Non-canonical amino acids as a tool for the thermal stabilization of enzymes

Protein Engineering Design and Selection, Journal Year: 2023, Volume and Issue: 36

Published: Jan. 1, 2023

Abstract Biocatalysis has become a powerful alternative for green chemistry. Expanding the range of amino acids used in protein biosynthesis can improve industrially appealing properties such as enantioselectivity, activity and stability. This review will specifically delve into thermal stability improvements that non-canonical (ncAAs) confer to enzymes. Methods achieve this end, use halogenated ncAAs, selective immobilization rational design, be discussed. Additionally, specific enzyme design considerations using ncAAs are discussed along with benefits limitations various approaches available enhance

Language: Английский

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Plastic degradation by insect hexamerins: Near-atomic resolution structures of the polyethylene-degrading proteins from the wax worm saliva

Science Advances, Journal Year: 2023, Volume and Issue: 9(38)

Published: Sept. 20, 2023

Plastic waste management is a pressing ecological, social, and economic challenge. The saliva of the lepidopteran Galleria mellonella larvae capable oxidizing depolymerizing polyethylene in hours at room temperature. Here, we analyze by cryo-electron microscopy (cryo-EM) G. mellonella's directly from native source. three-dimensional reconstructions reveal that buccal secretion mainly composed four hexamerins belonging to hemocyanin/phenoloxidase family, renamed Demetra, Cibeles, Ceres, previously unidentified factor termed Cora. Functional assays show this factor, as its counterparts Demetra also able oxidize degrade polyethylene. cryo-EM data x-ray analysis purified fractions they self-assemble primarily into three macromolecular complexes with striking structural differences likely modulate their activity. Overall, these results establish ground further explore hexamerins' functionalities, role vivo, eventual biotechnological application.

Language: Английский

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Enhanced Photoinduced Baeyer–Villiger Oxidation of Ketones by Introducing Trinuclear Ruthenium Clusters into Polyoxometalate-Based Metal–Organic Frameworks

Chemistry of Materials, Journal Year: 2023, Volume and Issue: 35(10), P. 3941 - 3950

Published: May 12, 2023

The development of solar-driven organic synthesis processes as an alternative to conventional thermo-catalytic technologies is great research significance in academia and industry. Herein, we looked into the photoinduced Baeyer–Villiger oxidation cyclohexanone based on Mukaiyama method for first time. We fabricated a crystalline polyoxometalate-based metal–organic framework photocatalyst, CR-SiW12, which represents example trinuclear ruthenium clusters involved construction frameworks. was efficiently converted ε-caprolactone under visible light (>400 nm) irradiation with CR-SiW12 catalyst, reaction turnover number frequency recorded 941 274.5 h–1, respectively, apparent quantum yield at 465 nm measured be 8.4%. Moreover, exhibited high structural stability reusability where remained 91.3% after five consecutive cycles. This work offers promising strategy accomplishing reactions green conditions.

Language: Английский

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Enzymatic Oxy‐ and Amino‐Functionalization in Biocatalytic Cascade Synthesis: Recent Advances and Future Perspectives

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Aug. 28, 2023

Biocatalytic cascades are a powerful tool for building complex molecules containing oxygen and nitrogen functionalities. Moreover, the combination of multiple enzymes in one pot offers possibility to minimize downstream processing waste production. In this review, we illustrate various recent efforts development multi-step syntheses involving C-O C-N bond-forming produce high value-added compounds, such as pharmaceuticals polymer precursors. Both vitro vivo examples discussed, revealing respective advantages drawbacks. The use engineered boost outcome is also addressed current co-substrate cofactor recycling strategies presented, highlighting importance atom economy. Finally, tools overcome challenges multi-enzymatic oxy- amino-functionalization reactions including flow systems with immobilized biocatalysts confined nanomaterials.

Language: Английский

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Steglich esterification: A versatile synthetic approach toward the synthesis of natural products, their analogues/derivatives

Heliyon, Journal Year: 2023, Volume and Issue: 10(1), P. e23416 - e23416

Published: Dec. 9, 2023

The exploitation of natural products and their analogues in the field pharmacology has been regarded as great importance. It can be attributed to fact that these scaffolds exhibit diverse chemical properties, distinct biological activities zenith specificity biochemical processes, enabling them act favorable structures for lead compounds. synthesis a crafty hard-to-achieve task. Steglich esterification reaction played significant role area. is mild efficient technique constructing ester linkages. This involves establishment moiety via carbodiimide-based condensation carboxylic acid with an alcohol, thiol or amine catalyzed by dimethyl aminopyridine (DMAP). Specifically, labile reagents multiple reactive sites are esterified efficiently classical modified conditions, which accounts synthetic utility. review encloses performance forging linkage executing total derivatives since 2018.

