The E factor at 30: a passion for pollution prevention

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(5), P. 1704 - 1728

Published: Jan. 1, 2023

Publication of the E Factor drew attention to problem waste in chemicals manufacture. Thirty yeas later it is abundantly clear that underlying cause global environmental problems, from climate change plastic pollution.

Language: Английский

---

Methyltransferases: Functions and Applications

ChemBioChem, Journal Year: 2022, Volume and Issue: 23(18)

Published: June 13, 2022

In this review the current state-of-the-art of S-adenosylmethionine (SAM)-dependent methyltransferases and SAM are evaluated. Their structural classification diversity is introduced key mechanistic aspects presented which then detailed further. Then, catalytic as a target for drugs, approaches to utilise cofactor in synthesis with different supply regeneration The use analogues also described. Finally O-, N-, C- S-MTs, their synthetic applications potential compound diversification given.

Language: Английский

---

From Ground-State to Excited-State Activation Modes: Flavin-Dependent “Ene”-Reductases Catalyzed Non-natural Radical Reactions

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(9), P. 1446 - 1457

Published: April 11, 2024

ConspectusEnzymes are desired catalysts for chemical synthesis, because they can be engineered to provide unparalleled levels of efficiency and selectivity. Yet, despite the astonishing array reactions catalyzed by natural enzymes, many reactivity patterns found in small molecule have no counterpart living world. With a detailed understanding mechanisms utilized catalysts, we identify existing enzymes with potential catalyze that currently unknown nature. Over past eight years, our group has demonstrated flavin-dependent "ene"-reductases (EREDs) various radical-mediated selectivity, solving long-standing challenges asymmetric synthesis.This Account presents development EREDs as general radical reactions. While developed multiple generating radicals within protein active sites, this account will focus on examples where flavin mononucleotide hydroquinone (FMNhq) serves an electron transfer initiator. initial mechanistic hypotheses were rooted electron-transfer-based initiation commonly used synthetic organic chemists, ultimately uncovered emergent unique site. We begin covering intramolecular discussing how activates substrate reduction altering redox-potential alkyl halides templating charge complex between flavin-cofactor. Protein engineering been modify fundamental photophysics these reactions, highlighting opportunity tune systems further using directed evolution. This section highlights range coupling partners termination available reactions.The next intermolecular role enzyme-templated ternary complexes among cofactor, halide, partner gating ensure it only occurs when both substrates bound highlight applications activation mode, including olefin hydroalkylation, carbohydroxylation, arene functionalization, nitronate alkylation. also discusses favor steps elusive solution reductive nitroalkanes. aware several recent EREDs-catalyzed photoenzymatic transformations from other groups. discuss results papers context nuances substrates.These biocatalytic often complement state-of-the-art small-molecule-catalyzed making valuable addition chemist's toolbox. Moreover, underlying principles studied potentially operative cofactor-dependent proteins, opening door different types enzyme-catalyzed anticipate serve guide inspire broad interest repurposing access new transformations.

Language: Английский

---

Making Enzymes Suitable for Organic Chemistry by Rational Protein Design

ChemBioChem, Journal Year: 2022, Volume and Issue: 23(14)

Published: April 7, 2022

This review outlines recent developments in protein engineering of stereo- and regioselective enzymes, which are prime interest organic pharmaceutical chemistry as well biotechnology. The widespread application enzymes was hampered for decades due to limited enantio-, diastereo- regioselectivity, the reason why most chemists were not interested biocatalysis. attitude began change with advent semi-rational directed evolution methods based on focused saturation mutagenesis at sites lining binding pocket. Screening constitutes labor-intensive step (bottleneck), is various research groups continuing develop techniques generation small smart mutant libraries. Rational enzyme design, traditionally an alternative evolution, provides collections mutants require minimal screening. approach first thermostabilization, did enter field stereoselectivity until later. Computational guides such Rosetta algorithms, HotSpot Wizard metric, machine learning (ML) contribute significantly decision making. newest advancements show that CAST/ISM rational design no longer separate tracks, instead, they have started merge. Indeed, researchers utilizing two approaches learned from each other. Today, toolbox includes primarily because possibility controlling by has ensured reliability when facing synthetic challenges. also written hope undergraduate graduate education will include more so than past.

