Light-Driven Deracemization by a Designed Photoenzyme

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 12, 2025

The creation of enzymes with abiological abilities offers exciting opportunities to access new-to-nature biocatalysis beyond that found in nature. Here, we repurpose a novel protein scaffold, CTB10, as an artificial photoenzyme through genetic code expansion. It enables catalytic deracemization cyclopropane, process remains inaccessible traditional due its thermodynamically unfavorable Following structural optimization directed evolution, broad substrate scope high enantioselectivities is achieved. Furthermore, the crystal structure CTB10-based photoenzyme-substrate complex well demonstrates how chiral cavity sculpted promote efficient and selective light-enabled deracemization. Therefore, this study unlocks potential for achieving challenging biocatalysis.

Language: Английский

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Repurposing Visible‐Light‐Excited Ene‐Reductases for Diastereo‐ and Enantioselective Lactones Synthesis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 24, 2024

Abstract Repurposing enzymes to catalyze non‐natural asymmetric transformations that are difficult achieve using traditional chemical methods is of significant importance. Although radical C−O bond formation has emerged as a powerful approach for constructing oxygen‐containing compounds, controlling the stereochemistry poses great challenge. Here we present development dual bio‐/photo‐catalytic system comprising an ene‐reductase and organic dye achieving stereoselective lactonizations. By integrating directed evolution photoinduced single electron oxidation, repurposed engineered ene‐reductases steer formations (one hydrolactonizations lactonization‐alkylations while two bonds lactonization‐oxygenations). This catalysis gave new diverse array enantioenhanced 5‐ 6‐membered lactones with vicinal stereocenters, part which bears quaternary stereocenter (up 99 % enantiomeric excess, up 12.9 : 1 diastereomeric ratio). Detailed mechanistic studies, including computational simulations, uncovered synergistic effect enzyme externally added organophotoredox catalyst Rh6G.

Language: Английский

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Chemogenetic Evolution of Diversified Photoenzymes for Enantioselective [2 + 2] Cycloadditions in Whole Cells

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19030 - 19041

Published: July 8, 2024

Artificial photoenzymes with novel catalytic modes not found in nature are high demand; yet, they also present significant challenges the field of biocatalysis. In this study, a chemogenetic modification strategy is developed to facilitate rapid diversification photoenzymes. This integrates site-specific chemical conjugation various artificial photosensitizers into natural protein cavities and iterative mutagenesis cell lysates. Through rounds directed evolution, prominent visible-light-activatable photoenzyme variants were developed, featuring thioxanthone chromophore. They successfully enabled enantioselective [2 + 2] photocycloaddition 2-carboxamide indoles, class UV-sensitive substrates that traditionally challenging for known Furthermore, versatility demonstrated whole-cell photobiocatalysis, enabling efficient synthesis enantioenriched cyclobutane-fused indoline tetracycles. These findings significantly expand photophysical properties photoenzymes, critical factor enhancing their potential harnessing excited-state reactivity stereoselective transformations.

Language: Английский

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Multilevel Stimuli–Responsive Smart “Sandwich” Label with Physical Unclonable Functions Bionic Wrinkles and Space‐Selective Fluorescence Patterns

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

Published: Oct. 31, 2024

Abstract With the increasing popularity of internet, it brings convenience to lives while also increases security risks. Physical Unclonable Functions (PUFs) can generate random, unclonable, and unique identifiers using their inherent physical characteristics, which have broad prospects in anti‐counterfeiting. Herein, inspired by irregular tree bark fissures random skin wrinkles found nature, a method for creating complex micro‐wrinkles with unclonable patterns is proposed simply stretching hydrogels. The texture information contained digitized into binary codes an adaptive threshold algorithm. Additionally, novel “sandwich” label multilevel intelligent anti‐counterfeiting system proposed. first‐level involves photoluminescence encryption adjustable luminescence within visible light range modulated at different excitation wavelengths; second‐level includes strain‐related mechanical encryption, third‐level consists highly micro‐wrinkles. certification difficulty as grade increases, thereby enhancing security. Furthermore, space‐selective doping rare earth metal–organic framework (RE‐MOF) fluorescent materials hydrogels achieved through use screen‐printing technology. concept smart PUF labels will further enhance current levels counterfeiting prevention.

Language: Английский

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Dramatic enhancement in lithium-ion battery capacity through synergistic effects of electronic transitions in light-assisted organic coordination cathode material Co(bpy)(dhbq)2

Energy storage materials, Journal Year: 2024, Volume and Issue: 74, P. 103891 - 103891

Published: Nov. 5, 2024

Language: Английский

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