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

Metals have been used as antimicrobial agents since antiquity, but throughout most of history their modes of action have remained unclear. Recent studies indicate that different metals cause discrete and distinct types of injuries to microbial cells as a result of oxidative stress, protein dysfunction or membrane damage. Here, we describe the chemical and toxicological principles that underlie the antimicrobial activity of metals and discuss the preferences of metal atoms for specific microbial targets. Interdisciplinary research is advancing not only our understanding of metal toxicity but also the design of metal-based compounds for use as antimicrobial agents and alternatives to antibiotics.

Antimicrobial activity of metals: mechanisms, molecular targets and applications

The antibacterial action of silver is utilized in numerous consumer products and medical devices. Metallic silver, silver salts, and also silver nanoparticles are used for this purpose. The state of research on the effect of silver on bacteria, cells, and higher organisms is summarized. It can be concluded that the therapeutic window for silver is narrower than often assumed. However, the risks for humans and the environment are probably limited.

Silver as Antibacterial Agent: Ion, Nanoparticle, and Metal

Applications of nanotechnology in water and wastewater treatment

A systematic and detailed study for size-specific antibacterial efficacy of silver nanoparticles (AgNPs) synthesized using a co-reduction approach is presented here. Nucleation and growth kinetics during the synthesis process was precisely controlled and AgNPs of average size 5, 7, 10, 15, 20, 30, 50, 63, 85, and 100 nm were synthesized with good yield and monodispersity. We found the bacteriostatic/bactericidal effect of AgNPs to be size and dose-dependent as determined by the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of silver nanoparticles against four bacterial strains. Out of the tested strains, Escherichia coli MTCC 443 and Staphylococcus aureus NCIM 5201 were found to be the most and least sensitive strains regardless of AgNP size. For AgNPs with less than 10 nm size, the antibacterial efficacy was significantly enhanced as revealed through delayed bacterial growth kinetics, corresponding MIC/MBC values and disk diffusion tests. AgNPs of the smallest size, i.e., 5 nm demonstrated the best results and mediated the fastest bactericidal activity against all the tested strains compared to AgNPs having 7 nm and 10 nm sizes at similar bacterial concentrations. TEM analysis of AgNP treated bacterial cells showed the presence of AgNPs on the cell membrane, and AgNPs internalized within the cells.

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Size-controlled silver nanoparticles synthesized over the range 5–100 nm using the same protocol and their antibacterial efficacy

For nearly a decade, researchers have debated the mechanisms by which AgNPs exert toxicity to bacteria and other organisms. The most elusive question has been whether the AgNPs exert direct “particle-specific” effects beyond the known antimicrobial activity of released silver ions (Ag+). Here, we infer that Ag+ is the definitive molecular toxicant. We rule out direct particle-specific biological effects by showing the lack of toxicity of AgNPs when synthesized and tested under strictly anaerobic conditions that preclude Ag(0) oxidation and Ag+ release. Furthermore, we demonstrate that the toxicity of various AgNPs (PEG- or PVP- coated, of three different sizes each) accurately follows the dose–response pattern of E. coli exposed to Ag+ (added as AgNO3). Surprisingly, E. coli survival was stimulated by relatively low (sublethal) concentration of all tested AgNPs and AgNO3 (at 3–8 μg/L Ag+, or 12–31% of the minimum lethal concentration (MLC)), suggesting a hormetic response that would be counterproductive t...

Negligible Particle-Specific Antibacterial Activity of Silver Nanoparticles

This work examines the effect of nanocrystal diameter and surface coating on the reactivity of cerium oxide nanocrystals with H2O2 both in chemical solutions and in cells. Monodisperse nanocrystals were formed in organic solvents from the decomposition of cerium precursors, and subsequently phase transferred into water using amphiphiles as nanoparticle coatings. Quantitative analysis of the antioxidant capacity of CeO2–x using gas chromatography and a luminol test revealed that 2 mol of H2O2 reacted with every mole of cerium(III), suggesting that the reaction proceeds via a Fenton-type mechanism. Smaller diameter nanocrystals containing more cerium(III) were found to be more reactive toward H2O2. Additionally, the presence of a surface coating did not preclude the reaction between the nanocrystal surface cerium(III) and hydrogen peroxide. Taken together, the most reactive nanoparticles were the smallest (e.g., 3.8 nm diameter) with the thinnest surface coating (e.g., oleic acid). Moreover, a benchmark tes...

