Where Chemocatalysis Meets Biocatalysis: In Water

Chemical Reviews, Год журнала: 2022, Номер 123(9), С. 5262 - 5296

Опубликована: Дек. 6, 2022

Chemoenzymatic catalysis, by definition, involves the merging of sequential reactions using both chemocatalysis and biocatalysis, typically in a single reaction vessel. A major challenge, solution to which, however, is associated with numerous advantages, run such one-pot processes water: majority enzyme-catalyzed take place water as Nature's medium, thus enabling broad synthetic diversity when due option use virtually all types enzymes. Furthermore, cheap, abundantly available, environmentally friendly, making it, principle, an ideal medium. On other hand, most routinely performed today organic solvents (which might deactivate enzymes), appearing make it difficult combine biocatalysis toward cascades water. Several creative approaches solutions that enable combinations chemo- be realized applied problems are presented herein, reflecting state-of-the-art this blossoming field. Coverage has been sectioned into three parts, after introductory remarks: (1) Chapter 2 focuses on historical developments initiated area research; (2) 3 describes key post-initial discoveries have advanced field; (3) 4 highlights latest achievements provide attractive main question compatibility between (used predominantly aqueous media) (that remains solvents), Chapters covering mainly literature from ca. 2018 present. 5 6 brief overview where field stands, challenges lie ahead, ultimately, prognosis looking future chemoenzymatic catalysis synthesis.

Язык: Английский

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Expanding the Synthetic Toolbox through Metal–Enzyme Cascade Reactions

Chemical Reviews, Год журнала: 2023, Номер 123(9), С. 5297 - 5346

Опубликована: Янв. 10, 2023

The combination of metal-, photo-, enzyme-, and/or organocatalysis provides multiple synthetic solutions, especially when the creation chiral centers is involved. Historically, enzymes and transition metal species have been exploited simultaneously through dynamic kinetic resolutions racemates. However, more recently, linear cascades appeared as elegant solutions for preparation valuable organic molecules combining bioprocesses metal-catalyzed transformations. Many advantages are derived from this symbiosis, although there still bottlenecks to be addressed including successful coexistence both catalyst types, need compatible reaction media mild conditions, or minimization cross-reactivities. Therefore, here also provided by means coimmobilization, compartmentalization strategies, flow chemistry, etc. A comprehensive review presented focusing on period 2015 early 2022, which has divided into two main sections that comprise first use metals independent catalysts but working in an orchestral sequential manner, later their application bionanohybrid materials coimmobilization adequate supports. Each part classified different subheadings, based catalyzed catalyst, while development nonasymmetric stereoselective processes was considered section.

Язык: Английский

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Introducing Savie: A Biodegradable Surfactant Enabling Chemo- and Biocatalysis and Related Reactions in Recyclable Water

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 4266 - 4278

Опубликована: Фев. 8, 2023

Savie is a biodegradable surfactant derived from vitamin E and polysarcosine (PSar) developed for use in organic synthesis recyclable water. This includes homogeneous catalysis (including examples employing only ppm levels of catalyst), heterogeneous catalysis, biocatalytic transformations, including multistep chemoenzymatic sequence. Use frequently leads to significantly higher yields than do conventional surfactants, while obviating the need waste-generating solvents.

Язык: Английский

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Building Enzymes through Design and Evolution

ACS Catalysis, Год журнала: 2023, Номер 13(19), С. 12436 - 12444

Опубликована: Сен. 7, 2023

Designing efficient enzymes is a formidable challenge at the forefront of modern biocatalysis. Here, we review recent developments in field and illustrate how interplay between computational design advanced protein engineering has given rise to with diverse activities. Natural proteins have been re-engineered computationally embed designed catalytic sites, affording active catalysts that can be optimized through laboratory evolution enhance efficiency selectivity. Computational tools reliably generate stable de novo shapes backbone geometries beyond those found nature, which serve as idealized templates for hosting sites. Genetic code reprogramming methods used introduce additional functional elements into sites expand range chemistries accessible designer enzymes. Finally, emergence powerful based on deep learning promises transformative impact by greatly increasing speed model accuracy. By bringing together latest experimental enzyme design, are optimistic ambition building useful biocatalysts from scratch within reach.

