biomass , 2004 .

[43]  C. Lapierre,et al.  Thioacidolysis of Spruce Lignin: GC-MS Analysis of the Main Dimers Recovered After Raney Nickel Desulphuration , 1991 .

[44]  D. Argyropoulos,et al.  Condensation of lignin in dioxane-water-HCl , 1987 .

[45]  C. Lapierre,et al.  Preparative Thioacidolysis of Spruce Lignin: Isolation and Identification of Main Monomeric Products , 1986 .

[46]  E. Cowling,et al.  Comparative Studies on Cellulolytic Enzyme Lignin and Milled Wood Lignin of Sweetgum and Spruce , 1975 .