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

Since the discovery of highly conducting polyacetylene by Shirakawa, MacDiarmid, and Heeger in 1977, π-conjugated systems have attracted much attention as futuristic materials for the development and production of the next generation of electronics, that is, organic electronics. Conceptually, organic electronics are quite different from conventional inorganic solid state electronics because the structural versatility of organic semiconductors allows for the incorporation of functionality by molecular design. This versatility leads to a new era in the design of electronic devices. To date, the great number of π-conjugated semiconducting materials that have either been discovered or synthesized generate an exciting library of π-conjugated systems for use in organic electronics. 11 However, some key challenges for further advancement remain: the low mobility and stability of organic semiconductors, the lack of knowledge regarding structure property relationships for understanding the fundamental chemical aspects behind the structural design, and realization of desired properties. Organic field-effect transistors (OFETs) are a kind of device consisting of an organic semiconducting layer, a gate insulator layer, and three terminals (drain, source, and gate electrodes). OFETs are not only essential building blocks for the next generation of cheap and flexible organic circuits, but they also provide an important insight into the charge transport of πconjugated systems. Therefore, they act as strong tools for the exploration of the structure property relationships of πconjugated systems, such as parameters of field-effect mobility (μ, the drift velocity of carriers under unit electric field), current on/off ratio (the ratio of the maximum on-state current to the minimum off-state current), and threshold voltage (the minimum gate voltage that is required to turn on the transistor). 17 Since the discovery of OFETs in the 1980s, they have attracted much attention. Research onOFETs includes the discovery, design, and synthesis of π-conjugated systems for OFETs, device optimization, development of applications in radio frequency identification (RFID) tags, flexible displays, electronic papers, sensors, and so forth. It is beyond the scope of this review to cover all aspects of π-conjugated systems; hence, our focus will be on the performance analysis of π-conjugated systems in OFETs. This should make it possible to extract information regarding the fundamental merit of semiconducting π-conjugated materials and capture what is needed for newmaterials and what is the synthesis orientation of newπ-conjugated systems. In fact, for a new science with many practical applications, the field of organic electronics is progressing extremely rapidly. For example, using “organic field effect transistor” or “organic field effect transistors” as the query keywords to search the Web of Science citation database, it is possible to show the distribution of papers over recent years as shown in Figure 1A. It is very clear

Semiconducting π-conjugated systems in field-effect transistors: a material odyssey of organic electronics.

Graphene, a two-dimensional, single-layer sheet of sp(2) hybridized carbon atoms, has attracted tremendous attention and research interest, owing to its exceptional physical properties, such as high electronic conductivity, good thermal stability, and excellent mechanical strength. Other forms of graphene-related materials, including graphene oxide, reduced graphene oxide, and exfoliated graphite, have been reliably produced in large scale. The promising properties together with the ease of processibility and functionalization make graphene-based materials ideal candidates for incorporation into a variety of functional materials. Importantly, graphene and its derivatives have been explored in a wide range of applications, such as electronic and photonic devices, clean energy, and sensors. In this review, after a general introduction to graphene and its derivatives, the synthesis, characterization, properties, and applications of graphene-based materials are discussed.

Graphene-Based Materials: Synthesis, Characterization, Properties, and 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

The chemical reduction of graphene oxide is a promising route towards the large scale production of graphene for commercial applications. The current state-of-the-art in graphene oxide reduction, consisting of more than 50 types of reducing agent, will be reviewed from a synthetic chemistry point of view. Emphasis is placed on the techniques, reaction mechanisms and the quality of the produced graphene. The reducing agents are reviewed under two major categories: (i) those which function according to well-supported mechanisms and (ii) those which function according to proposed mechanisms based on knowledge of organic chemistry. This review will serve as a valuable platform to understand the efficiency of these reducing agents for the reduction of graphene oxide.

Chemical reduction of graphene oxide: a synthetic chemistry viewpoint

Light-matter strong coupling allows for the possibility of entangling the wave functions of different molecules through the light field. We hereby present direct evidence of non-radiative energy transfer well beyond the Forster limit for spatially separated donor and acceptor cyanine dyes strongly coupled to a cavity. The transient dynamics and the static spectra show an energy transfer efficiency approaching 37 % for donor-acceptor distances ≥100 nm. In such systems, the energy transfer process becomes independent of distance as long as the coupling strength is maintained. This is consistent with the entangled and delocalized nature of the polaritonic states.

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Energy Transfer between Spatially Separated Entangled Molecules.

Two birds with one stone: the simultaneous production of two important bulk chemicals, methanol and ethylene glycol, from CO(2) and ethylene oxide has been achieved under mild conditions by the highly efficient homogeneous catalytic hydrogenation of ethylene carbonate in the presence of a (PNP)Ru(II) catalyst.

Catalytic Hydrogenation of Cyclic Carbonates: A Practical Approach from CO2 and Epoxides to Methanol and Diols

We report the synthesis of cobalt complexes of novel iminopyridine–oxazoline (IPO) ligands and their application to the asymmetric hydroboration of 1,1-disubstituted aryl alkenes. The new catalysts afforded α-alkyl-β-pinacolatoboranes with exclusive regioselectivity in high yields with up to 99.5% ee. Furthermore, we have applied this method to an efficient synthesis of naproxen.

Cobalt-Catalyzed Enantioselective Hydroboration of 1,1-Disubstituted Aryl Alkenes

The iron pincer complex (IPC) is found to be optimal as precatalyst in the transformation of various alkenes.

Iron‐Catalyzed, Atom‐Economical, Chemo‐ and Regioselective Alkene Hydroboration with Pinacolborane

An extremely efficient cobalt catalyst for the hydroboration of both vinylarenes and aliphatic α-olefins with pinacolborane is described, providing the anti-Markovnikov products with excellent regio- and chemoselectivity, broad functional-group tolerance, and high turnover numbers (up to 19,800). The alkene hydroboration route is further extended to a two-step, one-pot hydroboration and cross-coupling of alkylboronates with aryl chlorides.

Lei Zhang

Papers

Energy Transfer between Spatially Separated Entangled Molecules.

Catalytic Hydrogenation of Cyclic Carbonates: A Practical Approach from CO2 and Epoxides to Methanol and Diols

Cobalt-Catalyzed Enantioselective Hydroboration of 1,1-Disubstituted Aryl Alkenes

Iron‐Catalyzed, Atom‐Economical, Chemo‐ and Regioselective Alkene Hydroboration with Pinacolborane

A Cobalt-Catalyzed Alkene Hydroboration with Pinacolborane†