Theoretical Calculation–Driven Metal–Organic Framework Nanozymes: Catalytic Mechanisms and Applications DOI
Ziyu Zhang,

Zhishuang Yuan,

Ziyan Zhang

et al.

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 24, 2024

ABSTRACT Metal–organic framework (MOF) nanozymes have garnered widespread attention in the field of biomimetic catalysis due to their highly controllable porous structure and surface functionalization, enabling them mimic catalytic activity specificity natural enzymes while offering greater stability reusability. In recent years, significant progress has been made theoretical computation studies MOF nanozymes' reactions, providing deep insights into analytical mechanisms. This review comprehensively gathers latest research calculation–driven on mechanisms applications. First, methods that can be used for calculations nanozymes, especially density functional theory (DFT), are reviewed help deeply analyze active site distribution, electron transfer pathways, adsorption activation reactants nanozymes. Subsequently, this contribution these calculation revealing reaction mechanism (such as sites enzyme‐like activity), specific role energy changes key steps. Finally, looks forward challenges opportunities future design application accurately predicting activities, understanding complex mechanisms, guiding synthesis new nanozyme materials. By integrating with experimental research, study is expected forge avenues provide effective strategies addressing fields sensing, biomedicine, environmental protection.

Language: Английский

Breaking the pH Limitation of Nanozymes: Mechanisms, Methods, and Applications DOI
Kaizheng Feng, Guancheng Wang, Shi Wang

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(31)

Published: April 14, 2024

Although nanozymes have drawn great attention over the past decade, activities of peroxidase-like, oxidase-like, and catalase-like are often pH dependent with elusive mechanism, which largely restricts their application. Therefore, a systematical discussion on pH-related catalytic mechanisms together methods to overcome this limitation is in need. In review, various exhibiting pH-dependent collected root causes for dependence comprehensively analyzed. Subsequently, regulatory concepts including environment reconstruction direct activity improvement break restriction summarized. Moreover, applications pH-independent sensing, disease therapy, pollutant degradation overviewed. Finally, current challenges future opportunities development suggested. It anticipated that review will promote further design broaden application range higher efficiency.

Language: Английский

Citations

68
Spatial engineering of single-atom Fe adjacent to Cu-assisted nanozymes for biomimetic O2 activation DOI Creative Commons
Ying Wang, Vinod K. Paidi, Weizhen Wang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 12, 2024

Abstract The precise design of single-atom nanozymes (SAzymes) and understanding their biocatalytic mechanisms hold great promise for developing ideal bio-enzyme substitutes. While considerable efforts have been directed towards mimicking partial bio-inspired structures, the integration heterogeneous SAzymes configurations homogeneous enzyme-like mechanism remains an enormous challenge. Here, we show a spatial engineering strategy to fabricate dual-sites with atomic Fe active center adjacent Cu sites. Compared planar Fe–Cu dual-atomic sites, vertically stacked geometry in FePc@2D-Cu–N–C possesses highly optimized scaffolds, favorable substrate affinity, fast electron transfer. These characteristics SAzyme induces biomimetic O 2 activation through homogenous enzymatic pathway, resembling functional mechanistic similarity natural cytochrome c oxidase. Furthermore, it presents appealing alternative P450 3A4 drug metabolism drug–drug interaction. findings are expected deepen fundamental atomic-level next-generation nanozymes.

Language: Английский

Citations

42
Tailored Metal‐Organic Framework‐Based Nanozymes for Enhanced Enzyme‐Like Catalysis DOI Open Access
Zhichao Yu,

Zhenjin Xu,

Ruijin Zeng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 19, 2024

Abstract The global crisis of bacterial infections is exacerbated by the escalating threat microbial antibiotic resistance. Nanozymes promise to provide ingenious solutions. Here, we reported a homogeneous catalytic structure Pt nanoclusters with finely tuned metal–organic framework (ZIF‐8) channel structures for treatment infected wounds. Catalytic site normalization showed that active aggregates fine‐tuned pore modifications had capacity 14.903×10 5 min −1 , which was 18.7 times higher than particles in monodisperse state ZIF‐8 (0.793×10 ). In situ tests revealed change from homocleavage heterocleavage hydrogen peroxide at interface nanozyme one key reasons improvement activity. Density‐functional theory and kinetic simulations reaction jointly determine role center substrate together. Metabolomics analysis developed nanozyme, working conjunction reactive oxygen species, could effectively block energy metabolic pathways within bacteria, leading spontaneous apoptosis rupture. This pioneering study elucidates new ideas regulation artificial enzyme activity provides perspectives development efficient substitutes.