Antioxidant Properties of Cerium Oxide Nanocrystals as a Function of Nanocrystal Diameter and Surface Coating

The most persistent question regarding the toxicity of silver nanoparticles (AgNPs) is whether this toxicity is due to the nanoparticles themselves or the silver ions (Ag(+)) they release. The present study investigates the role of surface coating and the presence of dissolved organic carbon on the toxicity of AgNPs to Daphnia magna and tests the hypothesis that the acute toxicity of AgNPs is a function of dissolved Ag produced by nanoparticle dissolution. Toxicity of silver nitrate (AgNO3) and AgNPs with surface coatings-gum arabic (AgGA), polyethylene glycol (AgPEG), and polyvinylpyrrolidone (AgPVP)-at 48 h was assessed in US Environmental Protection Agency moderately hard reconstituted water alone and augmented with Suwannee River dissolved organic carbon (DOC). As expected, AgNO3 was the most toxic to D. magna and AgPVPs were the least toxic. In general, Suwannee River DOC presence reduced the toxicity of AgNO3, AgGAs, and AgPEG, while the toxicity of AgPVPs was unaffected. The measured dissolved Ag concentrations for all AgNPs and AgNO3 at the 48-h median lethal concentration in moderately hard reconstituted water were similar. The presence of Suwannee River DOC decreased the ratio of measured dissolved Ag to measured total Ag concentration. These results support the hypothesis that toxicity of AgNPs to D. magna is a function of dissolved Ag concentration from these particles.

Silver nanoparticle toxicity to Daphnia magna is a function of dissolved silver concentration.

To fully understand the biological and environmental impacts of nanomaterials requires studies that address both sublethal end points and multigenerational effects. Here, we use a nematode to examine these issues as they relate to exposure to two different types of quantum dots, core (CdSe) and core–shell (CdSe/ZnS), and to compare the effect to those observed after cadmium salt exposures. The strong fluorescence of the core–shell QDs allowed for the direct visualization of the materials in the digestive track within a few hours of exposure. Multiple end points, including both developmental and locomotive, were examined at QD exposures of low (10 mg/L Cd), medium (50 mg/L Cd), and high concentrations (100 mg/L Cd). While the core–shell QDs showed no effect on fitness (lifespan, fertility, growth, and three parameters of motility behavior), the core QDs caused acute effects similar to those found for cadmium salts, suggesting that biological effects may be attributed to cadmium leaching from the more solub...

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Toxicity of quantum dots and cadmium salt to Caenorhabditis elegans after multigenerational exposure.

Nanocrystalline ceria is an interesting inorganic material for biological application that can exhibit antioxidant properties due to facile electron transfer between cerium(III) and cerium(IV). In this work, ceria nanocrystals with uniform and tunable size, surface chemistry, and variable cerium(III) content were formed via the high temperature thermal decomposition of ceria precursors including cerium acetylacetonate hydrate, cerium oleylamine, and cerium nitrate hexahydrate. When combined with organic acid and amine surfactants at temperatures between 260 and 320 °C, these cerium precursors decomposed to yield near-spherical cerium oxide nanocrystals with diameters ranging from 3 to 10 nm. For all shapes of nanocrystals, the smallest primary particle sizes had the most cerium(III) content. Both poly(acrylic acid)–octyl amine as well as oleic acid could be used to transfer the hydrophobic nanocrystals into water; acute in vitro toxicology studies revealed that even at high concentrations (e.g., 10 ppm) 3...

Hema L. Puppala

Papers

Negligible Particle-Specific Antibacterial Activity of Silver Nanoparticles

Antioxidant Properties of Cerium Oxide Nanocrystals as a Function of Nanocrystal Diameter and Surface Coating

Silver nanoparticle toxicity to Daphnia magna is a function of dissolved silver concentration.

Toxicity of quantum dots and cadmium salt to Caenorhabditis elegans after multigenerational exposure.

High Temperature Decomposition of Cerium Precursors To Form Ceria Nanocrystal Libraries for Biological Applications