Tuning iron spin states in single-atom nanozymes enables efficient peroxidase mimicking

Wei, Xiaoqian; Song, Shaojia; Song, Weiyu; Wen, Yating; Xu, Weiqing; Chen, Yifeng; Wu, Zhichao; Qin, Ying; Jiao, Lei; Wu, Yu; Sha, Meng; Huang, Jiajia; Cai, Xiaoli; Zheng, Lirong; Hu, Lili; Gu, Wenling; Eguchi, Miharu; Asahi, Toru; Yamauchi, Yusuke; Zhu, Chengzhou

doi:10.1039/d2sc05679h

Cited by 40 publications

(26 citation statements)

References 53 publications

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“…Furthermore, the apparent ratio of the intensities of the signals (1:2:2:1) was considered typical for the OH· radicals being trapped in DMPO (5,5‐Dimethyl‐1‐Pyrroline‐N‐oxide, a free radical trapping agent) as a characteristic resonance phenomenon. [ 44 ] Although the relative signal intensity increases with time, the weak signal intensity at the onset of catalysis could be attributed to the tendency of the H 2 O 2 ‐catalyzed decomposition of OH· at the catalytic interface to further adsorb at the surface and lead to a decrease in the number of detectable hydroxyl radicals in the liquid phase, which would be further explained in the subsequent analysis of the surface adsorption model.…”

Section: Resultsmentioning

confidence: 99%

Enzyme‐Encapsulated Protein Trap Engineered Metal–Organic Framework‐Derived Biomineral Probes for Non‐Invasive Prostate Cancer Surveillance

Tang

Gong

et al. 2023

Adv Funct Materials

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A paper‐based naked‐eye recognition assay with enzyme‐encapsulated protein engineered metal–organic framework‐derived biominerals is developed for direct quantification of sarcosine in urine samples for screening of prostate cancer individuals. The detection strategy stems from the successful construction of a cascade response model, which involves the introduction of a cascade enzymatic catalytic reaction on Pt nanoparticles (NPs)‐loaded porous CeO2 by integrating a sarcosine oxidase as a special recognition unit and a chromogenic substrate as a signal molecule reporter. Pt NPs‐loaded CeO2 is subjected to a one‐step thermal treatment based on multilayered mesoporous Ce‐based metal–organic framework, and the calcined CeO2 exhibits the same distinct porous graded structure. Importantly, introduction of Pt NPs sharply enhances the peroxidase‐like activity of CeO2, which is considered to be caused by the difference in the adsorption behavior of hydrogen peroxide on the CeO2 surface and Pt/CeO2 obtained by density functional theory calculations. On the basis of this, the probe is used on a mass‐producible paper‐based working platform and 3D‐printed device to specifically screen for minor differences in sarcosine between urine samples from cancer patients and normal individuals. Enzyme‐assisted cascade catalytic reaction can be extended by replacing different recognition units for multiple analytes.

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Section: Resultsmentioning

confidence: 99%

Enzyme‐Encapsulated Protein Trap Engineered Metal–Organic Framework‐Derived Biomineral Probes for Non‐Invasive Prostate Cancer Surveillance

Tang

Gong

et al. 2023

Adv Funct Materials

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“…As shown in Figure 5B and Table S6, one doublet was fitted. The doublet can be assigned to the Fe low‐spin (LS) state 35,36 . Therefore, it can be inferred that Fe in Fe 1 TiO 2 is low‐spin structure.…”

Section: Resultsmentioning

confidence: 99%

“…The doublet can be assigned to the Fe low-spin (LS) state. 35,36 Therefore, it can be inferred that Fe in Fe 1 TiO 2 is low-spin structure.…”

Section: Mechanism Studiesmentioning

confidence: 99%

Embedding isolated Fe species in titania increases olefins for oxidative propane dehydrogenation

et al. 2023

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Metal oxide-based catalysts are widely studied in oxidative propane dehydrogenation (OPDH), but they usually suffered from the low olefin activity, which is believed to be related to the active centers of metal-oxygen species. Herein, we report an effective cation-exchange strategy towards the development of TiO 2 nanosheets embedded isolated Fe species (Fe 1 TiO 2 ) as a highly-active and stable catalyst for OPDH. It exhibits an olefin yield of 38.2% at 520 C, 10.9 and 2.4 times higher than that of pure TiO 2 (3.5%) and Fe 2 O 3 (15.6%), respectively; and it shows a superior 100-h durability.The isolated Fe species embedded in Fe 1 TiO 2 are demonstrated to serve as active centers. Multiple characterizations including in situ Fourier transform infrared spectroscopy (FT-IR) and theoretical calculations demonstrate that the isolated Fe species in Fe 1 TiO 2 are favorable for the generation of olefins, which produce propylene (C 3 ) through an appropriate Fe H dehydrogenation pathway with a low energy barrier.

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“…Single-atom nanozymes featuring well-defined M–N x (M = Fe, Co, Pt, Mn, and Cu) sites are new enzyme-mimicking candidates, which have been widely applied in tumor therapy, disinfection, and other fields. − The maximum atom utilization and similarity of M–N x sites to those of natural metalloenzymes endow SAzymes with a higher catalytic activity than conventional nanozymes. − However, they have a limited catalytic activity compared to natural enzymes, which restricts their performance and further application. Recently, the manipulation of the surrounding atomic configuration of SAzymes has been widely adopted to improve their catalytic activity. − For example, the catalytic performance of SAzymes can be regulated by tuning the coordination numbers of the single metal sites. − Likewise, replacing coordinated nitrogen with other elements to form Fe/CoN 3 P or FeN 3 S could enhance enzyme-like activity via near–range interactions. − Heteroatom doping (for example, with phosphorus and boron) of the carbon matrix can also enhance the peroxidase-like (POD-like) activity of the Fe center through long–range interactions. , Despite the significant advances made, the active sites in SAzymes are still generally two-dimensional (2D) and isolated catalytic units.…”

Section: Introductionmentioning

confidence: 99%

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

Líu

et al. 2023

J. Am. Chem. Soc.

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

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Tuning iron spin states in single-atom nanozymes enables efficient peroxidase mimicking

Abstract: The large-scale application of nanozymes remains a significant challenge owing to their unsatisfactory catalytic performances. Featuring unique electronic structure and coordination environment, single-atom nanozymes provide great opportunities to vividly mimic...

Cited by 40 publications

References 53 publications

Enzyme‐Encapsulated Protein Trap Engineered Metal–Organic Framework‐Derived Biomineral Probes for Non‐Invasive Prostate Cancer Surveillance

Enzyme‐Encapsulated Protein Trap Engineered Metal–Organic Framework‐Derived Biomineral Probes for Non‐Invasive Prostate Cancer Surveillance

Embedding isolated Fe species in titania increases olefins for oxidative propane dehydrogenation

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

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