Liposome-Boosted Peroxidase-Mimicking Nanozymes Breaking the pH Limit

Peroxidase-mimicking nanozymes such as Fe₃O₄ nanoparticles are promising substitutes for natural enzymes like horseradish peroxidase. However, most such nanozymes work efficiently only in acidic conditions. In this work, the influence of various liposomes on nanozyme activity was studied. By introducing negatively charged liposomes, peroxidase-mimicking nanozymes achieved oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in neutral and even alkaline conditions, although the activity towards anionic 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) was inhibited. The Fe₃O₄ nanoparticles adsorbed on the liposomes without disrupting membrane integrity as confirmed by fluorescence quenching, dye leakage assays, and cryo-electron microscopy. Stabilization of the blue-colored oxidized products of TMB by electrostatic interactions was believed to be the reason for the enhanced activity. This work has introduced lipids to nanozyme research, and it also has practically important applications for using nanozymes at neutral pH, such as the detection of hydrogen peroxide and glucose.     

The Fe-N-C Nanozyme with Both Accelerated and Inhibited Biocatalytic Activities Capable of Accessing Drug–Drug Interactions

Emerging as a cost-effective and robust enzyme mimic, nanozymes have drawn increasing attention with broad applications ranging from cancer therapy to biosensing. Developing nanozymes with both accelerated and inhibited biocatalytic properties in a biological context is intriguing to peruse more advanced functions of natural enzymes, but remains challenging, because most nanozymes are lack of enzyme-like molecular structures. By re-visiting and engineering the well-known Fe-N-C electrocatalyst that has a heme-like Fe-N_x active sites, herein, it is reported that Fe-N-C could not only catalyze drug metabolization but also had inhibition behaviors similar to cytochrome P450 (CYP), endowing it a potential replacement of CYP for preliminary evaluation of massive potential chemicals, drug dosing guide, and outcome prediction. In addition, in contrast to electrocatalysts, the highly graphitic framework of Fe-N-C may not be obligatory for a competitive CYP-like activity.     

The Fe‐N‐C Nanozyme with Both Accelerated and Inhibited Biocatalytic Activities Capable of Accessing Drug–Drug Interactions

Emerging as a cost‐effective and robust enzyme mimic, nanozymes have drawn increasing attention with broad applications ranging from cancer therapy to biosensing. Developing nanozymes with both accelerated and inhibited biocatalytic properties in a biological context is intriguing to peruse more advanced functions of natural enzymes, but remains challenging, because most nanozymes are lack of enzyme‐like molecular structures. By re‐visiting and engineering the well‐known Fe‐N‐C electrocatalyst that has a heme‐like Fe‐N_x active sites, herein, it is reported that Fe‐N‐C could not only catalyze drug metabolization but also had inhibition behaviors similar to cytochrome P450 (CYP), endowing it a potential replacement of CYP for preliminary evaluation of massive potential chemicals, drug dosing guide, and outcome prediction. In addition, in contrast to electrocatalysts, the highly graphitic framework of Fe‐N‐C may not be obligatory for a competitive CYP‐like activity.     

Self‐Assembly and Compartmentalization of Nanozymes in Mesoporous Silica‐Based Nanoreactors

Herein, to mimic complex natural system, polyelectrolyte multilayer (PEM)‐coated mesoporous silica nanoreactors were used to compartmentalize two different artificial enzymes. PEMs coated on the surface of mesoporous silica could serve as a permeable membrane to control the flow of molecules. When assembling hemin on the surface of mesoporous silica, the hemin‐based mesoporous silica system possessed remarkable peroxidase‐like activity, especially at physiological pH, and could be recycled more easily than traditional graphene–hemin nanocompounds. The hope is that these new findings may pave the way for exploring novel nanoreactors to achieve compartmentalization of nanozymes and applying artificial cascade catalytic systems to mimic cell organelles or important biochemical transformations     

Recent Advances in Common Transition Metal-Based Single-Atom Nanozymes and Their Applications in Pollutant Detection and Degradation

Nanozymes can be used as favorable substitutes for natural enzymes because of their strong catalytic activity and good stability. At the same time, research on single-atom catalysts (SACs) with isolated metal atoms as active centers is also in full swing, showing excellent performance in a variety of catalytic reactions. With the in-depth study of SACs, people have a comprehensive understanding of them and put forward the concept of single-atom nanozymes (SAzymes) by combining nanozymes with SACs. As a new type of nanomaterial, SAzymes have attracted great interest due to their remarkable catalytic activity and rapid energy conversion. However, most applications of SAzymes are mainly in the fields of biomedicine and biosensing, and less research has been done in the field of the environment. Based on the amazing ability of nanozymes to detect and degrade pollutants, SAzymes are also used in the environmental field, and even they will show better capabilities. This review mainly analyses common transition metal-based SAzymes and describes their applications in the field of environmental pollutants.     

