Because of the high catalytic activities and substrate specificity, natural enzymes have been widely used in industrial, medical, and biological fields, etc. Although promising, they often suffer from intrinsic shortcomings such as high cost, low operational stability, and difficulties of recycling. To overcome these shortcomings, researchers have been devoted to the exploration of artificial enzyme mimics for a long time. Since the discovery of ferromagnetic nanoparticles with intrinsic horseradish peroxidase-like activity in 2007, a large amount of studies on nanozymes have been constantly emerging in the next decade. Nanozymes are one kind of nanomaterials with enzymatic catalytic properties. Compared with natural enzymes, nanozymes have the advantages such as low cost, high stability and durability, which have been widely used in industrial, medical, and biological fields. A thorough understanding of the possible catalytic mechanisms will contribute to the development of novel and high-efficient nanozymes, and the rational regulations of the activities of nanozymes are of great significance. In this review, we systematically introduce the classification, catalytic mechanism, activity regulation as well as recent research progress of nanozymes in the field of biosensing, environmental protection, and disease treatments, etc. in the past years. We also propose the current challenges of nanozymes as well as their future research focus. We anticipate this review may be of significance for the field to understand the properties of nanozymes and the development of novel nanomaterials with enzyme mimicking activities.

Nanozymes: Classification, Catalytic Mechanisms, Activity Regulation, and Applications

Nanozymes are nanomaterials with intrinsic enzyme-like characteristics that have been booming over the past decade because of their capability to address the limitations of natural enzymes such as low stability, high cost, and difficult storage. Along with the rapid development and ever-deepening understanding of nanoscience and nanotechnology, nanozymes hold promise to serve as direct surrogates of traditional enzymes by mimicking and further engineering the active centers of natural enzymes. In 2007, we reported the first evidence that Fe3O4 nanoparticles (NPs) have intrinsic peroxidase-mimicking activity, and since that time, hundreds of nanomaterials have been found to mimic the catalytic activity of peroxidase, oxidase, catalase, haloperoxidase, glutathione peroxidase, uricase, methane monooxygenase, hydrolase, and superoxide dismutase. Uniquely, a broad variety of nanomaterials have been reported to simultaneously exhibit dual- or multienzyme mimetic activity. For example, Fe3O4 NPs show pH-dependent peroxidase-like and catalase-like activities; Prussian blue NPs simultaneously possess peroxidase-, catalase-, and superoxide dismutase-like activity; and Mn3O4 NPs mimic all three cellular antioxidant enzymes including superoxide dismutase, catalase, and glutathione peroxidase. Taking advantage of the physiochemical properties of nanomaterials, nanozymes have shown a broad range of applications from in vitro detection to replacing specific enzymes in living systems. With the emergence of the new concept of "nanozymology", nanozymes have now become an emerging new field connecting nanotechnology and biology. Since the landmark paper on nanozymes was published in 2007, we have extensively explored their catalytic mechanism, established the corresponding standards to quantitatively determine their catalytic activities, and opened up a broad range of applications from biological detection and environmental monitoring to disease diagnosis and biomedicine development. Here we mainly focus on our progress in the systematic design and construction of functionally specific nanozymes, the standardization of nanozyme research, and the exploration of their applications for replacing natural enzymes in living systems. We also show that, by combining the unique physicochemical properties and enzyme-like catalytic activities, nanozymes can offer a variety of multifunctional platforms with a broad of applications from in vitro detection to in vivo monitoring and therapy. For instance, targeting antibody-conjugated ferromagnetic nanozymes simultaneously provide three functions: target capture, magnetic separation, and nanozyme color development for target detection. We finally will address the prospect of nanozyme research to become "nanozymology". We expect that nanozymes with unique physicochemical properties and intrinsic enzyme-mimicking catalytic properties will attract broad interest in both fundamental research and practical applications and offer new opportunities for traditional enzymology.

Nanozymes: From New Concepts, Mechanisms, and Standards to Applications.

Graphene is a two-dimensional carbon material with a honeycomb lattice and Dirac-like low-energy excitations. When Zeeman and spin-orbit interactions are neglected, its Landau levels are fourfold degenerate, explaining the 4e2/h separation between quantized Hall conductivity values seen in recent experiments. In this Letter we derive a criterion for the occurrence of interaction-driven quantum Hall effects near intermediate integer values of e2/h due to charge gaps in broken symmetry states.

Quantum Hall Ferromagnetism in Graphene

Nanozyme, a term defined for nanomaterial with enzyme-like properties, has attracted significant research attention owing to its striking merits. Recently, a surge of nanozymes have been demonstrated to catalyze some typical enzymatic reactions mimicking oxidase, peroxidase and catalase. Especially, nanozymes with peroxidase-like activity have grown into a big family due to their broad range of applications in the field of biosensing and immunoassay. Since inorganic nanoparticles possess the advantages of high stability and easy surface modification, nanozymes have been emerging alternatives to natural enzymes to some extent. In this Review, we briefly summarize several typical nanozymes and then focus our attention on their enormous applications with respect to analytical chemistry. Representative examples would be discussed in detail from the literatures of last 10 years. Additionally, the current challenges and future directions about nanozymes are speculated at the end of this review.