Язык: Английский

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Green chemistry and biocatalysis: Engineering a sustainable future

Catalysis Today, Год журнала: 2024, Номер 431, С. 114571 - 114571

Опубликована: Фев. 17, 2024

Язык: Английский

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Enzymatic Cascade for the Synthesis of 2,5‐Furandicarboxylic Acid in Biphasic and Microaqueous Conditions: ‘Media‐Agnostic’ Biocatalysts for Biorefineries

ChemSusChem, Год журнала: 2022, Номер 15(9)

Опубликована: Апрель 19, 2022

5-hydroxymethylfurfural (HMF) is produced upon dehydration of C6 sugars in biorefineries. As the product, it remains either aqueous solutions, or situ extracted to an organic medium (biphasic system). For subsequent oxidation HMF 2,5-furandicarboxylic acid (FDCA), 'media-agnostic' catalysts that can be efficiently used different conditions, from biphasic, and (microaqueous) media, are interest. Here, concept a one-pot biocatalytic cascade for production FDCA was reported, using galactose oxidase (GalOx) formation 2,5-diformylfuran (DFF), followed by lipase-mediated peracid DFF FDCA. GalOx maintained its catalytic activity exposure range solvents with only 1 % (v/v) water. The (DFF) successfully established ethyl acetate-based biphasic microaqueous systems. To validate concept, reaction conducted at 5 water, integrated where subsequently oxidized catalyzed Candida antarctica lipase B.

Язык: Английский

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Recent developments in the enzymatic modifications of steroid scaffolds

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(18), С. 3559 - 3583

Опубликована: Янв. 1, 2024

This review highlights the recent advancements in enzymatic modifications of steroid scaffolds, emphasizing hydroxylation, ketoreduction, dehydrogenation, cascade reactions, and other modifications.

Язык: Английский

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Engineering the thermal stability of a polyphosphate kinase by ancestral sequence reconstruction to expand the temperature boundary for an industrially applicable ATP regeneration system

Applied and Environmental Microbiology, Год журнала: 2024, Номер 90(2)

Опубликована: Янв. 18, 2024

ATP-dependent energy-consuming enzymatic reactions are widely used in cell-free biocatalysis. However, the direct addition of large amounts expensive ATP can greatly increase cost, and production is often difficult to achieve as a result. Although polyphosphate kinase (PPK)-polyphosphate-based regeneration system has potential solve this challenge, generally poor thermal stability PPKs limits widespread use method. In paper, we evaluated PPK from

Язык: Английский

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Waste Valorization in a Sustainable Bio‐Based Economy: The Road to Carbon Neutrality

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Сен. 6, 2024

Abstract The development of sustainable chemistry underlying the quest to minimize and/or valorize waste in carbon‐neutral manufacture chemicals is followed over last four five decades. Both chemo‐ and biocatalysis have played an indispensable role this odyssey. particular developments protein engineering, metagenomics bioinformatics preceding three decades a crucial supporting facilitating widespread application both whole cell cell‐free biocatalysis. pressing need, driven by climate change mitigation, for drastic reduction greenhouse gas (GHG) emissions, has precipitated energy transition based on decarbonization defossilization organic production. latter involves biomass CO 2 as feedstock green electricity generated using solar, wind, hydroelectric or nuclear energy. use polysaccharides feedstocks will underpin renaissance carbohydrate with pentoses hexoses base bio‐based solvents polymers environmentally friendly downstream products. availability inexpensive solar led increasing attention electro(bio)catalysis photo(bio)catalysis which turn leading myriad innovations these fields.

Язык: Английский

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One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

ACS Catalysis, Год журнала: 2023, Номер 13(14), С. 9404 - 9414

Опубликована: Июль 1, 2023

Direct valorization of biomass into value-added chemicals is attractive yet challenging. Herein, we report a one-pot synthesis 2,5-bis(hydroxymethyl)furan (BHMF) and its diacetate from inexpensive fructose sugar syrup in the aqueous phase via sequential chemical dehydration, biocatalytic reduction, esterification. A robust alcohol dehydrogenase Escherichia coli (EcYjgB) was identified for HMF with high catalytic efficiencies toward 5-hydroxymethylfurfural (HMF) (kcat/Km, 1300 s–1 mM–1) as well NADPH (9700 mM–1). Recombinant E. harboring EcYjgB (E. coli_EcYjgB) showed tolerance highly toxic strongly inhibitory biobased furans, enabling smooth reduction 1 M 0.5 furfural. Its practicality demonstrated by gram-scale BHMF 79% isolated yield at approximately 126 g/L substrate loading. Biocatalytic process intensification realized improving cell membrane permeability using ethyl acetate, providing up to 15 h productivity. concurrent cascade producing constructed combining coli_EcYjgB Mycobacterium smegmatis acyltransferase (MsAcT) variant N94A, affording desired product 93% h. Starting crude obtained dehydration organic solvent evaporation, were produced >99 88% yields, respectively. Finally, direct these furan-based products sugars performed chemobiocatalysis, without isolation any intermediates, resulting yields 59% (relative sugar). This work may pave way scalable production renewable biomass.

Язык: Английский

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