Autoxidation Catalysis for Carbon–Carbon Bond Cleavage in Lignin

Gu, Nina X.; Palumbo, Chad T.; Bleem, Alissa C.; Sullivan, Kevin P.; Haugen, Stefan J.; Woodworth, Sean P.; Ramirez, Kelsey J.; Kenny, Jacob K.; Stanley, Lisa D.; Katahira, Rui; Stahl, Shannon S.; Beckham, Gregg T.

doi:10.1021/acscentsci.3c00813

Cited by 6 publications

(1 citation statement)

References 54 publications

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“…Oxidation and reduction reactions stand as prominent methods for lignin depolymerization, which can be conducted through various approaches, with or without catalysts. ,− A comprehensive review by Lange et al has emphasized the potential of peroxide-based methods in achieving efficient lignin depolymerization, highlighting various oxidative routes . Oxidation pathways, including autoxidation catalysis, the use of oxygen, , hydrogen peroxide, − or peracetic acid, − facilitate the cleavage of interunit linkage, side-chain modification, and phenolic ring cleavage . Oxidation by peracetic acid, especially, results in cleavage of β-O-4′ bonds and ring opening of phenolic rings to form carboxylic acid .…”

Section: Introductionmentioning

confidence: 99%

Oxidative Carboxylation of Lignin: Exploring Reactivity of Different Lignin Types

Andriani,

Lawoko

2024

Biomacromolecules

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The increased interest in the utilization of lignin in biobased applications is evident from the rise in lignin valorization studies. The present study explores the responsiveness of lignin toward oxidative valorization using acetic acid and hydrogen peroxide. The pristine lignins and their oxidized equivalents were analyzed comprehensively using NMR and SEC. The study revealed ring opening of phenolic rings yielding muconic acidand ester-end groups and side-chain oxidations of the benzylic hydroxyls. Syringyl units were more responsive to these reactions than guaiacyl units. The high selectivity of the reaction yielded oligomeric oxidation products with a narrower dispersity than pristine lignins. Mild alkaline hydrolysis of methyl esters enhanced the carboxylic acid content of oxidized lignin, presenting the potential to adjust the carboxylic acid content of lignin. While oxidation reactions in lignin valorization are well documented, this study showed the feasibility of employing optimized oxidation conditions to engineer tailored lignin-based material precursors.

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Section: Introductionmentioning

confidence: 99%

Oxidative Carboxylation of Lignin: Exploring Reactivity of Different Lignin Types

Andriani,

Lawoko

2024

Biomacromolecules

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Efficient and environmentally friendly techniques for extracting lignin from lignocellulose biomass and subsequent uses: A review

Alam,

Greco,

Rajabimashhadi

et al. 2024

Cleaner Materials

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Catalytic carbon–carbon bond cleavage in lignin via manganese–zirconium-mediated autoxidation

Palumbo,

Gu,

Bleem

et al. 2024

Nat Commun

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Efforts to produce aromatic monomers through catalytic lignin depolymerization have historically focused on aryl–ether bond cleavage. A large fraction of aromatic monomers in lignin, however, are linked by various carbon–carbon (C–C) bonds that are more challenging to cleave and limit the yields of aromatic monomers from lignin depolymerization. Here, we report a catalytic autoxidation method to cleave C–C bonds in lignin-derived dimers and oligomers from pine and poplar. The method uses manganese and zirconium salts as catalysts in acetic acid and produces aromatic carboxylic acids as primary products. The mixtures of the oxygenated monomers are efficiently converted to cis,cis-muconic acid in an engineered strain of Pseudomonas putida KT2440 that conducts aromatic O-demethylation reactions at the 4-position. This work demonstrates that autoxidation of lignin with Mn and Zr offers a catalytic strategy to increase the yield of valuable aromatic monomers from lignin.

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Autoxidation Catalysis for Carbon–Carbon Bond Cleavage in Lignin

Cited by 6 publications

References 54 publications

Oxidative Carboxylation of Lignin: Exploring Reactivity of Different Lignin Types

Oxidative Carboxylation of Lignin: Exploring Reactivity of Different Lignin Types

Efficient and environmentally friendly techniques for extracting lignin from lignocellulose biomass and subsequent uses: A review

Catalytic carbon–carbon bond cleavage in lignin via manganese–zirconium-mediated autoxidation

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