Over the past few decades, researchers have established artificial enzymes as highly stable and low-cost alternatives to natural enzymes in a wide range of applications. A variety of materials including cyclodextrins, metal complexes, porphyrins, polymers, dendrimers and biomolecules have been extensively explored to mimic the structures and functions of naturally occurring enzymes. Recently, some nanomaterials have been found to exhibit unexpected enzyme-like activities, and great advances have been made in this area due to the tremendous progress in nano-research and the unique characteristics of nanomaterials. To highlight the progress in the field of nanomaterial-based artificial enzymes (nanozymes), this review discusses various nanomaterials that have been explored to mimic different kinds of enzymes. We cover their kinetics, mechanisms and applications in numerous fields, from biosensing and immunoassays, to stem cell growth and pollutant removal. We also summarize several approaches to tune the activities of nanozymes. Finally, we make comparisons between nanozymes and other catalytic materials (other artificial enzymes, natural enzymes, organic catalysts and nanomaterial-based catalysts) and address the current challenges and future directions (302 references).

Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes

Coinage metals, such as Au, Ag, and Cu, have been important materials throughout history.1 While in ancient cultures they were admired primarily for their ability to reflect light, their applications have become far more sophisticated with our increased understanding and control of the atomic world. Today, these metals are widely used in electronics, catalysis, and as structural materials, but when they are fashioned into structures with nanometer-sized dimensions, they also become enablers for a completely different set of applications that involve light. These new applications go far beyond merely reflecting light, and have renewed our interest in maneuvering the interactions between metals and light in a field known as plasmonics.2–6

In plasmonics, the metal nanostructures can serve as antennas to convert light into localized electric fields (E-fields) or as waveguides to route light to desired locations with nanometer precision. These applications are made possible through a strong interaction between incident light and free electrons in the nanostructures. With a tight control over the nanostructures in terms of size and shape, light can be effectively manipulated and controlled with unprecedented accuracy.3,7 While many new technologies stand to be realized from plasmonics, with notable examples including superlenses,8 invisible cloaks,9 and quantum computing,10,11 conventional technologies like microprocessors and photovoltaic devices could also be made significantly faster and more efficient with the integration of plasmonic nanostructures.12–15 Of the metals, Ag has probably played the most important role in the development of plasmonics, and its unique properties make it well-suited for most of the next-generation plasmonic technologies.16–18

1.1. What is Plasmonics?
Plasmonics is related to the localization, guiding, and manipulation of electromagnetic waves beyond the diffraction limit and down to the nanometer length scale.4,6 The key component of plasmonics is a metal, because it supports surface plasmon polariton modes (indicated as surface plasmons or SPs throughout this review), which are electromagnetic waves coupled to the collective oscillations of free electrons in the metal.

While there are a rich variety of plasmonic metal nanostructures, they can be differentiated based on the plasmonic modes they support: localized surface plasmons (LSPs) or propagating surface plasmons (PSPs).5,19 In LSPs, the time-varying electric field associated with the light (Eo) exerts a force on the gas of negatively charged electrons in the conduction band of the metal and drives them to oscillate collectively. At a certain excitation frequency (w), this oscillation will be in resonance with the incident light, resulting in a strong oscillation of the surface electrons, commonly known as a localized surface plasmon resonance (LSPR) mode.20 This phenomenon is illustrated in Figure 1A. Structures that support LSPRs experience a uniform Eo when excited by light as their dimensions are much smaller than the wavelength of the light.



Figure 1

Schematic illustration of the two types of plasmonic nanostructures discussed in this article as excited by the electric field (Eo) of incident light with wavevector (k). In (A) the nanostructure is smaller than the wavelength of light and the free electrons ...



In contrast, PSPs are supported by structures that have at least one dimension that approaches the excitation wavelength, as shown in Figure 1B.4 In this case, the Eo is not uniform across the structure and other effects must be considered. In such a structure, like a nanowire for example, SPs propagate back and forth between the ends of the structure. This can be described as a Fabry-Perot resonator with resonance condition l=nλsp, where l is the length of the nanowire, n is an integer, and λsp is the wavelength of the PSP mode.21,22 Reflection from the ends of the structure must also be considered, which can change the phase and resonant length. Propagation lengths can be in the tens of micrometers (for nanowires) and the PSP waves can be manipulated by controlling the geometrical parameters of the structure.23

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Controlling the synthesis and assembly of silver nanostructures for plasmonic applications

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

Gold nanorods have been receiving extensive attention owing to their extremely attractive applications in biomedical technologies, plasmon-enhanced spectroscopies, and optical and optoelectronic devices. The growth methods and plasmonic properties of Au nanorods have therefore been intensively studied. In this review, we present a comprehensive overview of the flourishing field of Au nanorods in the past five years. We will focus mainly on the approaches for the growth, shape and size tuning, functionalization, and assembly of Au nanorods, as well as the methods for the preparation of their hybrid structures. The plasmonic properties and the associated applications of Au nanorods will also be discussed in detail.

