Coordination-Driven Self-Assembly Strategy-Activated Cu Single-Atom Nanozymes for Catalytic Tumor-Specific Therapy

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 4279 - 4293

Published: Feb. 6, 2023

How to optimize the enzyme-like catalytic activity of nanozymes improve their applicability has become a great challenge. Herein, we present an l-cysteine (l-Cys) coordination-driven self-assembly strategy activate polyvinylpyrrolidone (PVP)-modified Cu single-atom MoOx-Cu-Cys (denoted as MCCP SAzymes) aiming at tumor-specific therapy. The single atom content can be rationally modulated 10.10 wt %, which activates catalase (CAT)-like MoOx nanoparticles catalyze decomposition H2O2 in acidic microenvironments increase O2 production. Excitingly, maximized CAT-like efficiency is 138-fold higher than that typical MnO2 and exhibits 14.3-fold affinity natural catalase, demonstrated by steady-state kinetics. We verify well-defined l-Cys-Cu···O active sites match through l-Cys bridge-accelerated electron transfer from Cys-Cu disclosed density functional theory calculations. Simultaneously, high loading atoms also enable generation •OH via Fenton-like reaction. Moreover, under X-ray irradiation, converts 1O2 for cascading radiodynamic therapy, thereby facilitating multiple reactive oxygen species (ROS) radiosensitization achieve substantial antitumor.

Language: Английский

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Current Advances on the Single‐Atom Nanozyme and Its Bioapplications

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(10)

Published: Feb. 11, 2023

Nanozymes, a class of nanomaterials mimicking the function enzymes, have aroused much attention as candidate in diverse fields with arbitrarily tunable features owing to diversity crystalline nanostructures, composition, and surface configurations. However, uncertainty their active sites lower intrinsic deficiencies nanomaterial-initiated catalysis compared natural enzymes promote pursuing alternatives by imitating biological centers. Single-atom nanozymes (SAzymes) maximize atom utilization well-defined structure, providing an important bridge investigate mechanism relationship between structure catalytic activity. They risen new burgeoning alternative enzyme from vitro bioanalytical tool vivo therapy flexible atomic engineering structure. Here, focus is mainly on three parts. First, detailed overview single-atom catalyst synthesis strategies including bottom-up top-down approaches given. Then, according structural feature nanocatalysts, influence factors such central metal atom, coordination number, heteroatom doping, metal-support interaction are discussed representative applications (including antibacterial/antiviral performance, cancer therapy, biosensing) highlighted. In end, future perspective challenge facing demonstrated.

Language: Английский

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Regulating the N Coordination Environment of Co Single-Atom Nanozymes for Highly Efficient Oxidase Mimics

Nano Letters, Journal Year: 2023, Volume and Issue: 23(4), P. 1505 - 1513

Published: Feb. 3, 2023

Single-atom catalysts with well-defined atomic structures and precisely regulated coordination environments have been recognized as potential substitutes for natural metalloenzymes. Inspired by the metal structure of enzymes, we show here that oxidase-like activity single-atom Co greatly depends on their local N around catalytic sites. We synthesized a series different nitrogen numbers (Co–Nx(C), x = 2, 3, 4) demonstrated could be effectively tailored fine-tuning coordination. Among studied catalysts, Co–N3(C) three-coordinate atoms shows optimum oxygen adsorption robust reactive species (ROS) generation, thus presenting preferable activity. This work facilitates future development rational nanozyme designs targeting reactions at level.

Language: Английский

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Ti‐doped CeO₂ Stabilized Single‐Atom Rhodium Catalyst for Selective and Stable CO₂ Hydrogenation to Ethanol

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 9, 2022

Development of effective and stable catalysts for CO2 hydrogenation into ethanol remains a challenge. Herein, we report that Rh1 /CeTiOx single-atom catalyst constructed by embedding monoatomic Rh onto Ti-doped CeO2 support has shown super high selectivity (≈99.1 %), record-breaking turnover frequency (493.1 h-1 ), outstanding stability. Synergistic effects Ti-doption contribute to this excellent catalytic performance firstly facilitating oxygen vacancies formation generate oxygen-vacancy-Rh Lewis-acid-base pairs, which favor adsorption activation, cleavage C-O bonds in CHx OH* COOH* * CO* species, subsequent C-C coupling ethanol, secondly generating strong Rh-O bond Ti-doping-induced crystal reconstruction, contributes striking This work highlights the importance elaborating regulation design substantially improve performance.