Language: Английский

Citations

38
Regulating Reactive Oxygen Intermediates of Fe−N−C SAzyme via Second‐Shell Coordination for Selective Aerobic Oxidation Reactions DOI

Yuan Xu,

Yuanjie Ma,

Xinghua Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 19, 2024

Reactive oxygen species (ROS) regulation for single-atom nanozymes (SAzymes), e.g., Fe-N-C, is a key scientific issue that determines the activity, selectivity, and stability of aerobic reaction. However, poor understanding ROS formation mechanism on SAzymes greatly hampers their wider deployment. Herein, inspired by cytochromes P450 affording bound intermediates in O

Language: Английский

Citations

20
Covalent Coupling-Regulated rGO/VN Nanocomposite Enabling Nitrogen Defects to Remarkably Boost the Peroxidase-Like Catalytic Efficiency for the Ultrasensitive Colorimetric Assay of Uric Acid DOI
Xin Zhang,

Ziyan Yuan,

Ziting Lin

et al.

Analytical Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 9, 2025

It remains challenging to rationally design superior nanozymes and understand the underlying mechanism. Herein, a facile covalent coupling-modulated nitrogen defect is reported for significantly boosting peroxidase (POD)-like activity. Vanadium nitride (VN) nanoparticles are grown on graphene oxide (GO) via C–N bonding form VN/rGO nanocomposites by varying with VOx/GO ratio. The initial increasing GO amount enables formation of bond, dramatically POD-like Nevertheless, higher amount, defects decrease due forming mainly V2O3. defect-rich nanocomposite 20 wt % (VG-2) exhibits best catalytic efficiency (Vmax/Km = 0.0187 s–1), which 778-fold than that natural horseradish peroxidase. Theoretical calculations structure characterization reveal rich-N originate from VN binding onto rGO an rich-electron structure, impeding agglomeration, greatly reduces energy barrier rate-determining step reaction. Finally, coupling urate oxidase VG-2 as enzyme cascade, ultrasensitive selective colorimetric detection was developed uric acid (UA), one indicators kidney function or gout attacks, linear ranging 1–100 μM 0.1–2.5 mM limit 0.24 UA (S/N 3). proposed method applicable detecting in human serum samples satisfactorily. This work could inspire more effective insights into designing other robust through variety biochemical analysis biocatalysis applications.

Language: Английский

Citations

4
An iron-based single-atom nanozyme for multiple-channel sensing of epinephrine with wide pH responsivity and intelligence capabilities DOI
Dongyan Li, Hongxia Zhong, Yiru Chen

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: 507, P. 160341 - 160341

Published: Feb. 6, 2025

Language: Английский

Citations

2
Tuning Atomically Dispersed Metal Sites in Nanozymes for Sensing Applications DOI Open Access

Mingwang Liu,

Weiqing Xu,

Yinjun Tang

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

Abstract Nanozymes with atomically dispersed metal sites (ADzymes), especially single‐atom nanozymes, have attracted widespread attention in recent years due to their unique advantages mimicking the active of natural enzymes. These nanozymes not only maximize exposure catalytic but also possess superior activity performance, achieving challenging reactions. position ADzymes as highly promising candidates field sensing and biosensing. This review summarizes classification properties ADzymes, systematically highlighting some typical regulation strategies involving central metal, coordination environment, etc., achieve catalytical activity, specificity, multifunctionality. Then, we present advances different fields, including colorimetry, fluorescence, electrochemistry, chemiluminescence, photoelectrochemistry, electrochemiluminescence. Taking advantage resultant show great potential goal sensitivity, selectivity accuracy for detection various targets. Specifically, underlying mechanisms terms signal amplification were discussed detail. Finally, current challenges perspectives on development advanced are discussed.

