Biocatalytic conversion of fatty acids into drop-in biofuels: Towards sustainable energy sources

EFB Bioeconomy Journal, Journal Year: 2023, Volume and Issue: 3, P. 100049 - 100049

Published: March 10, 2023

Intensifying effects of global warming necessitates swift solutions for decarbonization. A big source the increasing atmospheric CO 2 is burning transportation fuels. Although electrification light vehicles an important step to reduce emissions, carbon-based fuels will still be likely power up heavy-duty transport, marine and aviation some time. Thus, fastest way decarbonize these sectors could immediate transition carbon-neutral biofuels. Recently, conversion fatty acids into hydrocarbons, as "drop-in biofuels", emerging a promising alternative fossil However, current technologies rely on energy intensive chemical methods that are not quite eco-friendly. Therefore, enzymatic hydrocarbons present benign production method. In last decade, multiple enzymes have been discovered convert free alka(e)nes. Here, we introduce with description studies performed so far, especially regarding cell-free biocatalysis.

Language: Английский

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Efficient and Recyclable Photobiocatalytic System via Cofactor Regeneration for Chiral Aryl Alcohol Synthesis

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 12(1), P. 37 - 47

Published: Dec. 18, 2023

Integrating efficient enzyme catalysis and sustainable photocatalysis is considered an eco-friendly promising approach for substance conversion. In this work, employing a highly selective ketoreductase metal-free photocatalyst covalent organic framework (COF), we rationally constructed coimmobilized biocatalyzed artificial photosynthesis system mediated by cofactor regeneration chiral alcohol synthesis. COFs (denoted as TTA-T0 TTA-T2) were rapidly fabricated at moderate condition comparative studies, demonstrating that donor–acceptor (D–A) structural TTA-T2 possessed superior photochemical activity virtue of intramolecular charge transfer. With 98.3% yield NADH in 40 min, was applied to cascade NADH-dependent ChKRED20 the asymmetric reduction acetophenone, providing (R)-1-phenylethanol excellent enantioselectivity (ee > 99%). Further, into green matrix achieve protection well convenient recycling both enzyme. After optimizing loading amount other parameters, achieved satisfactory compatibility reusability, with more than 75% photobiocatalytic remaining after four batches operation. This work highlights potential advantages tailorable photocatalysts, strategy coimmobilizing enzymes photocatalysts could be extended solar-driven fine chemical production further development photosynthesis.

Language: Английский

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Catalytic Mechanism of Fatty Acid Photodecarboxylase: On the Detection and Stability of the Initial Carbonyloxy Radical Intermediate

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 11, 2024

In fatty acid photodecarboxylase (FAP), light-induced formation of the primary radical product RCOO⋅ from RCOO

Language: Английский

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Optimization and Engineering of Fatty Acid Photodecarboxylase for Substrate Specificity

ChemCatChem, Journal Year: 2021, Volume and Issue: 13(18), P. 4038 - 4046

Published: July 13, 2021

Abstract Fatty acid photodecarboxylase (FAP) is one of the few photoenzymes in nature. The ability FAP to convert fatty acids into alka(e)nes without need for reducing equivalents put this enzyme spotlight biocatalytic applications. Although it has been discovered only a years ago, many studies already emerged demonstrating its potential areas from biofuel production and enzymatic kinetic resolution being critical component multi‐enzyme cascades. While there have protein engineering modulating activity towards very short chain acids, no study yet addressed substrate selectivity within medium long range, where shows great promise synthesis drop‐in biofuels ubiquitous with lengths C12 C18. Here, after determining optimum expression assay conditions FAP, we screened 22 rationally designed mutant enzymes four naturally abundant substrates; : 0, C16 C18 0 1. Depending on type exchanged amino acid, observed shifts shorter or longer chains, compared wild enzyme. Notably, obtained two groups mutants; group high another that selective substrate. Moreover, measured light thermal stability as well engineered selectivity.