Language: Английский

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Mechanistic Investigation on C–C Bond Cleavage of Anthraquinone Catalyzed by an Atypical Nonheme Iron-Dependent Dioxygenase BTG13

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(2), P. 797 - 811

Published: Jan. 3, 2024

An atypical nonheme iron-dependent dioxygenase BTG13 with a rare iron coordination of four histidine residues and carboxylated-lysine (Kcx) was recently reported to catalyze the C4a–C10 bond cleavage anthraquinone. However, reaction mechanism remains elusive. Herein, detailed is studied using molecular dynamics simulations density functional theory calculations. The comprehensive mechanistic study shows that most favorable pathway for C–C anthraquinone involves two unusual steps: (1) hydrogen atom abstraction (HAA) from an sp3-hybridized carbon substrate by FeIII–O2•– (2) oxygen rebound radical via homolytic O–O cleavage, which activates FeIII–OOH form FeIV═O species. Furthermore, our results reveal Kcx could increase electron-donating ability ferrous iron, thereby boosting activation dioxygen species facilitating following HAA processes. This advances current knowledge reactions catalyzed oxygenases.

Language: Английский

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AlmA involved in the long-chain n -alkane degradation pathway in Acinetobacter baylyi ADP1 is a Baeyer–Villiger monooxygenase

Applied and Environmental Microbiology, Journal Year: 2024, Volume and Issue: 90(1)

Published: Jan. 3, 2024

Many

Language: Английский

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ALDELE: All-Purpose Deep Learning Toolkits for Predicting the Biocatalytic Activities of Enzymes

Journal of Chemical Information and Modeling, Journal Year: 2024, Volume and Issue: 64(8), P. 3123 - 3139

Published: April 4, 2024

Rapidly predicting enzyme properties for catalyzing specific substrates is essential identifying potential enzymes industrial transformations. The demand sustainable production of valuable industry chemicals utilizing biological resources raised a pressing need to speed up biocatalyst screening using machine learning techniques. In this research, we developed an all-purpose deep-learning-based multiple-toolkit (ALDELE) workflow catalysts. ALDELE incorporates both structural and sequence representations proteins, alongside ligands by subgraphs overall physicochemical properties. Comprehensive evaluation demonstrated that can predict the catalytic activities enzymes, particularly, it identifies residue-based hotspots guide engineering generates substrate heat maps explore scope given biocatalyst. Moreover, our models notably match empirical data, reinforcing practicality reliability approach through alignment with confirmed mutation sites. offers facile comprehensive solution integrating different toolkits tailored purposes at affordable computational cost therefore would be discovery new functional their exploitation industry.

Language: Английский

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Emergence of a distinct mechanism of C–N bond formation in photoenzymes

Nature, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 8, 2024

Language: Английский

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Photobiocatalytic Oxyfunctionalization with High Reaction Rate using a Baeyer–Villiger Monooxygenase from Burkholderia xenovorans in Metabolically Engineered Cyanobacteria

ACS Catalysis, Journal Year: 2021, Volume and Issue: 12(1), P. 66 - 72

Published: Dec. 10, 2021

Baeyer-Villiger monooxygenases (BVMOs) catalyze the oxidation of ketones to lactones under very mild reaction conditions. This enzymatic route is hindered by requirement a stoichiometric supply auxiliary substrates for cofactor recycling and difficulties with supplying necessary oxygen. The recombinant production BVMO in cyanobacteria allows substitution organic cosubstrates water as an electron donor utilization oxygen generated photosynthetic splitting. Herein, we report identification from Burkholderia xenovorans (BVMO Xeno ) that exhibits higher rates comparison currently identified BVMOs. We 10-fold increase specific activity cyclohexanone monooxygenase (CHMO Acineto Synechocystis sp. PCC 6803 (25 vs 2.3 U gDCW-1 at optical density OD750 = 10) initial rate 3.7 ± 0.2 mM h-1. While cells containing CHMO showed considerable reduction cyclohexanol, this unwanted side was almost completely suppressed , which attributed much faster lactone formation lower KM value toward cyclohexanone. Furthermore, whole-cell catalyst outstanding stereoselectivity. These results show that, despite self-shading cells, high activities can be obtained elevated cell densities even further increased through manipulation transport chain (PETC). up h-1 underline usefulness oxygenic chassis reactions. evolution contribute alleviating highly problematic mass-transfer limitation oxygen-dependent processes.

Language: Английский

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