When Nanozymes Meet Single‐Atom Catalysis

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(7), P. 2565 - 2576

Published: June 18, 2019

Nanomaterials with enzyme-like activities, coined nanozymes, have been researched widely as they offer unparalleled advantages in terms of low cost, superior activity, and high stability. The complex structure composition nanozymes has led to extensive investigation their catalytic sites at an atomic scale, in-depth understanding the biocatalysis occurring. Single-atom catalysts (SACs), characterized by atomically dispersed active sites, provided opportunities for mimicking metalloprotease bridging gap between natural enzymes nanozymes. In this Minireview, we illustrate unique properties discuss recent advances synthesis, characterization, applications SACs. Subsequently, outline impressive progress made single-atom sensing, degradation organic pollutants, therapeutic roles. Finally, present major challenges remaining a successful marriage

Language: Английский

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Single‐Atom Catalysts in Catalytic Biomedicine

Advanced Materials, Journal Year: 2020, Volume and Issue: 32(8)

Published: Jan. 13, 2020

The intrinsic deficiencies of nanoparticle-initiated catalysis for biomedical applications promote the fast development alternative versatile theranostic modalities. catalytic performance and selectivity are critical issues that challenging to be augmented optimized in biological conditions. Single-atom catalysts (SACs) featuring atomically dispersed single metal atoms have emerged as one most explored biomedicine recently due their preeminent activity superior distinct from nanosized counterparts. Herein, an overview pivotal significance SACs some underlying need addressed is provided, with a specific focus on applications. Their fabrication strategies, surface engineering, structural characterizations discussed briefly. In particular, triggering representative reactions providing fundamentals use discussed. A sequence paradigms summarized successful construction varied (e.g., cancer treatment, wound disinfection, biosensing, oxidative-stress cytoprotection) emphasis uncovering mechanisms understanding structure–performance relationships. Finally, opportunities challenges faced future SACs-triggered outlooked.

Language: Английский

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Advances in ultrahigh-throughput screening for directed enzyme evolution

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 49(1), P. 233 - 262

Published: Dec. 9, 2019

This review summarizes how ultrahigh-throughput screening methods employ cells and biomimetic compartments to access the vast, unexplored diversity of biocatalysts with novel functions derived from directed evolution metagenomics libraries.

Language: Английский

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Iron- and cobalt-catalyzed C(sp³)–H bond functionalization reactions and their application in organic synthesis

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(15), P. 5310 - 5358

Published: Jan. 1, 2020

This review highlights the developments in iron and cobalt catalyzed C(sp³)–H bond functionalization reactions with emphasis on their applications organic synthesis, i.e. natural products pharmaceuticals synthesis and/or modification.

Language: Английский

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Engineering single-atom catalysts toward biomedical applications

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(9), P. 3688 - 3734

Published: Jan. 1, 2022

Due to inherent structural defects, common nanocatalysts always display limited catalytic activity and selectivity, making it practically difficult for them replace natural enzymes in a broad scope of biologically important applications. By decreasing the size nanocatalysts, their selectivity will be substantially improved. Guided by this concept, advances now enter an era atomic-level precise control. Single-atom catalysts (denoted as SACs), characterized atomically dispersed active sites, strikingly show utmost atomic utilization, precisely located metal centers, unique metal-support interactions identical coordination environments. Such advantages SACs drastically boost specific per atom, thus provide great potential achieving superior functionally mimic or even outperform interest. Although does matter, is not clear whether guideline "the smaller, better" still correct developing at single-atom scale. Thus, clearly new, urgent issue address before further extending into biomedical applications, representing branch nanomedicine. This review begins providing overview recent synthesis strategies SACs, which serve basis discussion emerging achievements improving enzyme-like properties level. Then, we carefully compare structures functions various scales from nanoparticles, nanoclusters, few-atom clusters single atoms. Contrary conventional wisdom, are most catalytically reactions, especially those requiring multi-site auxiliary activities. After that, highlight roles toward To appreciate these advances, challenges prospects rapidly growing studies SACs-related nanomedicine also discussed review.

Language: Английский

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Design of Heme Enzymes with a Tunable Substrate Binding Pocket Adjacent to an Open Metal Coordination Site

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14307 - 14315

Published: June 21, 2023

The catalytic versatility of pentacoordinated iron is highlighted by the broad range natural and engineered activities heme enzymes such as cytochrome P450s, which position a porphyrin cofactor coordinating central atom below an open substrate binding pocket. This prowess has inspired efforts to design de novo helical bundle scaffolds that bind cofactors. However, designs lack large pocket hence, chemical transformations accessible limited. Here, with goal combining advantages P450 site geometry almost unlimited customizability protein design, we high-affinity heme-binding protein, dnHEM1, axial histidine ligand, vacant coordination for generating reactive intermediates, tunable distal binding. A 1.6 Å X-ray crystal structure dnHEM1 reveals excellent agreement model key features programmed intended. incorporation substitutions converted into proficient peroxidase stable neutral ferryl intermediate. In parallel, was redesigned generate enantiocomplementary carbene transferases styrene cyclopropanation (up 93% isolated yield, 5000 turnovers, 97:3 e.r.) reconfiguring accommodate calculated transition state models. Our approach now enables custom containing cofactors adjacent pockets variety shapes functionalities.

Language: Английский

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When Nanozymes Meet Single‐Atom Catalysis

Angewandte Chemie, Journal Year: 2019, Volume and Issue: 132(7), P. 2585 - 2596

Published: June 18, 2019

Abstract Nanomaterials with enzyme‐like activities, coined nanozymes, have been researched widely as they offer unparalleled advantages in terms of low cost, superior activity, and high stability. The complex structure composition nanozymes has led to extensive investigation their catalytic sites at an atomic scale, in‐depth understanding the biocatalysis occurring. Single‐atom catalysts (SACs), characterized by atomically dispersed active sites, provided opportunities for mimicking metalloprotease bridging gap between natural enzymes nanozymes. In this Minireview, we illustrate unique properties discuss recent advances synthesis, characterization, applications SACs. Subsequently, outline impressive progress made single‐atom sensing, degradation organic pollutants, therapeutic roles. Finally, present major challenges remaining a successful marriage

Language: Английский

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Iron catalysts with N-ligands for carbene transfer of diazo reagents

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(14), P. 4867 - 4905

Published: Jan. 1, 2020

This review provides an overview of the catalytic activity iron complexes nitrogen ligands in driving carbene transfers towards CC, C–H and X–H bonds. The reactivity diazo reagents is discussed as well proposed reaction mechanisms.

Language: Английский

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Enzyme Catalyst Engineering toward the Integration of Biocatalysis and Chemocatalysis

Trends in biotechnology, Journal Year: 2021, Volume and Issue: 39(11), P. 1173 - 1183

Published: Feb. 5, 2021

Language: Английский

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New-to-nature chemistry from old protein machinery: carbene and nitrene transferases

Current Opinion in Biotechnology, Journal Year: 2020, Volume and Issue: 69, P. 43 - 51

Published: Dec. 25, 2020

Language: Английский

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