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      Differences in S/G ratio in natural poplar variants do not predict catalytic depolymerization monomer yields

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          Abstract

          The ratio of syringyl (S) and guaiacyl (G) units in lignin has been regarded as a major factor in determining the maximum monomer yield from lignin depolymerization. This limit arises from the notion that G units are prone to C-C bond formation during lignin biosynthesis, resulting in less ether linkages that generate monomers. This study uses reductive catalytic fractionation (RCF) in flow-through reactors as an analytical tool to depolymerize lignin in poplar with naturally varying S/G ratios, and directly challenges the common conception that the S/G ratio predicts monomer yields. Rather, this work suggests that the plant controls C-O and C-C bond content by regulating monomer transport during lignin biosynthesis. Overall, our results indicate that additional factors beyond the monomeric composition of native lignin are important in developing a fundamental understanding of lignin biosynthesis.

          Abstract

          The ratio of syringyl (S) and guaiacyl (G) units in lignin has been regarded as a major factor in determining the maximum monomer yield. Here, the authors challenge this common conception using reductive catalytic fractionation in flow-through reactors as an analytical tool to depolymerize lignin in poplar with naturally varying S/G ratios.

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          Most cited references48

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          Bright Side of Lignin Depolymerization: Toward New Platform Chemicals

          Lignin, a major component of lignocellulose, is the largest source of aromatic building blocks on the planet and harbors great potential to serve as starting material for the production of biobased products. Despite the initial challenges associated with the robust and irregular structure of lignin, the valorization of this intriguing aromatic biopolymer has come a long way: recently, many creative strategies emerged that deliver defined products via catalytic or biocatalytic depolymerization in good yields. The purpose of this review is to provide insight into these novel approaches and the potential application of such emerging new structures for the synthesis of biobased polymers or pharmacologically active molecules. Existing strategies for functionalization or defunctionalization of lignin-based compounds are also summarized. Following the whole value chain from raw lignocellulose through depolymerization to application whenever possible, specific lignin-based compounds emerge that could be in the future considered as potential lignin-derived platform chemicals.
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            Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization

            Practical, high-yield lignin depolymerization methods could greatly increase biorefinery productivity and profitability. However, development of these methods is limited by the presence of interunit carbon-carbon bonds within native lignin, and further by formation of such linkages during lignin extraction. We report that adding formaldehyde during biomass pretreatment produces a soluble lignin fraction that can be converted to guaiacyl and syringyl monomers at near theoretical yields during subsequent hydrogenolysis (47 mole % of Klason lignin for beech and 78 mole % for a high-syringyl transgenic poplar). These yields were three to seven times those obtained without formaldehyde, which prevented lignin condensation by forming 1,3-dioxane structures with lignin side-chain hydroxyl groups. By depolymerizing cellulose, hemicelluloses, and lignin separately, monomer yields were between 76 and 90 mole % for these three major biomass fractions.
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              Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

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                Author and article information

                Contributors
                Gregg.beckham@nrel.gov
                yroman@mit.edu
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                2 May 2019
                2 May 2019
                2019
                : 10
                : 2033
                Affiliations
                [1 ]ISNI 0000 0001 2341 2786, GRID grid.116068.8, Department of Chemical Engineering, , Massachusetts Institute of Technology, ; 25 Ames St, Cambridge, MA 02139 USA
                [2 ]ISNI 0000 0001 2199 3636, GRID grid.419357.d, National Bioenergy Center, , National Renewable Energy Laboratory, ; 15013 Denver W Pkwy, Golden, CO 80401 USA
                [3 ]ISNI 0000 0004 0446 2659, GRID grid.135519.a, Oak Ridge National Laboratory, ; 1 Bethel Valley Rd, Oak Ridge, TN 37830 USA
                [4 ]ISNI 0000 0004 0446 2659, GRID grid.135519.a, The Center for Bioenergy Innovation, , Oak Ridge National Laboratory, ; Oak Ridge, TN 37830 USA
                Author information
                http://orcid.org/0000-0002-3480-212X
                http://orcid.org/0000-0002-0025-4233
                Article
                9986
                10.1038/s41467-019-09986-1
                6497657
                31048697
                76b5a7ba-c5fd-4691-8c6b-79519a62937b
                © The Author(s) 2019

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 14 November 2018
                : 9 April 2019
                Categories
                Article
                Custom metadata
                © The Author(s) 2019

                Uncategorized
                biosynthesis,heterogeneous catalysis,biofuels
                Uncategorized
                biosynthesis, heterogeneous catalysis, biofuels

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