Language: Английский

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Immobilization and Application of Fatty Acid Photodecarboxylase in Deep Eutectic Solvents

ChemBioChem, Journal Year: 2022, Volume and Issue: 23(23)

Published: Oct. 12, 2022

Since its discovery in 2017, the fatty acid decarboxylase (FAP) photoenzyme has been focus of extensive research, given ability to convert acids into alka(e)nes using merely visible blue light. Unfortunately, there are still some drawbacks that limit applicability this biocatalyst, such as poor solubility substrates aqueous media, photostability, and impossibility reusing catalyst for several cycles. In work, we demonstrate use FAP non-conventional media a free enzyme an immobilized preparation. Namely, deep eutectic solvents (DESs) proof-of-concept immobilization commercial His-tag selective carrier, thorough study reaction conditions each case, well reusability studies shown. We observed almost complete selectivity towards C18 decarboxylation over C16 when used DES, with product analytical yield up 81 % whole cells. Furthermore, applying obtained yields >10-fold higher than ones media.

Language: Английский

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Process intensification in oxidative biocatalysis

Current Opinion in Green and Sustainable Chemistry, Journal Year: 2022, Volume and Issue: 38, P. 100692 - 100692

Published: Aug. 31, 2022

In the last ten years, number of publications related to process intensification (PI) has been quadrupled. This increasing interest that created many innovations can be found not only in chemo-catalytic processes but also reached field enzymatic processes. The recent scientific and technological advances bioprocess have dedicated improving use enzymes selective oxidative reactions, obtaining more environmentally friendly resource efficient applications. this mini-review, we provide an overview different PI definitions, studies focusing on biocatalytic reactions regarding (i) non-conventional media, (ii) data analytics, (iii) reactor engineering, (iv) downstream processing. Remarking how other fields used for new goals (e.g., 4.0). Model-based simulations sensor technologies guarantee optimal automated with designs, together media enzyme immobilization, intensify oxidation

Language: Английский

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Chemoenzymatic Dynamic Kinetic Resolution of Secondary Alcohols and Amines Employing Copper-Based Photocatalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8347 - 8353

Published: June 8, 2023

A tandem photo- and biocatalytic dynamic kinetic resolution of secondary alcohols amines was achieved employing a commercially available lipase, Candida antarctica lipase B (CALB), heteroleptic copper complex. The process is an example using copper-based photocatalysis to promote hydrogen atom transfer (HAT) processes thiyl radicals. Screening 48 complexes 5 disulfides identified Cu(dtbbpy)(DPEPhos)BF4 (Ph3SiS)2 as optimal catalyst system the HAT process. catalytic represents general for radical-mediated racemization applicable both aliphatic aromatic (18 examples, 60 → 97% yield, 76 99% ee).

Language: Английский

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Continuous oxyfunctionalizations catalyzed by unspecific peroxygenase

Catalysis Science & Technology, Journal Year: 2022, Volume and Issue: 12(21), P. 6473 - 6485

Published: Jan. 1, 2022

Unspecific peroxygenase (UPO) has been shown to be a promising biocatalyst for oxyfunctionalization of broad range substrates with hydrogen peroxide (H 2 O ) as the cosubstrate.

Language: Английский

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Emerging Strategies for Asymmetric Synthesis: Combining Enzyme Promiscuity and Photo‐/Electro‐redox Catalysis

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(2)

Published: Jan. 27, 2023

Abstract As an emerging opportunity to expand the reactivity repertoire of enzymes achieve unnatural transformations in organic synthesis, enzyme promiscuity has attracted great interest recent years. The combination catalysis and photo‐/electro‐redox which can benefit from both exquisite selectivity unique chemical accessible photo‐/electro‐chemistry many advantages, such as new reactivity, high enantioselectivity, green yields. In past decades, most photoenzymatic enzymatic electrosynthesis mainly focused on exploiting regenerated cofactors function native activity. However, developments have demonstrated that combining unlock asymmetric reactions. This minireview highlights these strategies covers literature 2016 date. Furthermore, future development direction this field is prospected.

Language: Английский

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At-line monitoring of hydrogen peroxide released from its photocatalytic and continuous synthesis

Reaction Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 9(4), P. 777 - 781

Published: Jan. 1, 2024

Photocatalytic synthesis of H 2 O in a continuous operation set-up using nitrogen-doped carbon nanodots (N-CNDs) and simultaneous determination generated .

Language: Английский

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