Natural enzymes, exquisite biocatalysts mediating every biological process in living organisms, are able to accelerate the rate of chemical reactions up to 10(19) times for specific substrates and reactions. However, the practical application of enzymes is often hampered by their intrinsic drawbacks, such as low operational stability, sensitivity of catalytic activity to environmental conditions, and high costs in preparation and purification. Therefore, the discovery and development of artificial enzymes is highly desired. Recently, the merging of nanotechnology with biology has ignited extensive research efforts for designing functional nanomaterials that exhibit various properties intrinsic to enzymes. As a promising candidate for artificial enzymes, catalytically active nanomaterials (nanozymes) show several advantages over natural enzymes, such as controlled synthesis in low cost, tunability in catalytic activities, as well as high stability against stringent conditions. In this Account, we focus on our recent progress in exploring and constructing such nanoparticulate artificial enzymes, including graphene oxide, graphene-hemin nanocomposites, carbon nanotubes, carbon nanodots, mesoporous silica-encapsulated gold nanoparticles, gold nanoclusters, and nanoceria. According to their structural characteristics, these enzyme mimics are categorized into three classes: carbon-, metal-, and metal-oxide-based nanomaterials. We aim to highlight the important role of catalytic nanomaterials in the fields of biomimetics. First, we provide a practical introduction to the identification of these nanozymes, the source of the enzyme-like activities, and the enhancement of activities via rational design and engineering. Then we briefly describe new or enhanced applications of certain nanozymes in biomedical diagnosis, environmental monitoring, and therapeutics. For instance, we have successfully used these biomimetic catalysts as colorimetric probes for the detection of cancer cells, nucleic acids, proteins, metal ions, and other small molecules. In addition, we also introduce three exciting advances in the use of efficient modulators on artificial enzyme systems to improve the catalytic performance of existing nanozymes. For example, we report that graphene oxide could serve as a modulator to greatly improve the catalytic activity of lysozyme-stabilized gold nanoclusters at neutral pH, which will have great potential for applications in biological systems. We show that, through the incorporation of modulator into artificial enzymes, we can offer a facile but highly effective way to improve their overall catalytic performance or realize the catalytic reactions that were not possible in the past. We expect that nanozymes with unique properties and functions will attract increasing research interest and lead to new opportunities in various fields of research.

In this work, unmodified carbon nanodots are demonstrated as novel and environmentally-friendly fluorescence probes for the sensing of Hg(2+) and biothiols with high sensitivity and selectivity.

A synergistic graphene oxide-gold nanocluster (GO-AuNC) hybrid has been constructed as an enzyme mimic that is able to show high catalytic activity over a broad pH range, especially at neutral pH. Importantly, the target-functionalized hybrid has been applied as a robust nanoprobe for selective, quantitative, and fast colorimetric detection of cancer cells.

Creating artificial enzymes that mimic the complexity and function of natural systems has been a great challenge for the past two decades. In this Progress Report, the focus is on recently discovered "hidden talents" of gold nanomaterials in artificial enzymes, including mimicking of nuclease, esterase, silicatein, glucose oxidase, peroxidase, catalase, and superoxide dismutase. These unexpected enzyme-like activities can be ascribed to nano-gold itself or the functional groups present on surrounding monolayer. Along with introducing the mechanisms of the various enzyme-like activities, the design and development of gold-based biomimetic catalysts, the search for efficient modulators, and their potential applications in bionics, biosensing, and biomedical sciences are highlighted. Eventually, it is expected that the rapidly growing interest in gold-based nanozymes will certainly fuel the excitement and stimulate research in this highly active field.

No abstract

Herein, a pH stimuli-responsive vehicle for intracellular drug delivery using CeO2 capped mesoporous silica nanoparticles (MSN) is reported. β-Cyclodextrin-modified CeO2 nanoparticles could cap onto ferrocene-functionalized mesoporous silica through host-guest interactions. After internalization into A549 cells by a lysosomal pathway, the ferrocenyl moieties are oxidized to ferrocenium ions by CeO2 lids, which could trigger the uncapping of the CeO2 and cause the drugs release. Because of the pH-dependent toxicity, the CeO2 here behaves as a multi-purpose entity that not only acts as a lid but also exhibits a synergistic antitumor effect on cancer cells. Meanwhile, the cell protective effect of CeO2 nanoparticles alone is demonstrated, which ensures that the dissolved CeO2 nanoparticles can be non-toxic to normal cells.

As an RNA-guided nuclease, CRISPR-Cas9 offers facile and promising solutions to mediate genome modification with respect to versatility and high precision. However, spatiotemporal manipulation of CRISPR-Cas9 delivery remains a daunting challenge for robust effectuation of gene editing both in vitro and in vivo. Here, we designed a near-infrared (NIR) light–responsive nanocarrier of CRISPR-Cas9 for cancer therapeutics based on upconversion nanoparticles (UCNPs). The UCNPs served as “nanotransducers” that can convert NIR light (980 nm) into local ultraviolet light for the cleavage of photosensitive molecules, thereby resulting in on-demand release of CRISPR-Cas9. In addition, by preparing a single guide RNA targeting a tumor gene (polo-like kinase-1), our strategies have successfully inhibited the proliferation of tumor cell via NIR light–activated gene editing both in vitro and in vivo. Overall, this exogenously controlled method presents enormous potential for targeted gene editing in deep tissues and treatment of a myriad of diseases.

To examine the mechanism of the network formation of silk fibroin (SF), monodispersed colloidal particles (MDCPs) are used as well defined foreign substrates to quantify their effect on the primary nucleation of β‐crystallites in molecular networks (silk nanofibrils) and the hierarchical network formation of SF. It follows that MDCPs are capable of accelerating the SF gelation by reducing the multistep nucleation barrier, which gives rise to a high density of silk fibril domain networks due to the increase of primary nucleation sites. Consequently, through governing the change in the hierarchical mesoscopic structure, the macroscopic performance of silk materials (e.g., the rheological properties of SF hydrogels and the tensile stress of fibers) can be controlled directly. As SF hydrogels represent a typical example of weak fibril domain–domain network interactions, the increase of fibril domain density leads to weaker gels. On the other hand, SF fibers correspond to strong fibril domain–domain network interactions, the increase of fibril domain density ends up with much tougher fibers. The knowledge obtained provides a facile strategy in controlling the complex hierarchical structure and macroscopic performance of SF materials, and offers useful routes for general design and functionalization of soft materials.