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

Carbon quantum dots (CQDs, C-dots or CDs), which are generally small carbon nanoparticles (less than 10 nm in size) with various unique properties, have found wide use in more and more fields during the last few years. In this feature article, we describe the recent progress in the field of CQDs, focusing on their synthetic methods, size control, modification strategies, photoelectric properties, luminescent mechanism, and applications in biomedicine, optronics, catalysis and sensor issues.

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Carbon quantum dots: synthesis, properties and applications

The emerging graphene quantum dots (GQDs) and carbon dots (C-dots) have gained tremendous attention for their enormous potentials for biomedical applications, owing to their unique and tunable photoluminescence properties, exceptional physicochemical properties, high photostability, biocompatibility, and small size. This article aims to update the latest results in this rapidly evolving field and to provide critical insights to inspire more exciting developments. We comparatively review the properties and synthesis methods of these carbon nanodots and place emphasis on their biological (both fundamental and theranostic) applications.

Glowing Graphene Quantum Dots and Carbon Dots: Properties, Syntheses, and Biological Applications

Reactive oxygen species

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

We report a facile green approach for in situ growth of silver nanoparticles (AgNPs) on the surface of graphene quantum dots (GQDs). GQDs serve as both reducing agent and stabilizer, and no additional reducing agent and stabilizer is necessary. The GQDs/AgNPs hybrid exhibits a superior absorbance fading response toward the reduction of H2O2. A simple colorimetric procedure is thus proposed for ultrasensitive detection of H2O2 without additional chromogenic agent. It provides a record detection limit of 33 nM for the detection of H2O2 by the AgNPs-based sensing system. This colorimetric sensing system is further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase for the oxidation of glucose and formation of H2O2, giving rise to a detection limit of 170 nM. The favorable performances of the GQDs/AgNPs hybrid are due to the peroxidase-like activity of GQDs.

In Situ Growth of Silver Nanoparticles on Graphene Quantum Dots for Ultrasensitive Colorimetric Detection of H2O2 and Glucose

The interactions of imidazolium ionic liquids (ILs), i.e., dibutylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, and 1-butyl-3-methylimidazolium nitrate, with bovine serum albumin (BSA) were studied by monitoring the spectral behaviors of IL-BSA aqueous systems. The intrinsic fluorescence of BSA at 340 nm excited at 230 nm is obviously quenched by these ILs due to complex dynamic collision and their quenching constants are at the order of 10(2) L mol(-1). However, no fluorescence quenching is observed within the same region when excited at 280 nm, which is widely used for probing protein conformations. Thermodynamic investigations reveal that the combination between ILs and BSA is entropy driven by predominantly hydrophobic and electrostatic interactions, leading to the unfolding of polypeptides within BSA. The influence of the ILs on the conformation of BSA follows a sequence of BmimNO(3) > BmimCl ≈ BbimCl. Molecular docking shows that cationic imidazolium moieties of ILs enter the subdomains of protein and interact with the hydrophobic residues of domain III. An agreement between fluorescence spectroscopic investigations and molecular docking is reached. It is found that the fluorescence of BSA at λ(ex) 230 nm arising from aromatic amino acids Trp and Tyr is almost as sensitive as that achieved at λ(ex) 280 nm for elucidating the protein conformational changes, which provides a valid and new probe for the investigation of binding kinetics between molecules/ions and proteins.

New insight into molecular interactions of imidazolium ionic liquids with bovine serum albumin.

Ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6), as a green solvent, was successfully used for the direct extraction of dsDNA The extraction efficiency and the distribution coefficient values indicated that trace amounts of DNA at the levels of <5 ng μL-1 facilitate quantitative fast extraction, while proteins and metal species do not interfere A total of 30% of the DNA in ionic liquid at ∼20 ng μL-1 was back extracted into aqueous phase in phosphate−citrate buffer with a single−stage extraction The extraction is demonstrated to be endothermic with an enthalpy of 343 kJ moL-1 The extraction mechanisms were proposed and verified by 31P NMR and FT-IR spectra Interactions between cationic 1-butyl-3-methylimidazolium (Bmim+) and P−O bonds of phosphate groups in the DNA strands take place both in the dissolved BmimPF6 in aqueous phase and at the interface of the two phases This interaction consequently led to the transformation of DNA conformations, along with a reduction of ethid

Xu-Wei Chen

Papers

In Situ Growth of Silver Nanoparticles on Graphene Quantum Dots for Ultrasensitive Colorimetric Detection of H2O2 and Glucose

New insight into molecular interactions of imidazolium ionic liquids with bovine serum albumin.

Direct Extraction of Double-Stranded DNA Into Ionic Liquid 1-Butyl-3-methylimidazolium Hexafluorophosphate and Its Quantification

The production of pH-sensitive photoluminescent carbon nanoparticles by the carbonization of polyethylenimine and their use for bioimaging

Quantum-Dot-Conjugated Graphene as a Probe for Simultaneous Cancer-Targeted Fluorescent Imaging, Tracking, and Monitoring Drug Delivery