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

Functional Nanomaterials for Phototherapies of Cancer

Although progress has recently been made toward understanding the health and environmental consequences of these materials, challenges ramain for future research.

http://pubs.acs.org/doi/pdf/10.1021/es062726m

Assessing the risks of manufactured nanomaterials.

This Account reviews our main achievements in the field of excited-state properties of fullerene derivatives. The photosensitizing and electron-acceptor features of some relevant classes of functionalized fullerene materials are highlighted, considering the impact of functionalization on fullerene characteristics. In addition, the unique optimization in terms of redox potentials, water-solubility, and singlet oxygen generation is presented for several novel fullerene-based materials.

Excited-state properties of C(60) fullerene derivatives.

Chemistry and Biology of the Enediyne Anticancer Antibiotics

Here we report the preparation of a water-miscible fullerene carboxylic acid (2) and its biological activity-cytotoxicity and G-selective DNA cleaving ability. What is truly remarkable is that the biological activity of C{sub 60} was observed only under irradiation with visible light and not in the dark, suggesting that fullerenes may serve as useful photosensitive biochemical probes. We have found, for the first time, that even low-energy visible light is surfficient to induce biological activity in fullerene derivatives. Among the numerous implications of the present findings, the most exciting prospect includes the use of fullerene derivatives for photodynamic therapy. 18 refs., 2 figs., 1 tab.

Photoinduced biochemical activity of fullerene carboxylic acid

Two different classes of water-soluble fullerene derivatives, detergent-type and sphere-type, were synthesized. The derivatives were evaluated for their biological activities including cytotoxicity, DNA cleavage, and inhibition of HIV-protease and other enzymes. Both classes of compounds display generally similar behavior except for their cytotoxicity spectra against several cell lines. The fullerene derivatives bearing N-methylpyrrole were found to be photo-inactive with respect to DNA cleaving activity and cytotoxicity. A study on the kinetics for the inhibition of HIV-protease with detergent type derivative revealed that the compound is a potent fullerene-based HIV protease inhibitor, inhibiting the enzyme activity in a reversible and competitive manner with a Ki value of 0.32 μM.

Biological Activity of Water-Soluble Fullerenes. Structural Dependence of DNA Cleavage, Cytotoxicity, and Enzyme Inhibitory Activities Including HIV-Protease Inhibition

Man-designed bleomycin with altered sequence specificity in DNA cleavage

Dynemicin A, which is a hybrid antitumor antibiotic containing anthraquinone and enediyne cores, effectively breaks DNA strands upon irradiation with visible light of long wavelength. The preferential cutting sites of visible light induced DNA cleavage with dynemicin A are on the 3'-side of purine bases such as in 5'-AT and 5'-GT sequences. The observed nucleotide cutting specificity is remarkably similar to that of NADPH- (or thiol) induced DNA breakage with dynemicin A, suggesting the presence of the same DNA-cleaving intermediate. Indeed, the photoproduct of dynemicin A is chromatographically identical with the reaction product (dynemicin H) of the thiol-activated dynemicin A. On the basis of the present results, a reasonable mechanism for the visible light induced DNA cleavage of dynemicin A has been proposed.

Visible light induced DNA cleavage by the hybrid antitumor antibiotic dynemicin A.

Pioglitazone Improves Insulin Signaling Defects in Skeletal Muscle from Wistar Fatty (fa/fa) Rats

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