Solar energy driven C–C bond cleavage in a lignin model compound with a D–π–A organic dye-sensitized photoanode

Kim, Saerona; Kang, Hyeong Cheol; Cai, Chun; Li, Shuuya; Yoo, Kicheon; Wijethunga, Udani K.; Zheng, Weiwei; Yoo, Chang Geun; Sherman, Benjamin D.; Lee, Jae‐Joon; Leem, Gyu

doi:10.1039/d3se00194f

Cited by 11 publications

(6 citation statements)

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“…Also, the chemical shift at around δH/δC 5.93/106.16 ppm appeared after the oxidative reaction, indicating the cleavage product P1 . ,, The peaks at δH/δC 9.67/200.87 (D a ) and δH/δC 4.63/83.48 (D b ) were assigned to the C/H correlations of C a /H a and C b /H b , respectively, of product derived from G unit P2 . In the reaction at pH 5, the contours at δH/δC 5.42/80.44 in the aliphatic region and δH/δC 7.33/105.73 in the aromatic region correspond to the C/H correlations of C β /H β and C 2/6 /H 2/6 , respectively, from the oxidized C α -ketone ( P4 ) structure (A ox ). , Based on the above results and aforementioned studies, we propose a pH-dependent breakdown of β-O-4 aryl ether bonds in phenolic LMC via enzymatic oxidation catalyzed by PcLiP01, as shown in Figure S6. When the cationic radical Int 1 is produced through the SET from S1 to Cpd I/II , deprotonation occurs due to the very low p K a of phenol radical cations (p K a (ArOH) •+ ≈ −2.0), , leading to the prevalence of phenoxy radicals 1a compared to radical cations.…”

Section: Resultsmentioning

confidence: 98%

“…Our recent study reported the first approach, photocatalytic chemoselective cleavage of the C(aryl)–C(sp3) σ-bond in a phenolic lignin model compound (LMC) at room temperature, by using a photoelectrocatalytic (PEC) process (Figure b). This system yielded excellent selectivity (>90%) for C–C bond cleavage of a phenolic LMC at room temperature in the presence of aminoxyl mediators resulting in producing a value-added aromatic chemical, 2,6-dimethoxybenzoquinone (DMBQ) . However, this work has been limited to studying a relatively simple phenolic LMC that lacks the additional electron-rich moieties in real lignin.…”

Section: Introductionmentioning

confidence: 99%

“…Copyright 2012 John Wiley & Sons), hydrogen atom transfer-mediated (HAT) dye-sensitized photoelectrochemical cell (DSPEC) system b (Adapted from ref . Copyright 2021 American Chemical Society), and D−π–A organic dye-based DSPEC system c (Adapted from ref . Copyright 2023 Royal Society of Chemistry).…”

Section: Introductionmentioning

confidence: 99%

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Lignin Peroxidase-Catalyzed Selective Cleavage of C–C Bonds in Lignin at Room Temperature

Nguyen,

Kim,

Yoo

et al. 2024

ACS Catal.

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Selective oxidative cleavage of C−C linkages is a challenge for chemical transformations including lignin depolymerization. This study reports recombinant Phanerochaete chrysosporium lignin peroxidase isozyme 1 (PcLiP01)-catalyzed nonpolar C−C σ-bond cleavage in lignin model compounds (LMCs), dehydrogenative polymer (DHP), and real milled wood lignin (MWL) to produce a targeted value-added aromatic compound, 2,6-dimethoxy-1,4-benzoquinone (DMBQ) under mild conditions. Notably, according to pH-dependent redox reactions with both phenolic and nonphenolic LMCs, C aryl −C α cleavage products of the LMCs were dominant under low pH ∼ 3 compared to pH ∼ 5. Furthermore, the oxidative conversion of DHP and MWL using PcLiP01 showed 12 and 5 mg/g substrate yields of DMBQ, respectively. These findings offer an approach to support a C−C bond cleavage reaction with less-reactive nonphenolic LMCs and provide valuable insights into the oxidative conversion of lignin to the value-added chemical DMBQ with PcLiP01.

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Lignin Peroxidase-Catalyzed Selective Cleavage of C–C Bonds in Lignin at Room Temperature

Nguyen,

Kim,

Yoo

et al. 2024

ACS Catal.

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“…Given the similarities in the mechanism, including the light absorption and ion/electron transport, the success of the ideal device design for solar hydrogen production can be expanded toward other types of "articial leaf," such as producing chemical fuels from solar energy via CO 2 reduction, 46 PEC ammonia synthesis, 47 and biomass valorisation. 48 In summary, to fabricate membrane-embedded PEC watersplitting devices, three key characteristics must be satised:…”

Section: Membrane-embedded Pec Water-splitting Devicesmentioning

confidence: 99%

Designing idealised devices for bias-free solar water splitting

Park,

Kim,

Kim

et al. 2024

Sustainable Energy Fuels

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“…For example, the most recent one is on the cleavage of C–C/C–O bonds in lignin using dye-sensitized photoelectrosynthetic solar cells. This method presents a promising direction for the sustainable production of chemicals based on lignin [ 111 , 112 ].…”

Section: Lignin-based Networkmentioning

confidence: 99%

Synthesis and Applications of Hybrid Polymer Networks Based on Renewable Natural Macromolecules

Getya

Gitsov

2023

Molecules

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Macromolecules obtained from renewable natural sources are gaining increasing attention as components for a vast variety of sustainable polymer-based materials. Natural raw materials can facilitate continuous-flow production due to their year-round availability and short replenishment period. They also open new opportunities for chemists and biologists to design and create “bioreplacement” and “bioadvantaged” polymers, where complex structures produced by nature are being modified, upgraded, and utilized to create novel materials. Bio-based macromonomers are expected not only to compete with but to replace some petroleum-based analogs, as well. The development of novel sustainable materials is an ongoing and very dynamic process. There are multiple strategies for transforming natural macromolecules into sophisticated value-added products. Some methods include chemical modification of macromolecules, while others include blending several components into one new system. One of the most promising approaches for incorporating renewable macromolecules into new products is the synthesis of hybrid networks based on one or more natural components. Each one has unique characteristics, so its incorporation into a network brings new sustainable materials with properties that can be tuned according to their end-use. This article reviews the current state-of-the-art and future potential of renewable natural macromolecules as sustainable building blocks for the synthesis and use of hybrid polymer networks. The most recent advancements and applications that involve polymers, such as cellulose, chitin, alginic acid, gellan gum, lignin, and their derivatives, are discussed.

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Solar energy driven C–C bond cleavage in a lignin model compound with a D–π–A organic dye-sensitized photoanode

Abstract: Chemoselective C–C bond cleavage remains a challenge in organic synthesis and for the degradation of polymers because of the relatively high bond dissociation energy of C–C σ-bonds at room temperature....

Cited by 11 publications

References 53 publications

Lignin Peroxidase-Catalyzed Selective Cleavage of C–C Bonds in Lignin at Room Temperature

Lignin Peroxidase-Catalyzed Selective Cleavage of C–C Bonds in Lignin at Room Temperature

Designing idealised devices for bias-free solar water splitting

Synthesis and Applications of Hybrid Polymer Networks Based on Renewable Natural Macromolecules

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