Language: Английский

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Competitive Adsorption: Reducing the Poisoning Effect of Adsorbed Hydroxyl on Ru Single‐Atom Site with SnO₂for Efficient Hydrogen Evolution

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: July 21, 2022

Ruthenium (Ru) has been theoretically considered a viable alkaline hydrogen evolution reaction electrocatalyst due to its fast water dissociation kinetics. However, strong affinity the adsorbed hydroxyl (OH

Language: Английский

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Atomic‐Level Regulation of Cobalt Single‐Atom Nanozymes: Engineering High‐Efficiency Catalase Mimics

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 6, 2023

Nanozymes aim to mimic the highly evolved active centers of natural enzymes. Despite progress in nanozyme engineering, their catalytic performance is much less favorable compared with This study shows that precise control over atomic configuration Co single-atom nanozymes (SAzymes) enables rational regulation catalase-like guided by theorical calculations. The constructed Co-N3 PS SAzyme exhibits an excellent activity and kinetics, exceeding representative controls Co-based SAzymes different configurations. Moreover, we developed ordered structure-oriented coordination design strategy for rationally engineering established a correlation between structure enzyme-like performance. work demonstrates efficient sites

Language: Английский

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Engineering Single-Atom Sites into Pore-Confined Nanospaces of Porphyrinic Metal–Organic Frameworks for the Highly Efficient Photocatalytic Hydrogen Evolution Reaction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(49), P. 22747 - 22758

Published: Nov. 25, 2022

As a type of heterogeneous catalyst expected for the maximum atom efficiency, series single-atom catalysts (SACs) containing spatially isolated metal single atoms (M-SAs) have been successfully prepared by confining M-SAs in pore-nanospaces porphyrinic metal–organic frameworks (MOFs). The MOF composites M-SAs@Pd-PCN-222-NH2 (M = Pt, Ir, Au, and Ru) display exceptionally high persistent efficiency photocatalytic hydrogen evolution reaction with turnover number (TON) up to 21713 32 h beginning/lasting frequency (TOF) larger than 1200/600 h–1 based on under visible light irradiation (λ ≥ 420 nm). photo-/electrochemical property studies density functional theory calculations disclose that close proximity catalytically active Pt-SAs Pd–porphyrin photosensitizers confinement stabilization effect chemical binding could accelerate electron–hole separation charge transfer pore-nanospaces, thus promoting catalytic H2 lasting effectiveness.

Language: Английский

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Heteroatom‐Driven Coordination Fields Altering Single Cerium Atom Sites for Efficient Oxygen Reduction Reaction

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(28)

Published: April 4, 2023

For current single-atom catalysts (SACs), modulating the coordination environments of rare-earth (RE) single atoms with complex electronic orbital and flexible chemical states is still limited. Herein, cerium (Ce) SAs supported on a P, S, N co-doped hollow carbon substrate (Ce SAs/PSNC) for oxygen reduction reaction (ORR) are reported. The as-prepared Ce SAs/PSNC possesses half-wave potential 0.90 V, turnover frequency value 52.2 s

Language: Английский

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Dimensionality Engineering of Single-Atom Nanozyme for Efficient Peroxidase-Mimicking

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16835 - 16842

Published: July 24, 2023

In nature, enzymatic reactions occur in well-functioning catalytic pockets, where substrates bind and react by properly arranging the sites amino acids a three-dimensional (3D) space. Single-atom nanozymes (SAzymes) are new type of with active similar to those natural metalloenzymes. However, centers current SAzymes two-dimensional (2D) architectures lack collaborative substrate-binding features limits their activity. Herein, we report dimensionality engineering strategy convert conventional 2D Fe–N-4 into 3D structures integrating oxidized sulfur functionalities onto carbon plane. Our results suggest that could serve as binding for assisting substrate orientation facilitating desorption H2O, resulting an outstanding specific activity up 119.77 U mg–1, which is 6.8 times higher than FeN4C SAzymes. This study paves way rational design highly single-atom nanozymes.

Language: Английский

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Se‐Containing MOF Coated Dual‐Fe‐Atom Nanozymes With Multi‐Enzyme Cascade Activities Protect Against Cerebral Ischemic Reperfusion Injury

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 32(36)

Published: May 31, 2022

Abstract The atomically monodispersed dual‐atom nanozyme not only possesses the advantages of homogeneous active centers and high atomic utilization efficiency but also exhibits amazing synergistic effect for higher catalytic activities than single‐atom nanozyme. However, how to construct with multi‐enzyme cascade capacity protecting against brain tissue damage is a great challenge. Herein, coping secondary caused by explosive generation reactive oxygen species(ROS) during cerebral ischemia‐reperfusion, antioxidant system constructed encapsulating dual‐Fe‐atom (Fe 2 NC) in selenium‐containing MOF (Se‐MOF) shell layer. designed superoxide dismutase‐like, catalase‐like, even oxidase‐like Fe 1 nanozyme, moreover, Se‐MOF layer acts as glutathione peroxidase mimic, improves stability biocompatibility NC obviously. has been demonstrated be main reason activity density functional theory calculations. In vitro vivo results reveal that multifunctional NC@Se nanoparticles can counteract oxidative inhibit neural apoptosis after ischemia‐reperfusion injury effectively eliminating intracellular ROS potentially inhibiting ASK1/JNK apoptotic signaling pathway.

Language: Английский

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