Light-driven biocatalytic oxidation

Yun, Chul‐Ho; Kim, Jin-Hyun; Hollmann, Frank; Park, Chan Beum

doi:10.1039/d2sc03483b

Cited by 24 publications

(6 citation statements)

References 135 publications

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“…Our artificial wood photocatalyst is further combined with unspecific peroxygenase (EC 1.11.2.1) from Agrocybe aegerita ( Aae UPO) to accomplish the oxyfunctionalization of hydrocarbons, which produces numerous value-added compounds for pharmaceutical, bulk, and fine chemical industries. Aae UPO is an ideal and green biocatalyst to catalyze the selective oxygenation of inert C–H bonds using H 2 O 2 under mild conditions, − whereas traditional metal catalysts require toxic oxidants and harsh conditions . However, UPOs suffer from the oxidative inactivation of their heme active sites at elevated concentrations of H 2 O 2 , which can be addressed by in situ H 2 O 2 supply.…”

Section: Introductionmentioning

confidence: 99%

Biosolar Oxygenation of Hydrocarbons by Photocatalytic Artificial Wood

Jang,

Aurangzeb Khan,

Hollmann

et al. 2024

ACS Sustainable Chem. Eng.

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Lignin is the most abundant renewable and sustainable source of aromatic compounds to replace fossil resources, causing environmental issues. However, most lignin generated from pulping and biorefinery processes is combusted or discarded as waste. In this work, we first propose a photocatalytic artificial wood platform consisting of lignin and cellulose, inspired by woody cell walls, where lignin is arranged around cellulose fibers. The wood-mimetic particles were fabricated through reconstitution after the complete dissolution of lignin and cellulose. Intensive characterization revealed that the introduction of cellulose suppressed lignin’s self-aggregation, which limits its practical photocatalytic applications. As a result, the artificial wood photocatalyst exhibited a 3.2 times higher production rate of H2O2 from oxygen and water than lignin under solar light. The wood-mimetic photocatalyst was further coupled with an unspecific peroxygenase (UPO) biocatalyst to catalyze the selective oxygenation of inert C–H bonds using H2O2 as an oxidant. The wood-UPO hybrid catalyst demonstrated a universal photobiocatalytic oxyfunctionalization of various hydrocarbons with a higher total turnover number and turnover frequency than the lignin-UPO catalyst. This work suggests a practical strategy to utilize waste lignin as a photocatalyst and further demonstrates sustainable biosolar oxygenation reactions using sunlight and water as green energy and electron sources, respectively.

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Section: Introductionmentioning

confidence: 99%

Biosolar Oxygenation of Hydrocarbons by Photocatalytic Artificial Wood

Jang,

Aurangzeb Khan,

Hollmann

et al. 2024

ACS Sustainable Chem. Eng.

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“…30,31 The rapidly expanding eld of photobiocatalysis is devoted to the creation of novel light-dependent biocatalytic processes. [32][33][34][35][36][37] The link between the photochemical process and the enzymatic transformation will be used to group reports in this evaluation. We will clarify crucial terms and concentrate on subtle mechanistic differences that set several techniques apart from one another.…”

Section: Introductionmentioning

confidence: 99%

Novel applications of photobiocatalysts in chemical transformations

Singh,

Sinha,

Nainwal

et al. 2024

RSC Adv.

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“…This dilemma has led to the development of a multitude of in situ hydrogen peroxide generating systems for UPO catalysis, ranging from physicochemical to enzymatic supply cascades [14] . Among those systems, the use of visible light as a cheap, readily available energy source for the reduction of O 2 in combination with a diverse catalyst repertoire has been a reoccurring theme [5,14–19] . One of the earliest examples of these systems utilizes flavin mononucleotide (FMN) as a photocatalyst for in situ hydrogen peroxide production [16] …”

Section: Introductionmentioning

confidence: 99%

“…[14] Among those systems, the use of visible light as a cheap, readily available energy source for the reduction of O 2 in combination with a diverse catalyst repertoire has been a reoccurring theme. [5,[14][15][16][17][18][19] One of the earliest examples of these systems utilizes flavin mononucleotide (FMN) as a photocatalyst for in situ hydrogen peroxide production. [16] Flavin and its derivates have been widely used within the field of organic redox photocatalysis in the last decades, enabling a variety of classical redox chemistry, including halogenation and cyanation.…”

Section: Introductionmentioning

confidence: 99%

Light‐Controlled Biocatalysis by Unspecific Peroxygenases with Genetically Encoded Photosensitizers

Püllmann,

Homann,

Karl

et al. 2023

Angew Chem Int Ed

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Fungal unspecific peroxygenases (UPOs) have gained substantial attention for their versatile oxyfunctionalization chemistry paired with impressive catalytic capabilities. A major drawback, however, remains their sensitivity towards their co‐substrate hydrogen peroxide, necessitating the use of smart in situ hydrogen peroxide generation methods to enable efficient catalysis setups. Within this report, we introduce flavin‐containing protein photosensitizers as a new general tool for light‐controlled in situ hydrogen peroxide production. The use of light as an abundant, inexpensive, and switchable induction agent enables efficient spatial control of enzymatic activity. By genetically fusing FbFPs and UPOs, we have created two virtually self‐sufficient photo‐enzymes (PhotUPO), which have been thoroughly characterized. Subsequent testing of a versatile substrate panel with the two divergent PhotUPOs revealed two stereoselective conversions. The catalytic performance of the fusion protein was optimized through enzyme and substrate loading variation, enabling up to 24300 turnover numbers (TONs) for the sulfoxidation of methyl phenyl sulfide. The PhotUPO concept was upscaled to a 100 mg substrate preparative scale, enabling the extraction of enantiopure alcohol products.

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Light-driven biocatalytic oxidation

Abstract: Enzymes are the catalyst of choice for highly selective reactions, offering nature-inspired approaches for sustainable chemical synthesis. Oxidative enzymes (e.g., monooxygenases, peroxygenases, oxidases, or dehydrogenases) catalyze a variety of enantioselective...

Cited by 24 publications

References 135 publications

Biosolar Oxygenation of Hydrocarbons by Photocatalytic Artificial Wood

Biosolar Oxygenation of Hydrocarbons by Photocatalytic Artificial Wood

Novel applications of photobiocatalysts in chemical transformations

Light‐Controlled Biocatalysis by Unspecific Peroxygenases with Genetically Encoded Photosensitizers

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