Gold nanorods and their plasmonic properties

Chemistries that Facilitate Nanotechnology Kim E. Sapsford,† W. Russ Algar, Lorenzo Berti, Kelly Boeneman Gemmill,‡ Brendan J. Casey,† Eunkeu Oh, Michael H. Stewart, and Igor L. Medintz*,‡ †Division of Biology, Department of Chemistry and Materials Science, Office of Science and Engineering Laboratories, U.S. Food and Drug Administration, Silver Spring, Maryland 20993, United States ‡Center for Bio/Molecular Science and Engineering Code 6900 and Division of Optical Sciences Code 5611, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States College of Science, George Mason University, 4400 University Drive, Fairfax, Virginia 22030, United States Department of Biochemistry and Molecular Medicine, University of California, Davis, School of Medicine, Sacramento, California 95817, United States Sotera Defense Solutions, Crofton, Maryland 21114, United States

Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology.

Au@Pt nanostructures as oxidase and peroxidase mimetics for use in immunoassays.

Bimetallic alloy nanoparticles (NPs) exhibit unique optical and catalytic properties that are dependent on their morphology and composition. In this paper, a general and facile way was developed to prepare Ag-related bimetallic alloy NPs with hollow/porous structures, including AgAu, AgPd, and AgPt. The formation of the alloy structures is evidenced by high-resolution transmission electron microscopy (TEM), scanning transmission electron microscopy−energy-dispersive X-ray analysis (STEM-EDX) mapping, and ultraviolet−visible−near-infrared (UV−vis−NIR) absorption spectra. AgM alloy NPs exhibit peroxidase-like activity. A unique composition dependence is found and can be used to tailor the catalytic activity. In addition to the recent discoveries about peroxidase mimetics on Fe3O4 NPs and sheetlike FeS nanostructures, our findings suggest a new type of candidate as peroxidase mimics. Furthermore, for noble metals, apart from size and shape, tailoring the composition poses another effective way to tune the ca...

Design of AgM Bimetallic Alloy Nanostructures (M = Au, Pd, Pt) with Tunable Morphology and Peroxidase-Like Activity

Intrinsic catalytic activity of Au nanoparticles with respect to hydrogen peroxide decomposition and superoxide scavenging.

Au nanorods @ Pt nanodots core/shell nanostructures, prepared by the Au nanorods (NRs)-mediated growth, exhibit dual functional enzyme-like (peroxidase and oxidase-like) activities. From the viewpoint of enzyme mimics, the relationship between apparent enzyme kinetic parameters and nanomaterials structure is investigated in order to rationally design the catalytic activity. Using peroxidase-like properties of the Au@Pt NRs, the determination of hydrogen peroxide (H2O2) was demonstrated with a limit of detection (LOD) of 4.5 × 10−5 M and a linear range of 4.5 × 10−5–1 × 10−3 M using o-phenylenediamine (OPD) as chromogenic substrate. Furthermore, in combination with highly specific reactions provided by natural enzymes, selective detections of glucose and lipophilic cholesterol were demonstrated with similar LODs and linear ranges. Additionally, owing to the specific oxidase-like activity of the Au@Pt NRs (ascorbate oxidase), interference of ascorbic acid in the detection of glucose could be eliminated. In conclusion, considering the flexibility in the design of nanomatererials, there is a lot of space to improve their activity and explore their potential applications, especially in relatively harsh conditions.

Au@Pt core/shell nanorods with peroxidase- and ascorbate oxidase-like activities for improved detection of glucose

The island growth mode of Pt was employed to guide the forma-tion of PdPt alloy nanodots on gold nanorods (Au@PdPt NRs). Well-defined alloy nanodots, with tunable Pd/Pt ratios from 0.2 to 5, distribute homogeneously on the surface of the Au NR. Formation of nanodots shell leads to the red-shift and broadening of the longitudinal surface plasmon resonance (LSPR) band of the Au NRs. The Au@PdPt alloy NRs exhibit catalytic activity toward oxidation of often-used chromogenic substrates by dissolved oxygen under mild conditions, suggesting a new type of oxidase mimics. Composition dependence catalytic activity is observed for the oxidation of ascorbic acid (AA) and 3,3',5,5'-tetramethylbenzidine (TMB) and for the reduction of p-nitrophenol. For AA and TMB, catalytic activity enhances quickly at lower Pd/Pt ratios and tends to saturate at higher Pd/Pt ratios. For p-nitrophenol reduction, catalytic activity shows a nice linear relationship with Pd/Pt ratio owing to much higher catalytic activity of Pd. In conclusion, proper alloying of Pd and Pt presents an effective route to tailor the catalytic activity. Interesting, alloy nanodots can also catalyze the oxidation of Fe (II) to Fe (III) by dissolved oxygen. Thus, based on the competitive oxidation of TMB and Fe (II), selective detection of the latter can be achieved.

Xiaona Hu

Papers

Au@Pt nanostructures as oxidase and peroxidase mimetics for use in immunoassays.

Design of AgM Bimetallic Alloy Nanostructures (M = Au, Pd, Pt) with Tunable Morphology and Peroxidase-Like Activity

Intrinsic catalytic activity of Au nanoparticles with respect to hydrogen peroxide decomposition and superoxide scavenging.

Au@Pt core/shell nanorods with peroxidase- and ascorbate oxidase-like activities for improved detection of glucose

Formation of PdPt alloy nanodots on gold nanorods: tuning oxidase-like activities via composition