Vacancy‐Engineered Nanoceria: Enzyme Mimetic Hotspots for the Degradation of Nerve Agents

Organophosphorus‐based nerve agents, such as paraoxon, parathion, and malathion, inhibit acetylcholinesterase, which results in paralysis, respiratory failure, and death. Bacteria are known to use the enzyme phosphotriesterase (PTE) to break down these compounds. In this work, we designed vacancy‐engineered nanoceria (VE CeO₂ NPs) as PTE mimetic hotspots for the rapid degradation of nerve agents. We observed that the hydrolytic effect of the nanomaterial is due to the synergistic activity between both Ce³⁺ and Ce⁴⁺ ions located in the active site‐like hotspots. Furthermore, the catalysis by nanoceria overcomes the product inhibition generally observed for PTE and small molecule‐based PTE mimetics.     

Bioinspired Nanozymes with pH‐Independent and Metal Ions‐Controllable Activity: Field‐Programmable Logic Conversion of Sole Logic Gate System

In nature, different environmental factors make organisms to be programmed into different forms. However, it is difficult and significant to realize the field‐programmable logic conversion of sole logic system for molecular logic gates. Here, the concept of pH‐programmable “logic conversion” on the single logic gate based on the peculiar enzyme‐mimicking activity is presented. Inspired by natural enzymes with high pH‐stability and metal ions‐stimulated activity, pH‐independent and metal ions‐controllable catalase mimics (Co₃O₄ nanozymes) are designed by protein‐directed method. Although pH cannot directly change the activity of nanozymes, pH can change the existence state of metal ions and then the electron transfer rate on nanozymes. So, versatile roles of metal ions for catalase‐like and electrocatalytic activities are discovered on the premise of pH‐independency. For the proof‐of‐concept, OR/INHIBIT‐ and INHIBIT/AND‐switchable logic gates are facilely constructed using pH as the environmental stimulus and metal ions as inputs. Hence, the transformation of logic gate functions is realized without the change of logic gate elements and input molecules. This contribution may not only broaden the species and application area of nanozymes, but also open novel avenues for the molecular logic conversion and the metal ions sensor.     

纳米酶及其分析检测应用研究进展

在纳米材料基础上诞生的纳米酶推动了化学、材料学以及生物学等学科的发展。纳米酶克服了天然酶的许多缺点,如价格昂贵、易失活和储存条件要求苛刻等,对生物传感、免疫分析、癌症诊断和治疗等领域产生了巨大的影响。 本论文主要介绍了迄今发现的纳米酶种类、纳米酶调控方式以及纳米酶在分析检测中的应用进展。 此外,针对纳米酶未来发展方向提出了一些思考和建议。     

Nanoisozymes: Crystal‐Facet‐Dependent Enzyme‐Mimetic Activity of V2O5 Nanomaterials

Nanomaterials with enzyme‐like activity (nanozymes) attract significant interest owing to their applications in biomedical research. Particularly, redox nanozymes that exhibit glutathione peroxidase (GPx)‐like activity play important roles in cellular signaling by controlling the hydrogen peroxide (H₂O₂) level. Herein we report, for the first time, that the redox properties and GPx‐like activity of V₂O₅ nanozyme depends not only on the size and morphology, but also on the crystal facets exposed on the surface within the same crystal system of the nanomaterials. These results suggest that the surface of the nanomaterials can be engineered to fine‐tune their redox properties to act as “nanoisozymes” for specific biological applications.     

Carbon Nanozymes: Enzymatic Properties,Catalytic Mechanism,and Applications

Nanozymes have advantages over natural enzymes, such as facile production on large scale, long storage time, low costs, and high stability in harsh environments. Carbon nanomaterials (CNMs), including fullerenes, carbon nanotubes, graphene, carbon quantum dots, and graphene quantum dots, have become a star family in materials science. As a new class of nanozymes, the catalytic activity of CNMs and their hybrids has been extensively reported. In this Minireview, recent progress of CNMs based artificial enzymes, focusing on those with peroxidase‐like activity, has been summarized. The enzymatic properties, catalytic mechanisms, and novel applications of CNM nanozymes in sensing, therapy, and environmental engineering are discussed in detail. Additionally, we also highlight the remaining challenges and unsolved problems. With the fast development of bionanotechnology, the unique enzymatic properties and advantages of CNM nanozymes have received much attention and will continue to be an active and challenging field for the years to come.