Nanozyme: An emerging alternative to natural enzyme for biosensing and immunoassay

As a new generation of artificial enzymes, nanozymes have the advantages of high catalytic activity, good stability, low cost, and other unique properties of nanomaterials. Due to their wide range of potential applications, they have become an emerging field bridging nanotechnology and biology, attracting researchers in various fields to design and synthesize highly catalytically active nanozymes. However, the thorough understanding of experimental phenomena and the mechanisms beneath practical applications of nanozymes limits their rapid development. Herein, the progress of experimental and computational research of nanozymes on two issues over the past decade is briefly reviewed: (1) experimental development of new nanozymes mimicking different types of enzymes. This covers their structures and applications ranging from biosensing and bioimaging to therapeutics and environmental protection. (2) The catalytic mechanism proposed by experimental and theoretical study. The challenges and future directions of computational research in this field are also discussed.

Recent Advances in Nanozyme Research

Gold nanoparticles (AuNPs) with simultaneous plasmonic and biocatalytic properties provide a promising approach to developing versatile bioassays However, the combination of AuNPs’ intrinsic enzyme-mimicking properties with their surface-enhanced Raman scattering (SERS) activities has yet to be explored Here we designed a peroxidase-mimicking nanozyme by in situ growing AuNPs into a highly porous and thermally stable metal–organic framework called MIL-101 The obtained AuNPs@MIL-101 nanozymes acted as peroxidase mimics to oxidize Raman-inactive reporter leucomalachite green into the active malachite green (MG) with hydrogen peroxide and simultaneously as the SERS substrates to enhance the Raman signals of the as-produced MG We then assembled glucose oxidase (GOx) and lactate oxidase (LOx) onto AuNPs@MIL-101 to form AuNPs@MIL-101@GOx and AuNPs@MIL-101@LOx integrative nanozymes for in vitro detection of glucose and lactate via SERS Moreover, the integrative nanozymes were further explored for monitoring

Surface-Enhanced Raman Scattering Active Gold Nanoparticles with Enzyme-Mimicking Activities for Measuring Glucose and Lactate in Living Tissues

Graphene oxide nanoribbons (GONRs) annealed at the low temperature of 400 °C (aGONRs-400) are developed as an excellent room-temperature (RT) ferromagnet. The saturated magnetization (Ms) of aGONRs-400 is high, up to 0.39 emu/g at room temperature, and the RT ferromagnetism (FM) exhibits excellent ambient stability with Ms preserved for over half a year. The preferential distribution of the magnetic phenolic hydroxyl toward the edges, which contributes to the long-range ferromagnetic couplings, was confirmed by X-ray photoemission spectroscopy measurement and gradient annealing analysis. The approach of low-temperature annealing is proved to be efficient both to remove the prominent nonmagnetic epoxy groups on the basal plane of GONRs or transform them to magnetic hydroxyl groups and to preserve the magnetic phenolic hydroxyl at the edges to realize a strong and ambient stable FM.

Realization of Ambient-Stable Room-Temperature Ferromagnetism by Low-Temperature Annealing of Graphene Oxide Nanoribbons.

The sizeable direct bandgap, high mobility, and long spin lifetimes at room temperature offer black phosphorus (BP) potential applications in spin-based semiconductor devices. Toward these applications, a critical step is creating a magnetic response in BP, which is arousing much interest. It is reported here that ambient degradation of BP, which is immediate and inevitable and greatly changes the semiconducting properties, creates magnetic moments, and any degree of degradation leads to notable paramagnetism. Its Landau factor g measured is ≈1.995, revealing that the magnetization mainly results from spin rather than orbital moments. Such magnetism most likely results from the unsaturated phosphorus in the vacancies which are stabilized by O adatoms. It can be tuned by changing any one of the ambient factors of ambient temperature, humidity, and light intensity, and can be stabilized by exposing BP in argon. The findings highlight the importance of evaluating the effect of ambient degradation-induced magnetism on BP's spin-based devices. The work seems an essential milestone toward the forthcoming research upsurge on BP's magnetism.

Yu Deng

Papers

Surface-Enhanced Raman Scattering Active Gold Nanoparticles with Enzyme-Mimicking Activities for Measuring Glucose and Lactate in Living Tissues

Realization of Ambient-Stable Room-Temperature Ferromagnetism by Low-Temperature Annealing of Graphene Oxide Nanoribbons.

Ambient Degradation-Induced Spin Paramagnetism in Phosphorene.