Language: Английский

Citations

2
Visualization of the Distance-Dependent Synergistic Interaction in Heterogeneous Dual-Site Catalysis DOI

Shuaiwei Jiang,

Jiawei Xue,

Tong Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 29084 - 29093

Published: Oct. 11, 2024

Understanding the characteristics of interfacial hydroxyl (OH) at solid/liquid electrochemical interface is crucial for deciphering synergistic catalysis. However, it remains challenging to elucidate influences spatial distance between OH and neighboring reactants on reaction kinetics atomic level. Herein, we visualize distance-dependent interaction in heterogeneous dual-site catalysis by using ex-situ infrared nanospectroscopy situ spectroscopy techniques. These spectroscopic techniques achieve direct identification distribution species reveal that facilitates reactant deprotonation process depending site distances catalysts. Via modulating Ir-Co pair distances, find dynamic equilibrium generation consumption accounts high-efficiency synergism optimized 7.9 Å. At farther or shorter inaccessibility resistance with intermediates lead accumulation, thereby diminishing effect. Hence, a volcano-shaped curve has been established mass activity formic acid oxidation as probe reaction. This notion could also be extended oxophilic metals, like Ir-Ru pairs, where volcano curves further evidence universal significance distances.

Language: Английский

Citations

7
Boosting Peroxidase-Mimetic Activity of FeMn-NCe Dual-Atom Radiosensitizing Nanozymes for Augmented Radiodynamic Immunotherapy DOI
Bo Chen, Yinggang Wang,

Min Mu

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Dual-atom nanozymes (DAzymes) have garnered considerable attention as catalysts for reactive oxygen species (ROS)-based therapies, effectively leveraging ROS generation within the tumor microenvironment (TME). Herein, we introduce FeMn-NCe DAzymes, which are meticulously engineered enhanced peroxidase (POD)-mimetic activity and potent radiosensitization to advance radioimmunotherapy. Density functional theory (DFT) calculations reveal that DAzymes lower energy barrier increase substrate affinity, enabling highly efficient catalytic performance. Within TME, these efficiently convert overexpressed hydrogen peroxide (H2O2) into hydroxyl radicals (•OH), potentially activating cGAS-STING immune pathway. This POD-mimetic catalysis is further accelerated under X-ray irradiation, significantly enhancing radiosensitization. Additionally, a uniform coating of ultrasmall gold nanoparticles on enhances absorption cancer cells. The incorporation STING agonist diABZI onto induces long-term antitumor immunity, reprograms immunosuppressive suppresses growth metastasis following single low-dose treatment. work highlights valuable strategy designing radiodynamic immunotherapy.

Language: Английский

Citations

1
Bioinspired Carbon Dots with Multi‐Enzyme Activity, Single‐Atom Catalytic, High Efficiency ROS Scavenging and Antioxidant Therapy for Rheumatoid Arthritis DOI
Qian He, Ruijiao Li, Jiawen Liu

et al.

Advanced Healthcare Materials, Journal Year: 2025, Volume and Issue: unknown

Published: May 19, 2025

Abstract Carbon dots (CDs) with enzyme‐like activity have garnered significant attention due to their ability mimic the catalytic functions of natural enzymes, making them suitable for specific biochemical reactions in biological environments. However, development CDs multi‐enzyme activities remains a challenge inherent complexity incorporating multiple into single nanostructure. Here, synthesis active are successfully demonstrated via hydrothermal process utilizing hemin chloride and urea as precursors. Detailed structural theoretical investigations reveal that possess highly graphitized π‐electron system single‐atom iron centers arranged monodisperse, four‐coordinate configuration nitrogen atoms. This distinctive imparts activities, including superoxide dismutase catalase, which contribute efficient scavenging reactive oxygen species. Furthermore, encapsulating these within macrophage membranes enables selective targeting inflammatory sites circumvention immune clearance collagen‐induced arthritis rat model, offering targeted effective antioxidant therapy rheumatoid arthritis.

Language: Английский

Citations

1