Language: Английский

---

Reshaping Substrate-Binding Pocket of Leucine Dehydrogenase for Bidirectionally Accessing Structurally Diverse Substrates

ACS Catalysis, Journal Year: 2022, Volume and Issue: 13(1), P. 158 - 168

Published: Dec. 13, 2022

Steric hindrance modification-based pocket reshaping is an effective approach for enzyme–substrate acceptance evolution. However, previous studies were limited to using the unidirectional trait of bulky substrates as a measure fitness. In this endeavor, we conducted steric bidirectional Exiguobacterium sibiricum leucine dehydrogenase (EsLeuDH) elucidating differences in molecular mechanism on adaptability between and small substrates. A site-directed mutagenesis library generated based specifically chosen sites building blocks enabled substrate specificity EsLeuDH be extended both aliphatic 1a aromatic 1h; catalytic efficiency toward 1b–g increased by 2.5–16.3-fold. Kinetic parameter determination revealed that mutants was attributed decreased Km enhanced kcat values, respectively. Structure-based computational analysis provided insights into strengthening attenuating directions, which reshaped with favorable attack distance expanded catalytical binding space, Our study elucidates difference different types implementation reshaping, potential applications divergent evolution amino acid family members other oxidoreductases analogous substrate-binding pocket.

Language: Английский

---

The green chemistry paradigm in modern organic synthesis

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

---

Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: Feb. 6, 2023

Abstract The combination of catalytic methods provides multiple advantages in organic synthesis, allowing access to diverse molecules a straightforward manner. Merging metal and enzyme catalysis is currently receiving great attention due the possibility assemble C−C coupling, olefin metathesis, hydration other reactions with exquisite stereospecificity displayed by enzymes. Thus, this minireview organized based on action species (Pd, Ru, Au, Ir, Fe…) different Special will be paid design sequential processes concurrent cascades, presenting solutions such as use surfactants or compartmentalization strategies for those cases where incompatibilities could hamper overall process.

Language: Английский

---

Deep Electroreductive Chemistry: Harnessing Carbon- and Silicon-Based Reactive Intermediates in Organic Synthesis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(12), P. 8038 - 8048

Published: May 31, 2023

ADVERTISEMENT RETURN TO ISSUEPREVViewpointNEXTDeep Electroreductive Chemistry: Harnessing Carbon- and Silicon-Based Reactive Intermediates in Organic SynthesisWen ZhangWen ZhangDepartment of Chemistry Chemical Biology, Cornell University, Ithaca, New York 14853, United StatesMore by Wen Zhanghttps://orcid.org/0000-0002-0704-3463, Weiyang GuanWeiyang GuanDepartment Guan, Jesus I. Martinez AlvaradoJesus AlvaradoDepartment Alvarado, Luiz F. T. NovaesLuiz NovaesDepartment Novaeshttps://orcid.org/0000-0003-1209-2865, Song Lin*Song LinDepartment States*Email: [email protected]More Linhttps://orcid.org/0000-0002-8880-6476Cite this: ACS Catal. 2023, 13, 12, 8038–8048Publication Date (Web):May 31, 2023Publication History Received14 March 2023Published online31 May inissue 16 June 2023https://pubs.acs.org/doi/10.1021/acscatal.3c01174https://doi.org/10.1021/acscatal.3c01174article-commentaryACS PublicationsCopyright © 2023 American Society. This publication is available under these Terms Use. Request reuse permissions free to access through this site. Learn MoreArticle Views8051Altmetric-Citations5LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated Crossref daily. Find more information about citation counts.The Altmetric Attention Score a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (3 MB) Get e-AlertscloseSUBJECTS:Alkyls,Anions,Halogens,Hydrocarbons,Inorganic compounds e-Alerts

Language: Английский

---

Focused rational iterative site-specific mutagenesis (FRISM): A powerful method for enzyme engineering

Molecular Catalysis, Journal Year: 2023, Volume and Issue: 553, P. 113755 - 113755

Published: Dec. 9, 2023

Language: Английский

---

Application of Immobilized Enzymes in Flow Biocatalysis for Efficient Synthesis

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(5), P. 1308 - 1326

Published: March 8, 2024

Flow chemistry as well biocatalysis contribute to achieve green industries and sustainable development. Now there is an approach that combines them, called flow biocatalysis, which attracts more attention. In enzyme immobilization plays a powerful role in promoting its This review begins with general introduction of then provides update on the application immobilized enzymes biocatalysis. Oxidation–reduction, hydrolysis–esterification, transferase reaction, condensation, carboxylation, multistep cascade reactions continuous-flow process are discussed detail.

Language: Английский

---